Do not write

3 outside the
box

Section A

Answer all questions in the spaces provided.

1 A reaction mechanism is a series of steps by which an overall reaction may proceed.

The reactions occurring in these steps may be deduced from a study of reaction rates.
Experimental evidence about initial rates leads to a rate equation. A mechanism is
then proposed which agrees with this rate equation.

Ethanal dimerises in dilute alkaline solution to form compound X as shown in the

following equation.

2CH3CHO → CH3CH(OH)CH2CHO
X

A chemist studied the kinetics of the reaction at 298 K and then proposed the following
rate equation.

Rate = k [CH3CHO][OH– ]

1 (a) Give the IUPAC name of compound X.

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

Thermodynamics 1 (b) The initial rate of the reaction at 298 K was found to be 2.2 × 10–3 mol dm–3 s–1 when
the initial concentration of ethanal was 0.10 mol dm–3 and the initial concentration of
sodium hydroxide was 0.020 mol dm–3.
Calculate a value for the rate constant at this temperature and give its units.

Calculation .........................................................................................................................

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

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

Units ..................................................................................................................................
(3 marks)

1 (c) The sample of X produced consists of a racemic mixture (racemate). Explain how this
racemic mixture is formed.

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

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

............................................................................................................................................
(2 marks)
Question 1 continues on the next page

Turn over 

(03)
WMP/Jun10/CHEM4
 Do not write Do not write
4 outside the 5 outside the
box box

1 (d) A three-step mechanism has been proposed for this reaction according to the following 1 (d) (iii) Use your knowledge of reaction mechanisms to deduce the type of reaction occurring
equations. in Step 2.

............................................................................................................................................
O O (1 mark)
Step 1 CH3 C + :OH :CH2 C + H2O
H H 1 (d) (iv) In the space below draw out the mechanism of Step 2 showing the relevant curly
arrows.

O:
O O O
Step 2 CH3 C + :CH2 C CH3 C CH2 C
H H H
H

O: OH
O O
Step 3 CH3 C CH2 C + H2O CH3 C CH2 C + :OH
H H
H H (2 marks)

1 (e) In a similar three-step mechanism, one molecule of X reacts further with one molecule
1 (d) (i) Using the rate equation, predict which of the three steps is the rate-determining step. of ethanal. The product is a trimer containing six carbon atoms.
Explain your answer.
Deduce the structure of this trimer.
Rate-determining step .......................................................................................................

Explanation ........................................................................................................................

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

1 (d) (ii) Deduce the role of ethanal in Step 1.

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

(1 mark)

13

Turn over 

(04) (05)
WMP/Jun10/CHEM4 WMP/Jun10/CHEM4
 Do not write 3 Do not write
2 outside the outside the
box box

1 (b) (i) Define the term standard enthalpy of formation.

Section A
............................................................................................................................................
Answer all questions in the spaces provided.
............................................................................................................................................
1 Calcium fluoride occurs naturally as the mineral fluorite, a very hard crystalline solid
that is almost insoluble in water and is used as a gemstone. ............................................................................................................................................

Tables 1 and 2 contain thermodynamic data. ............................................................................................................................................

(3 marks)
Table 1 (Extra space) ......................................................................................................................

Process ΔH / kJ mol–1
............................................................................................................................................
Ca(s) → Ca(g) +193
............................................................................................................................................
Ca(g) → Ca+(g) + e– +590

Ca+(g) → Ca2+(g) + e– +1150 1 (b) (ii) Write an equation, including state symbols, for the process that has an enthalpy
change equal to the standard enthalpy of formation of calcium fluoride.
F2(g) → 2F(g) +158

F(g) + e → F (g)
– –
–348
............................................................................................................................................
(1 mark)
Table 2
Name of enthalpy change ΔH / kJ mol–1 1 (b) (iii) Use data from the Tables 1 and 2 to calculate the standard enthalpy of formation for
calcium fluoride.
Enthalpy of lattice dissociation for calcium fluoride +2602
............................................................................................................................................
Enthalpy of lattice dissociation for calcium chloride +2237
............................................................................................................................................
Enthalpy of hydration for F– ions –506

Enthalpy of hydration for Cl– ions –364 ............................................................................................................................................

2+
Enthalpy of hydration for Ca ions –1650 ............................................................................................................................................

............................................................................................................................................
1 (a) Write an equation, including state symbols, for the process that occurs when the
calcium fluoride lattice dissociates and for which the enthalpy change is equal to the ............................................................................................................................................
lattice enthalpy. (3 marks)
(Extra space) .....................................................................................................................

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

Question 1 continues on the next page

Turn over 䊳

(02) (03)
WMP/Jun10/CHEM5 WMP/Jun10/CHEM5
 Do not write 5 Do not write
4 outside the outside the
box box

1 (c) Explain why the enthalpy of lattice dissociation for calcium fluoride is greater than that
for calcium chloride.
............................................................................................................................................
............................................................................................................................................
1 (e) Calcium fluoride crystals absorb ultra-violet light. Some of the energy gained is given
out as visible light. The name of this process, fluorescence, comes from the name of
the mineral, fluorite.
Use your knowledge of the equation ΔE = hν to suggest what happens to the electrons
in fluorite when ultra-violet light is absorbed and when visible light is given out.

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

............................................................................................................................................ ............................................................................................................................................
(2 marks)
............................................................................................................................................
1 (d) Calcium chloride dissolves in water. After a certain amount has dissolved, a saturated
solution is formed and the following equilibrium is established. ............................................................................................................................................
(2 marks)
CaCl2(s) Ca2+(aq) + 2Cl–(aq) (Extra space) ......................................................................................................................

1 (d) (i) Using data from Table 2, calculate the enthalpy change for this reaction. ............................................................................................................................................ 17

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

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

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

............................................................................................................................................
Turn over for the next question
............................................................................................................................................

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

1 (d) (ii) Predict whether raising the temperature will increase, decrease or have no effect on the
amount of solid calcium chloride that can dissolve in a fixed mass of water.
Explain your prediction.
(If you have been unable to obtain an answer to part (d) (i), you may assume that the
enthalpy change = –60 kJ mol–1. This is not the correct answer.)

Effect on amount of solid that can dissolve .......................................................................

Explanation ........................................................................................................................

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

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

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

Turn over 䊳

(04) (05)
WMP/Jun10/CHEM5 WMP/Jun10/CHEM5
 Do not write Do not write
14 outside the 15 outside the
box box

Section B 6 (c) Use your answers to parts (a) and (b) to explain why this reaction is not feasible at
high temperatures.
Answer all questions in the spaces provided.
Calculate the temperature at which the reaction becomes feasible.

6 Methanol can be regarded as a carbon-neutral fuel because it can be synthesised from Suggest why the industrial process is carried out at a higher temperature than you
carbon dioxide as shown in the equation below. have calculated.

CO2(g) + 3H2(g) CH3OH(g) + H2O(g) (If you have been unable to calculate values for ΔH and ΔS you may assume that they
are –61 kJ mol–1 and –205 J K–1 mol–1 respectively. These are not the correct values.)
Standard enthalpy of formation and standard entropy data for the starting materials
and products are shown in the following table. ............................................................................................................................................

CO2(g) H2(g) CH3OH(g) H2O(g) ............................................................................................................................................

ΔHf / kJ mol –1
–394 0 –201 –242 ............................................................................................................................................
–1 –1
S /JK mol 214 131 238 189
............................................................................................................................................

6 (a) Calculate the standard enthalpy change for this reaction. ............................................................................................................................................

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

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

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

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

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

............................................................................................................................................
(3 marks)
6 (b) Calculate the standard entropy change for this reaction.
............................................................................................................................................
............................................................................................................................................
............................................................................................................................................
............................................................................................................................................
............................................................................................................................................
(6 marks)
(Extra space) ......................................................................................................................
............................................................................................................................................
............................................................................................................................................

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

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

............................................................................................................................................
(3 marks)
Question 6 continues on the next page

Turn over 䊳

(14) (15)
WMP/Jun10/CHEM5 WMP/Jun10/CHEM5
 16 Do not write
outside the
6 Areas outside
the box will
box not be scanned
for marking

6 (d) Write an equation for the complete combustion of methanol. Use your equation to 4 The table below gives some values of standard enthalpy changes. Use these values to answer
explain why the combustion reaction in the gas phase is feasible at all temperatures. the questions.

............................................................................................................................................
–1
Name of enthalpy change ∆H / k J mol
............................................................................................................................................
Enthalpy of atomisation of chlorine +121
............................................................................................................................................ Electron affinity of chlorine –364
Enthalpy of atomisation of silver +289
............................................................................................................................................
First ionisation enthalpy of silver +732
............................................................................................................................................ Enthalpy of formation of silver chloride –127

............................................................................................................................................
4 (a) Calculate the bond enthalpy of a Cl – Cl bond.
............................................................................................................................................
.............................................................................................................................................
............................................................................................................................................ (1 mark)
(4 marks)
(Extra space) ...................................................................................................................... 4 (b) Explain why the bond enthalpy of a Cl – Cl bond is greater than that of a Br– Br bond.

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

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

............................................................................................................................................ .............................................................................................................................................
6 (e) Give one reason why methanol, synthesised from carbon dioxide and hydrogen, may .............................................................................................................................................
not be a carbon-neutral fuel.
(2 marks)
............................................................................................................................................
4 (c) Suggest why the electron affinity of chlorine is an exothermic change.
............................................................................................................................................
.............................................................................................................................................
............................................................................................................................................
.............................................................................................................................................
(1 mark)
(1 mark)
17

(16) (06)
WMP/Jun10/CHEM5 WMP/Jan10/CHEM5
 7 Areas outside
the box will
8 Areas outside
the box will
not be scanned not be scanned
for marking for marking

4 (d) The diagram below is an incomplete Born–Haber cycle for the formation of silver 4 (e) The enthalpy of lattice dissociation for silver chloride can also be calculated
chloride. The diagram is not to scale. theoretically assuming a perfect ionic model.

4 (e) (i) Explain the meaning of the term perfect ionic model.

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

Ag+(g) + Cl–(g) ...................................................................................................................................

(1 mark)

4 (e) (ii) State whether you would expect the value of the theoretical enthalpy of lattice
dissociation for silver chloride to be greater than, equal to or less than that for
Ag(s) + 12 Cl2 (g) silver bromide. Explain your answer.

Theoretical lattice enthalpy for silver chloride ........................................................

AgCl(s)
Explanation ...............................................................................................................

...................................................................................................................................
4 (d) (i) Complete the diagram by writing the appropriate chemical symbols, with state
symbols, on each of the three blank lines. (3 marks) ...................................................................................................................................
(3 marks)
4 (d) (ii) Calculate a value for the enthalpy of lattice dissociation for silver chloride. (Extra space) ............................................................................................................

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

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

................................................................................................................................... 4 (e) (iii) Suggest why your answer to part (d) (ii) is greater than the theoretical value for
the enthalpy of lattice dissociation for silver chloride.
...................................................................................................................................
(2 marks) ...................................................................................................................................

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

...................................................................................................................................
Question 4 continues on the next page (2 marks)

15

Turn over 

(07) (08)
WMP/Jan10/CHEM5 WMP/Jan10/CHEM5
 10 Areas outside
the box will
11 Areas outside
the box will
not be scanned not be scanned
for marking for marking

5 The simplified diagram below shows how the entropy of ammonia varies with temperature at 5 (e) An equation for the reaction in the Haber Process is shown below, together with some
a pressure of 100 kPa. In this diagram, ammonia is a solid at point A and a gas at point F. entropy data.
1 3
2 N2(g) + 2 H2(g) NH3(g) ∆H = –46.2 kJ mol –1

N2(g) H2(g) NH3(g)

F –1 –1
E S /JK mol 192 131 193

S / J K–1 mol–1
5 (e) (i) Calculate a value for the entropy change, ∆S , for the formation of one mole of
ammonia.
D
C
...................................................................................................................................

B ...................................................................................................................................
A
0
0 T Temperature / K ...................................................................................................................................

5 (a) State why the entropy value for ammonia is equal to zero at 0 K. ...................................................................................................................................
(2 marks)
.............................................................................................................................................
(1 mark) 5 (e) (ii) Give the equation that relates free-energy change, ∆G , to enthalpy change,
∆H , and entropy change, ∆S .
5 (b) Explain, in terms of the movement of particles, why the entropy value increases
between points A and B on the diagram. Use this equation to calculate the temperature at which the value of ∆G = 0 for
the formation of ammonia in the Haber Process.
............................................................................................................................................. (If you have been unable to calculate an answer to part (e) (i), you may assume
that ∆S = –81.4 J K mol–1 but this is not the correct value.)
.............................................................................................................................................
(1 mark)
Equation ....................................................................................................................
5 (c) Temperature T is marked on the diagram. What does the value of this temperature
Calculation ................................................................................................................
represent?
...................................................................................................................................
.............................................................................................................................................
(1 mark)
...................................................................................................................................
5 (d) Explain why there is a large entropy change between points D and E on the diagram.
...................................................................................................................................
(4 marks)
.............................................................................................................................................
(Extra space) ............................................................................................................
.............................................................................................................................................
5 (e) (iii) What can you deduce about the formation of ammonia if the reaction mixture is
(2 marks)
heated to a temperature above the value that you have calculated in part (e) (ii)?

...................................................................................................................................
(1 mark)
12
Turn over 

(10) (11)
WMP/Jan10/CHEM5 WMP/Jan10/CHEM5
 Do not write Do not write
2 outside the 3 outside the
box box

Section A 1 (c) Consider the following data.

Answer all questions in the spaces provided. ΔH / kJ mol–1

Enthalpy of lattice formation for CaF2 –2611
Enthalpy of hydration for Ca2+ ions –1650
1 Thermodynamics can be used to investigate the changes that occur when substances
such as calcium fluoride dissolve in water. Enthalpy of hydration for F– ions –506

1 (a) Give the meaning of each of the following terms.

Use these data to calculate a value for the enthalpy of solution for CaF2
1 (a) (i) enthalpy of lattice formation for calcium fluoride
............................................................................................................................................
............................................................................................................................................
............................................................................................................................................
............................................................................................................................................
............................................................................................................................................
............................................................................................................................................
............................................................................................................................................
............................................................................................................................................ (2 marks)
(2 marks)
7
1 (a) (ii) enthalpy of hydration for fluoride ions

............................................................................................................................................ Turn over for the next question

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

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

1 (b) Explain the interactions between water molecules and fluoride ions when the fluoride
ions become hydrated.

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

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

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

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

Turn over 䊳

(02) (03)
WMP/Jun11/CHEM5 WMP/Jun11/CHEM5
 5 Do not write
4 outside the
box

There are no questions printed on this page 2 When potassium nitrate (KNO3) dissolves in water the value of the enthalpy change
ΔH = +34.9 kJ mol–1 and the value of the entropy change ΔS = +117 J K–1 mol–1.

2 (a) Write an equation, including state symbols, for the process that occurs when potassium
nitrate dissolves in water.

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

2 (b) Suggest why the entropy change for this process is positive.

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

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

2 (c) Calculate the temperature at which the free-energy change, ΔG, for this process
is zero.

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

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

............................................................................................................................................
DO NOT WRITE ON THIS PAGE
ANSWER IN THE SPACES PROVIDED ............................................................................................................................................

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

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

2 (d) (i) Deduce what happens to the value of ΔG when potassium nitrate dissolves in water at
a temperature lower than your answer to part 2 (c).

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

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

2 (d) (ii) What does this new value of ΔG suggest about the dissolving of potassium nitrate
at this lower temperature?

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

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

Turn over 䊳

(04) (05)
WMP/Jun11/CHEM5 WMP/Jun11/CHEM5