1.

The enthalpy change of combustion of two fuels is listed below.

fuel

enthalpy of combustion/kJ mol

hydrogen, H2

280

octane, C8H18

5510

(a)

Calculate the enthalpy change per unit mass for each of the fuels.
Hydrogen:

Octane:

(3)

(b)

Suggest, giving two reasons, which substance is the more useful as a fuel for motor cars
and give your reasoning.
Reason 1.................................................................................................................
...............................................................................................................................
Reason 1.................................................................................................................
...............................................................................................................................
(2)

(c)

Suggest one disadvantage of using the fuel chosen in (b)

...............................................................................................................................
(1)
(Total 6 marks)

2.

The following table shows some properties of two different fuels.

Fuel

Hydrogen

Ethanol

H2

C2H5OH

Boiling temperature / C

252

78

Enthalpy of combustion per gram / kJ

143

30

Cost per tonne /

100

500

Formula

(a)

Write equations to show the complete combustion of:

(i)

hydrogen ..........................................................................................................
..........................................................................................................................

(ii)

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

(b)

Hydrogen and ethanol are used as motor car fuel. Suggest the advantages and
disadvantages of each of these fuels in this application. Use the table, and your answers to
part (a) above to help you.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
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(5)
(Total 9 marks)

3.

Read the passage below on EMISSION CONTROL straight through and then more carefully,
in order to answer the following questions.
EMISSION CONTROL
Photochemical smog, a brown haze just above the horizon, was first observed in Los Angeles in
the 1940s. Research showed that the smog was produced by the action of sunlight on air
containing a variety of pollutants, many of them produced by burning fuels.
In a conventional petrol engine, a mixture of fuel and air is ignited by a spark. Petrol is
essentially a hydrocarbon mixture so if combustion is complete the reaction products are carbon
dioxide and water. The proportions of air and fuel are vitally important; the most efficient is the
stoichiometric ratio. This is the ratio of air to fuel which, in theory, leads to complete
combustion of the fuel. In practice, incomplete combustion results in the formation of toxic
carbon monoxide and also leaves unburnt hydrocarbons which are the main cause of
photochemical smogs. There is also reaction between nitrogen and oxygen gases in the engine,
producing oxides of nitrogen, usually referred to as NOx.

Lean-burn engines use a higher air:fuel ratio. They work at lower temperatures, producing less
NOx but more unburnt hydrocarbons. Diesel engines also work at lower temperatures,
producing less of all the gaseous pollutants but significantly more solid particles such as carbon.
Catalytic converters are fitted to vehicle exhaust systems to deal with gaseous pollutants. The
earliest catalysts tried were metals such as nickel, copper and cobalt. These were relatively
cheap but were adversely affected by high temperatures and were poisoned by sulphur and
lead compounds in the fuel. Platinum was found to be very much more satisfactory. Very small
particles of the metal were supported on a ceramic honeycomb to increase its surface area.
Getting the right conditions for combustion is not easy. Carbon monoxide and unburnt
hydrocarbons need to be oxidised but the nitrogen oxides have to be reduced to nitrogen gas. An
ingenious solution is to use the nitrogen oxides to oxidise the other pollutants, but this still
requires some oxygen for complete removal of the hydrocarbons and carbon monoxide. Modern
three-way catalysts (so-called because they deal with all three types of pollutants) only work
effectively if the composition of the original air:petrol mixture is carefully controlled; too much
fuel will mean insufficient oxygen in the exhaust fumes. The exhaust system must therefore be
fitted with oxygen sensors linked back to an electronically controlled fuel injection system.
Efficiency is also improved by incorporating other platinum group metals such as rhodium and
sometimes palladium.

Catalysts for diesel-engined vehicles have to include an efficient filter to remove carbon
particles. This leads to a further problem because the solid carbon (soot) needs to be burned to
allow the filter to continue to work effectively. Soot combustion needs a temperature of 500
600C and the exothermic reaction with oxygen can raise it to as much as 1000 C,which can
damage the filter. This problem has been tackled by first converting all nitrogen oxides to
nitrogen dioxide (NO2) using a platinum catalyst, and then using the nitrogen dioxide to oxidise
the carbon, a reaction which takes place at 200 C.

The catalyst will only work if it is hot. Platinum needs a temperature of 240C but rhodium
helps by reducing this to 150C. This means that the catalyst is ineffective when the engine is
first started, a major problem under investigation. Unleaded fuel is essential and the introduction
of very low sulphur fuel has helped to eliminate the bad-egg smell noticed if hydrogen
sulphide is produced.
(573 words)
Adapted from Emission control by B. Harrison, Education in Chemistry, September 2000.

(a)

Why is the brown smog first seen in Los Angeles said to be photochemical?
(1)

(b)

Write a balanced equation for the reaction between carbon monoxide and nitrogen
monoxide (NO), producing carbon dioxide and nitrogen gas.
(1)

(c)

Explain what is meant by the incomplete combustion of a fuel.

(1)

(d)

Why do conventional petrol engines give higher NOx emissions than lean-burn or
diesel engines?
(1)

(e)

Three platinum group metals used in catalyst systems are mentioned in the passage.
Suggest another metal of this type which might be tried in the search for improved
catalysts.
(1)

(f)

Why has it been found necessary to change the composition of motor fuel for engines
fitted with converters?
(1)

(g)

Why are catalysts least effective when the engine is first started?
(1)

You are not asked to summarise the whole passage, nor to include equations in your summary.
At the end of your summary state the number of words you have used.
Credit will be given for answers written in good English, using complete sentences and using
technical words correctly and chemical names rather than formulae. Avoid copying long
sections from the original text. Numbers count as one word, as do standard abbreviations, units
and hyphenated words. Any title you give your passage does not count in your word total.
There are penalties for the use of words in excess of 120.
(Total 7 marks)

4.

Read the passage on BUILDING A BETTER BLEACH - A GREEN CHEMISTRY

CHALLENGE straight through and then more carefully. Answer the following questions.
BUILDING A BETTER BLEACH A GREEN CHEMISTRY CHALLENGE
Your dark red T-shirt has turned everyone elses white washing pink. The problem is how do
you remove the stain?

A stain is a colour where you dont want it, but stain removal is not actually removal at all.
Instead the stain molecules are altered chemically so they no longer reflect light in the same
way as before. We call it bleaching and chemistry is behind the process.

The active ingredient in household bleach, sodium hypochlorite (NaOCl), keeps white clothing
white and your toilet sparkling, but how does the bleach act on stain molecules? Bleaching is an
example of a redox reaction. The colour of the stain is a property caused by the chemical
structure of its molecules. When the bleach removes electrons from a molecule, the chemical
structure of the molecule is changed and properties like colour are altered. Any excess sodium
hypochlorite is washed away in the rinse water. However, oxidation with such chlorine-based
bleaches sometimes adds chlorine atoms to the stain molecules as well as removing electrons.
This can lead to the formation of hazardous by-products such as dioxins, which can persist in
the environment and accumulate in the food chain.

Non-chlorine bleaches to the rescue

If the release of chlorine-based bleaches on a large scale could be bad for the environment, what
else can we use to get rid of the stains? Alternative non-chlorine bleaches are available. They
contain hydrogen peroxide or other peroxide compounds. As hydrogen peroxide is a liquid it is
not actually present in solid non-chlorine bleaches such as Oxi-Clean. Solid non-chlorine
bleaches contain ingredients like perborate or percarbonate - solid compounds which react with
water to release hydrogen peroxide. Whilst removing stains, the hydrogen peroxide decomposes
to release highly reactive free radicals. These oxidise other molecules by removing electrons or
hydrogen atoms from them.

Hydrogen peroxide sounds like our ideal bleach. In addition to its use in household cleaners,
stain removers and hair dyes, it is now used in the pulp and paper, textile and laundry industries.
Best of all, hydrogen peroxide contains no chlorine atoms so produces no organochlorine
pollutants. So why not stop using chlorine-based bleaches altogether?

The challenge of replacing traditional chlorine bleaches with hydrogen peroxide is twofold.
Firstly, the peroxide oxidation process can be unselective. This means any molecules in the
vicinity that are exposed to the hydrogen peroxide get exposed to free radicals, and some
unwanted reactions might accompany the desired oxidation. Secondly, successful bleaching
with hydrogen peroxide requires higher temperatures and pressures and longer reaction times
than those needed for chlorine-based bleaches. On an industrial scale this means higher costs for
energy, equipment and labour.

However, the Institute for Green Oxidation Chemistry at Carnegie Mellon University, in the
USA, may have solved our bleaching problems. They have developed some heroic molecules
called tetraamido macrocyclic ligands or TAML for short. These molecules function as catalysts
in the hydrogen peroxide bleaching process and their presence allows the oxidation to proceed
at much lower temperatures and pressures. Like all catalysts, they are not consumed in the
process. This could make the process environmentally benign, meaning the materials used are
made from renewable resources, the process consumes minimal energy resources and does not
release polluting by-products into the environment.

So bleaching using TAML activated peroxide would be an ideal example of green chemistry in
action. Made from naturally occurring biochemicals, TAML catalysts reduce energy costs and
prevent pollution. In addition their highly selective nature means they can hunt and destroy
dye molecules in solution preventing dye transfer to other clothes, which may mean in the
future TAML could protect you and your pink-clothed family from further laundry mishaps.
[613 words]
(Source: adapted from Chem matters Demystifying Everyday Chemistry by Kathryn Parent, April 2004)

(a)

Name sodium hypochlorite, NaOCl, using Stock notation.

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

(b)

Explain what is meant by a free radical.

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

(c)

TAMLs can act as catalysts in the peroxide bleaching process. Explain how catalysts
increase the rate of a reaction.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)

(d)

Describe the THREE key features of an environmentally benign process.

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

(e)

Suggest why accumulation of dioxins in the food chain may be harmful to people.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)
(Total 7 marks)

5.

This question is about some of the chemicals used in car engines and their reactions.
(a)

Compound X, shown below, is one component of petrol.

H

C H

H C C C C C H
H
(i)

C H

CH

Name X.
...........................................................................................................................
(1)

(ii)

Give the empirical formula of X.

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

(iii)

X can be made by cracking decane, C10H22.

Assuming only one other product forms in a cracking reaction, deduce the
molecular formula of this other product.

(1)

(iv)

What is the sign of the enthalpy change for the reaction in which decane is
cracked? Give a reason for your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)

(v)

If the air supply in a car engine is poor, there is not enough air for carbon dioxide
to be produced.
Use this information to suggest ONE possible equation for the combustion of X in
this engine. Use the molecular formula of X in your equation.

(2)

(b)

When air enters a car engine, as well as the fuel burning, nitrogen and oxygen can react to
form nitrogen(II) oxide.
N2(g) + O2(g)
(i)

2NO(g)

H = + 180 kJ mol

What, if any, is the effect on the percentage of nitrogen(II) oxide in an equilibrium

mixture of these three gases if the pressure and temperature are increased?
Explain your answers.
Increase in pressure
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
Increase in temperature
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(ii)

In a car exhaust pipe, nitrogen(II) oxide passes over a catalytic converter.

The following reaction occurs.
2NO(g) + 2CO(g) N2(g) + 2CO2(g)

H = 746 kJ mol

Explain why this reaction speeds up when the car engine has been running for a
few minutes.
...........................................................................................................................
...........................................................................................................................
(1)

(iii)

A textbook says The catalytic converter converts the gases coming out of the
engine into less harmful ones.
State, with a reason, which of the four gases in the equation in (ii) you consider to
be least harmful.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)

(iv)

The diagram below shows the reaction profile for the change which occurs in the
catalytic converter.
E n e rg y

2 N O (g ) + 2 C O (g )
N 2 (g ) + 2 C O 2 (g )

P ro g re s s o f re a c tio n
On the diagram, show the activation energy, EA.
Add a line showing the reaction profile if no catalyst is present.
(2)
(Total 12 marks)

10

6.

(a)

Chlorofluorocarbons, CFCs, are useful compounds as they are non-flammable and

unreactive. In the stratosphere, the CCl bonds are broken producing free radicals.
(i)

Draw the structure of 1,1,2-trichloro-1,2,2-trifluoroethane.

(1)

(ii)

Suggest why CF bonds are not broken in the stratosphere, whereas CCl bonds
are.
...........................................................................................................................
(1)

(iii)

What are free radicals and what is needed to produce them from CFCs?
...........................................................................................................................
...........................................................................................................................
(2)

(b)

Draw the repeating units in

poly(chloroethene)

poly(tetrafluoroethene).

(2)
(Total 6 marks)

11

7.

(i)
Formula of substance
CH4 (g)
O2 (g)

Standard enthalpy of formation / kJ mol

75
0

CO2 (g)

394

H2O (g)

242

The equation for the complete combustion of methane at 150 C is:

CH4(g) + 2O2(g) CO2(g) + 2H2O(g)
Use the given data to calculate the enthalpy of combustion of methane under these
conditions.

(2)

(ii)

The standard enthalpy of combustion of methane is 891 kJ mol .

Explain why this is very different from the value you have calculated in (a)(i).
.....................................................................................................................................
.....................................................................................................................................
(1)

12

(iii)

Here are some data about different fuels:

Name

Formula

Standard state

Energy evolved
per gram / kJ

Relative cost
per kJ

hydrogen

H2

gas

143

C8H18

liquid

48.4

70

octane

State and explain the advantages and disadvantages of using hydrogen compared with
octane as a fuel for aeroplanes.
Use the data in the table above and your knowledge of the combustion of fuels to help
you.
.....................................................................................................................................
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13

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(4)
(Total 7 marks)

14

8.

Which of the following is not a greenhouse gas?

A

CH4

CO2

H2O

N2
(Total 1 mark)

15

9.

Which of the following fuels has the smallest carbon footprint?

A

petrol made from crude oil

hydrogen made from methane

ethanol made from sugar

coal
(Total 1 mark)

16

10.

Which of the following would not lead to a greater sustainability in an industrial process?
A

using a catalyst that improves atom economy

running the reaction at a higher temperature

using biofuels to run the process

recycling waste products

(Total 1 mark)

17

11.

Chlorine was used in swimming pools as a bactericide.

The amount of chlorine present can be determined by adding excess potassium iodide solution
to a known volume of swimming pool water. This reacts to form iodine:

Cl2(aq) + 2I (aq) I2(aq) + 2Cl (aq)

The amount of iodine formed is then found by titration with sodium thiosulfate solution of
known concentration.
The ionic equation for the reaction between iodine and sodium thiosulfate in aqueous solution is
2

I2(aq) + 2S2O3 (aq) S4O6 (aq) + 2I (aq)

A student carried out the determination of chlorine in a sample of swimming pool water.
A record of the measurements obtained is given below:
3

Volume of water sample tested

= 1000 cm

Final reading of burette

16.3 cm

Initial reading of burette

7 cm

Volume added from burette

9.3 cm

3
3
3
1

Concentration of sodium thiosulfate solution = 0.00500 mol dm

18

(a)

(i)

The record of measurements reveals faults both in the procedure and the recording
of measurements. State one fault in each of these.
Procedure .........................................................................................................
Recording of measurements .............................................................................
...........................................................................................................................
(2)

19

(ii)

Calculate the number of moles of sodium thiosulfate used in the titration.

(1)

20

(iii)

Use your answer to (ii) to calculate the number of moles of iodine which reacted.

(1)

(iv)

Deduce the concentration of chlorine, in mol dm , in the swimming pool water.

(1)

21

(b)

The disinfecting action of chlorine in swimming pools is due to the presence of chloric(I)
acid, HClO, formed by the reaction of chlorine with water.
In many swimming pools, chemicals other than chlorine are used to form chloric(I) acid.
This is partly because the use of chlorine gas causes much more corrosion of metal parts
in swimming pools than does chloric(I) acid.
Compounds used to chlorinate swimming pool water in this way include calcium
chlorate(I) and chlorine dioxide.
(i)

State and explain the type of reaction that occurs when chlorine attacks a metal,
using the example of iron.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

22

(ii)

Suggest one other reason why the use of chlorine is undesirable in swimming
pools.
...........................................................................................................................
(1)

23

(iii)

Give the formula for calcium chlorate(I).

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

24

(iv)

Chlorine dioxide, ClO2, undergoes a disproportionation reaction when it reacts

with water.
4ClO2 + 2H2O HClO + 3HClO3
Explain, in terms of oxidation numbers, why this is a disproportionation reaction.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

25

(c)

Discuss and explain the science communitys advice that CFCs should no longer be used
in aerosols, foams and refrigerants. Support your answer with one or more equations.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
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(6)
(Total 17 marks)

26