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Unit 2.13 (p236-247 in AS Chemistry textbook, p108-
114 in CGP AS Chemistry revision guide for Edexcel)
Global warming and climate change
NEED to know
The greenhouse effect is a vital factor in keeping our planet warm
enough for us to live on it.

The Sun emits electromagnetic radiation mostly as visible light, UV
radiation and infrared (IR) radiation.
When this solar radiation reaches the Earths atmosphere the UV
and IR radiation is mostly absorbed by atmospheric gases and some
is reflected back into space from clouds.
Visible light, IR and UV radiation reaching the Earths surface can
be reflected back into space (especially from light-coloured surfaces
such as snow) but the rest is absorbed by the Earth, which heats up.
The Earth radiates energy back out to space as IR radiation (heat).
Gases in the atmosphere can absorb some of this IR radiation and
re-emit it in all directions. Some gets back to Earth again and keeps
us warm.
This is called the greenhouse effect because gases in the atmosphere act
like the glass in a greenhouse, trapping some of the energy. If this didnt
happen and almost all the energy was lost to space, the Earth would be
about 30C cooler and we wouldnt be able to live here.







The table below shows the relative greenhouse factor and the global
warming potential for some of the most common greenhouse gases.

Greenhouse gas Formula Relative
greenhouse
factor
Global warming
potential
Carbon dioxide CO
2
1 1
Methane CH
4
30 20
Dinitrogen
oxide
N
2
O 200 300
Typical CFC E.g. CCl
3
F 21000 6500
Definition: Gases which contribute to the greenhouse effect are called greenhouse
gases and are classified according their relative greenhouse factors. This term
allows a comparison of the effect they will have on global warming. It is calculated
by comparing the effect gases have in absorbing IR radiation relative to the effect
of carbon dioxide, the most common greenhouse gas. The global warming
potential of a gas is calculated by combining their relative greenhouse factor
(ability to absorb IR radiation) and their half-life in the atmosphere (how long they
take to break down). It is a better measure of the true effects of releasing a gas into
the atmosphere over its whole lifetime.
The effect of humans burning fossil fuels and adding greenhouse
gases to the atmosphere is causing anthropogenic climate change.
Of course, the climate sometimes changes on earth naturally (for
example the Ice Ages which wiped out woolly mammoths), due to
processes such as the dissolving of carbon dioxide in seawater, plant
growth or solar activity, so it can be difficult to work out how much
of the change is due to humans.

Scientists think some human activities are particularly bad for the
atmosphere, such as air travel. High-flying jet aircraft produce frozen
water vapour trails called contrails. Although these are only water
they might be contributing to changes in the atmosphere as more
clouds may reflect more energy out of the Earths atmosphere.
Aircraft engines also produce nitrogen oxides which are greenhouse
gases and can destroy ozone in the upper atmosphere which
protects us (there is more about this later in this unit).


EXTENSION AND EXPERIMENTS: How science works

How do we tell if humans are causing climate change? This is quite a
difficult question to answer because the Earths climate system is very
complicated, and scientists are debating this question all the time. But
most scientists now agree that human activity is having a large effect on
the climate of our planet and is causing it to warm up, largely by
increasing the amount of carbon dioxide in the atmosphere. Lets have a
look at the evidence used to investigate this question.

In order to see if the climate is changing, we need to look at what it did in
the past. In order to work this out, scientists can use tree rings to work
out the temperature of the planet in the past (because trees grow wider
rings in their trunk in years with a high temperature). We can also use ice
cores (drilled from the Antarctic or Greenland ice sheets) to look at the
composition of the atmosphere in the past, because trapped bubbles of
air are found in the ice cores, and the air can be extracted and analysed.
This technique allows us to look very far in the past because scientists can
take very deep ice cores, reaching ice which was set down a long time
ago. We can also use historical records taken by people in previous
centuries, and from the 20
th
century we have very good records from
weather and climate monitoring stations, which record details about the
climate in a particular area. Satellites provide very detailed data about
the exact composition of the atmosphere over the whole globe.

Using all these techniques, scientists have pieced together a picture of
what the climate and atmosphere was like over thousands of years:


You can see that changes in carbon dioxide levels are followed very
closely by changes in temperature. The main piece of evidence for
anthropogenic climate change is that normally in the past, large changes
in temperature or carbon dioxide levels have only occurred very slowly
(normally over thousands of years). However, recently levels of carbon
dioxide and temperature have peaked very sharply, which does not fit the
previous pattern. The large increase over the last century is therefore
very likely to be due to human activities. Apart from this, the overall level
of CO
2
in the atmosphere is a concern because it is higher now than for
many millions of years. Although carbon dioxide is slowly removed from
the atmosphere (for example by dissolving in sea water and marine
sediments, and being absorbed by plants, which might eventually make
fossil fuel) most scientists are concerned that we are adding CO
2
to the
atmosphere much more quickly than it can be removed. This could lead
to species becoming extinct and the ice caps melting, as well as causing
problems for people. A more unpredictable climate would be bad for
everyone!

Quick Questions
1. Carbon dioxide has a lower relative greenhouse factor than other
gases. Why is it so significant when considering global warming and
climate change?
2. How can we tell the difference between natural and anthropogenic
climate change?
3. Greenhouse gases are the major cause of anthropogenic climate
change.
a. Name three greenhouse gases. (2 marks)
b. Explain how greenhouse gases keep the temperature in the
lower layer of the Earths atmosphere higher than it would
otherwise be. (3 marks)
c. What factors affect the contribution a gas makes to the
greenhouse effect? (2 marks)

Carbon neutrality and carbon footprint
NEED to know





When thinking about whether a process or fuel is carbon neutral it is
important to remember all the stages in its production. For instance at
first glance you might think that a wind farm would be carbon neutral
since it does not produce carbon dioxide directly. However when you
think about the carbon dioxide that was released during the process of
manufacturing the wind turbine and transporting it to the right place, as
well as making the infrastructure that supports delivery of the electricity
from the wind farm to homes, the situation is not so clear.





Some companies or individuals try to reduce their carbon footprint by
carbon offsetting, a process in which a project is put in place to be a net
sink of carbon, to make up for emissions. This could be building a
renewable energy source such as a solar or wind farm, or planting new
trees. But some companies have also tried to do this by carbon trading,
Definition: A fuel or process is carbon neutral if the carbon dioxide released in
using/doing it is the same as the carbon dioxide that was absorbed when it was
formed. Usually this definition is modified to include the idea that the fuel must be
able to be formed within a reasonable length of time, so that for example, oil which
can take thousands of years to form is not truly renewable but wood is.
Definition: Your carbon footprint is a measure of how much impact you have on
the environment in terms of greenhouse gases released. This is usually calculated
as tonnes or kilograms of CO
2
released (taking into account the global warming
potential of different greenhouse gases that might be released) in a process (or for
a fuel in g/kJ). The carbon footprint can be calculated for any individual, business or
process. An individuals carbon footprint is often calculated over a year.

whereby they pay some other company or individual to release less
carbon and the carbon footprint simply balances overall.
You should know about the reactions of CFCs and HCFCs with ozone,
which lead to the depletion the ozone layer. This is separate from their
effect as greenhouse gases. The ozone layer normally stops harmful
ultraviolet radiation from reaching the Earths surface, so a hole is bad
news! This is the reaction that occurs:
1. Firstly ozone is formed in the atmosphere when UV radiation makes
oxygen molecules break up to form oxygen free radicals. The
oxygen free radicals recombine with oxygen to form ozone:

2. CFCs are dissociated by UV radiation to form free radicals:

3. The chlorine free radical reacts with ozone:

4. The new chlorate free radical reacts with ozone and produces more
chlorine free radicals:

During this reaction the overall effect is to convert two molecules of
ozone to three molecules of oxygen. The chlorine radicals formed in the
reaction are not used up and so are catalytical radicals. One of the main
reasons this reaction is so harmful is that it can form a chain reaction.
Nitrogen oxides also damage the ozone layer by producing NO radicals
which act in the same way:

In this reaction the NO acts as a free radical catalyst again. Gases such as
CFCs have been gradually phased out and are now usually replaced with
HCFCs which do not break down to form free radicals.

EXTENSION AND EXPERIMENTS: How science works

Talking about carbon footprints can be a political issue. Take a look at this
map which plots greenhouse gas emissions per person globally. Most of
the emissions are produced by developed countries, but developing
countries such as India and China with large populations and increasingly
industrial economies might soon overtake this. It does not seem very fair
to say to these countries that they cannot enjoy the lifestyle that
countries in Western Europe and North America have enjoyed over the
last half-century. But tackling carbon emissions has to be a global task as
the effects of global warming will harm us all. So what should be done?


First the basic science had to be in place. For example in order to control
gases such as CFCs we first need to know the effects these gases have
very clearly. This was shown by scientists from the British Antarctic
Survey observing the atmosphere. In the 1970s they showed that the
concentration of ozone over the Antarctic was very low compared to
what had been previously measured. They measured it again in 1985 and
were surprised to find that it was even lower. They checked their
equipment and results to find out if they were right but got the same
result. When they published their results in a scientific journal, other
scientists read it and were very surprised too but a team looking at
satellite data also found evidence of the ozone hole. They hadnt noticed
it before in their results because their computers ignored measurements
below a certain level and treated them as errors.

Once scientists had worked together to find out the answer (and work
out what was causing the hole in the ozone layer) the political community
had to get involved to help solve the problem. They did this by agreeing
an international treaty called the Montreal Protocol of 1989, which
agreed that countries would stop using CFCs and other ozone-destroying
halogenoalkanes by the year 2000. Nowadays scientists have found
alternatives and CFCs are only used in a few applications where there is
no useable alternative.

The same international effort had to be brought to bear on the carbon
dioxide emissions problem. Again this was dealt with by an international
agreement called the Kyoto Protocol. Adopted by 37 countries in 1997,
this agreement recognised that not all countries contribute to global
warming equally and tried to reach a fair solution. A target of just over 5%
reduction in greenhouse gas emissions compared to 1990 levels, by the
year 2012, was agreed for developed countries, mostly in Europe and
North America. It was also agreed that other countries would also try to
reduce their emissions on a voluntary basis, and that developed countries
would try to help developing countries with this target, for instance by
giving advice and donating expertise and money to green technology and
the development of green energy resources in these countries.




Quick Questions

1) Decide whether you think these fuels are really carbon neutral and
give your reasons:
a) Petrol (1 mark)
b) Hydrogen made from reforming methane (1 mark)
c) A biofuel such as bioethanol (1 mark)
d) Solar-power (photovoltaic cells) (1 mark)
If you had to pick the most carbon neutral one of these fuels to power
a device, which would you choose? Apart from the emissions involved,
what other considerations do people have when picking a fuel?
(3 marks)
2) CFCs were invented in 1928. They were widely used in the 20
th
century
and are now being phased out.
a) What are the useful properties of CFCs? Name three typical uses for
these compounds. (6 marks)
b) Why was the use of CFCs banned by the Montreal Protocol?
(1 mark)
c) Write out the reactions of CCl
3
F which lead to ozone depletion.
(6 marks)
3) Do you think it is fair that some companies try to reduce their carbon
footprint by carbon trading? What problems can you see with this
system? (2 marks)

Reducing hazards and pollution in the chemical
industry
NEED to know
The modern chemical industry is trying to become greener by controlling
the pollution it makes, using less energy and using fewer finite resources.
One of the main problems is the disposal of solid waste. Many materials
can be recycled or re-used, such as glass, metal or paper. It is often much
cheaper and uses much less energy to recycle resources than make new
ones. For example, recycling aluminium means that the process of
extracting the aluminium by electrolysis does not need to be repeated,
and it also reduces the emission of PFC (perfluorocarbon) gases, which
are potent greenhouse gases.
If a material cannot be recycled, it must be disposed of, usually either by
incineration (combustion) or in landfill sites. Incineration produces
carbon dioxide and sometimes harmful materials such as dioxins, but it
has the advantage of producing heat which can be captured and used in
energy-recovery systems such as for heating a building. Landfill sites get
used up, and the waste can take a long time to be broken down by
bacteria in the soil. The other problem with landfill is that it produces
methane, which can be explosive and is a greenhouse gas. In order to
stop this happening, methane can be recovered from the site and used as
fuel, although this can be difficult. Sometimes it is just burned to produce
waste heat, but usually we would try to use this heat for something
useful.
Waste water which has been contaminated with pollutants cannot legally
be dumped straight into rivers or the sea, so chemical factories often
have to develop technologies to filter and purify the water and special
tanks to store it in. Waste gases include sulphur dioxide, which causes
acid rain and is a greenhouse gas. There are now controls in place which
set maximum concentrations that can legally be released into the
atmosphere. Often acidic gases are removed from flue gases by reacting
with limestone:

The result of this reaction (and of burning methane and many other
common reactions) is the release of carbon dioxide. Although this does
not have cause acid rain it is still a greenhouse gas so we would also like
to reduce the amount of carbon dioxide released. One way of doing this is
carbon capture (and sequestration).








Definition: Carbon capture is the technology which allows carbon dioxide to be
stored somewhere, usually in a liquefied form. There have been suggestions that
we could pump this liquid waste CO
2
1km under the ocean into porous rocks,
where it should remain stable because of the pressure and not cause any further
environmental damage. This process could be done at the same time as drilling for
natural gas or oil, pumping the CO
2
down instead of gas or oil up.

This picture shows how the plan to do carbon capture in the Miller oil
fields in the North Sea might look. Natural gas and oil are extracted, and
the carbon dioxide is liquefied in the power plant and pumped back down
a pipeline to the oil rig which can pump it down under mudrock which
forms a good seal to keep the CO
2
out of the atmosphere, maybe for
millions of years. A trial of this technology has already been used in
France at the Lacq power plant with great success.

EXTENSION AND EXPERIMENTS: How science works

Apart from discovering facts about the universe, scientists are often
involved in developing new technologies. In the area of green chemistry
this is particularly true. Scientists are trying to develop new renewable
resources before fossil fuels run out or become too expensive. Its not
just for fuel, because oil is also used to make plastics and to produce
chemicals such as ammonia, nitric acid, benzene, sulphuric acid and
ethanoic acid. Some of the new technologies that have been developed
are:
Bio oil from wheat: Wheat is renewable as a new source can be
grown each year. A type of oil which can be used for fuel is
produced from the wheat using a process called pyrolysis. The
straw is heated without oxygen so it does not burn, but breaks
down into smaller molecules. This material is then cooled quickly so
it does not react and this bio oil or pyrolysis oil can be used as a
fuel. The by-products (carbon solids and a mix of gases) can also be
used at the factory, so this process is relatively carbon neutral.
Ethanol from organic waste: Ethanol (used for many industrial
chemical processes) can be produced by fermenting plant material,
usually using a genetically modified bacterium. One such GM
micro-organism is KO11, a bacterium that was developed by the
microbiologist Lonnie Ingram in 1987. The pathways in this
bacterium that normally produce acids have been hijacked in the
GM organism to produce ethanol instead. Often this process can be
performed using a starting material that would normally have been
thrown away, such as corn stalks or rice hulls, so this is very
efficient. This is important because in some cases farmers grow
large areas of crops such as maize to be used for bio-ethanol
production, but land is also needed to grow food crops for our
increasing world population.
Starch and cellulose from plants: Both of these materials are
naturally produced by plants and can be used to make a variety of
materials such as plastic bags, paints, adhesives, insulation and a
fibre called lyocell (used for clothes and household textiles). These
materials have the advantage that they are usually biodegradable
unlike equivalent materials made from fossil fuels, and since they
are grown from plants they are renewable.



Quick Questions

1. Explain why plants are a sustainable resource. (1 mark)
2. Suggest reasons, apart from cost, that carbon capture might not go
ahead. (2 marks)
3. Why is removing sulphur dioxide from flue gases using limestone not a
total solution to the problem? (1 mark)
4. Suggest two reasons for the decline in the use of fossil fuels in the
chemical industry. (2 marks)

Increasing efficiency in the chemical industry
NEED to know
The development of new catalysts is an important way to improve the
efficiency of a chemical process. You should know from earlier in your
course that a catalyst speeds up a chemical reaction. Finding a more
efficient catalyst will not improve the yield (the proportion of products
made from the reactants) but will allow the same yield to be formed
more quickly. By using a better catalyst sometimes chemists can save
money and energy because they will not need to heat a reaction as much.
Catalysts are not used up in reactions so should last a long time, although
they are normally replaced sometimes due to wear and tear.





Try this example: propan-1-ol is produced from 1-bromopropane and
sodium hydroxide. What is the atom economy?
Firstly, write down the equation:

Then work out the molar masses of everything you need for the equation
[using Ar(H) = 1, Ar(C) = 12, Ar(O) = 16, Ar(Na) = 23 and Ar(Br) = 79.9].
Plug them into the equation like this:



Definition: Atom economy is a measure of how efficient a reaction is at turning
reactants into the products wanted (rather than waste products). A reaction with
high atom economy is efficient because it is expressed as a percentage. You need to
know this equation for atom economy:



This tells you that the majority of the starting materials are turned into
waste rather than the desired product. Even if the yield is 100% (the
reaction proceeds to completion) nearly 2/3 of the mass of the atoms in
the original material would be wasted. If scientists wanted to improve
efficiency in the factory making propan-1-ol they could therefore do this
by finding alternative starting materials which form a reaction with better
atom economy. Adding a catalyst would not change the atom economy
since the same reaction is occurring. Only altering the reaction used
would improve the atom economy.
Another way that chemical engineer can improve efficiency is to think
about the energy used in a chemical factory. This energy may be used for
heating reactants to start or maintain a reaction; to provide electricity for
electrolysis processes; to power distillation to separate, purify or
concentrate the products; to heat product material to dry it out; to treat
waste water; and to provide heating and hot water for the workers in the
plant. Making these processes more efficient and using more carbon
neutral and efficient energy sources can help to make the chemical
factory greener. Here are several examples of how chemists improve
processes by thinking about energy considerations:
Use electricity derived from more carbon-neutral fuel sources
(although this may not be under the control of the plant)
Reduce energy demand to save money and help the environment,
for instance by switching machines off overnight or using less
heating.
Reduce wasted energy caused by any leaking pipes or taps, and
improve insulation.
Use a heat exchanger to recover energy produced in reactions
which would normally be wasted and simply go up the chimneys.
This works by transferring energy from the reaction into water
pipes by conduction, and the energy saved here could be used to
provide heating and hot water for the plant.
Adjust your reaction conditions to use less heat, but keep the
reaction going quickly by using good catalysts or putting it under
pressure. If doing a reaction which uses oxygen, consider using pure
oxygen rather than air, so you are not heating other components in
the air.
Generate your own electricity, ideally from a carbon-neutral source.
Then you do not need to pay transmission costs.
Use microwaves to heat reactions, which speeds up the reaction
massively and can mean catalysts are not even needed. Modern
industrial microwaves work by producing an electric field, causing
polar molecules such as water to line up. The field switches
continually so the molecules are constantly moving, trying to line
up. Microwave energy is there converted into movement and
therefore thermal energy. The movement of the water molecules
heats up the other molecules around them. This process is much
more efficient than heating with a conventional oven and very high
temperatures can be reached. For example, if a reaction is heated
up by 60C, the rate will increase by 106 times.

EXTENSION AND EXPERIMENTS: How science works
You might wonder how scientists know which catalyst to choose for a
particular reaction. Sometimes they find out by accident when a bit of
another molecule contaminates the reaction and it goes faster. But
sometimes chemists search for a new catalyst by trying out different
molecules, or thinking about how the catalyst is speeding up the reaction
and trying to guess another molecule that would do the same. An
example of this is the production of ethanoic acid. Firstly, industrial
chemists had looked at this reaction and maximised the atom economy:
oxidising ethanol, or oxidising butane and naphtha (from fossil fuels) both
produce ethanoic acid but both reactions only have an atom economy of
35%. However if you instead react methanol with carbon monoxide you
get an atom economy of 100%, with no waste: CH
3
OH + CO CH
3
COOH.

This reaction still had some problems though, because it went really
slowly, unless you performed it at 300C and 700 atmospheres pressure,
with a cobalt catalyst and an iodide co-catalyst. And maintaining these
conditions is hazardous and expensive. A company called Monsanto
therefore did some more work on this and tested new catalysts out. They
realised that to get a catalyst with similar properties they could look in
the same column of the periodic table, and that elements further down
this column might be better because they would participate in the
reaction more. So they tried out rhodium, the next element down from
cobalt, and found that with this catalyst, they could reduce the
temperature to 150-200C and the pressure to 30-60 atmospheres. This
was called the Monsanto process.

But there were still some problems. Rhodium is really expensive (more
than gold!) and sometimes the rhodium and iodide ions formed insoluble
salts such as RhI
3
, which stops it acting as a catalyst, and contaminates
the products. You can stop this by adding water but then you have to do
more drying, which uses more energy. Also rhodium catalysed unwanted
side reactions (such as CO +H
2
O CO
2
+H
2
). So they tried again with the
next element down in that column of the periodic table, iridium. At first
this did not work as well as a catalyst, but then they discovered that
adding ruthenium as well made a really active and specific catalyst. With
this you avoid all the problems of rhodium but still get to use low
temperatures and pressures, and you dont get so many by-products. This
process is now called the Cativa process and is illustrated in the diagram
below:



You can see that the catalyst is recovered in the process. Scientists are
still trying to improve efficiency further, however, for instance by
producing the methanol which goes into the reaction from waste
products rather than from oil.

Quick Questions
1. Look at the flow diagram above which illustrates the Cativa process.
What steps are taken to:
a. produce a pure product
b. reduce costs
c. protect the environment? (3 marks)
2. Consider the addition reaction of bromine to propene. Work out
the atom economy of this reaction. (3 marks)
3. List four ways in which the chemical industry can be made more
sustainable. (4 marks)

Green chemistry Checklist
Before you try some exam questions check that you have learnt the
unit:
Students will be assessed on their ability to:

(a) Demonstrate an understanding that the processes in the
chemical industry are being reinvented to make them more
sustainable
(greener) by:
(i) changing to renewable resources
(ii) finding alternatives to very hazardous chemicals
(iii) discovering catalysts for reactions with higher atom
economies, e.g. the development of methods used to
produce ethanoic acid based on catalysts of cobalt, rhodium
and iridium
(iv) making more efficient use of energy, eg the use of
microwave energy to heat reactions in the pharmaceutical
industry
(v) reducing waste and preventing pollution of the environment

(b) discuss the relative effects of different greenhouse gases as
absorbers of IR and hence on global warming

(c) discuss the difference between anthropogenic and natural
climate change over hundreds of thousands of years

(d) demonstrate understanding of the terms carbon neutrality
and carbon footprint

(e) apply the concept of carbon neutrality to different fuels, such
as petrol, bio-ethanol and hydrogen

(f) discuss and explain, including the mechanisms for the
reactions, the science communitys reasons for recommending
that CFCs are no longer used due to their damaging effect on
the ozone layer.

Exam questions
The following questions are extracted from previous past papers. Questions marked with an asterix
were ones in which the quality of your written English was also assessed. Answers are provided at
the end for reference, but it is highly recommended you attempt the questions on your own before
reading the answers.
January 2009
Q18c. iv.* Explain why fire retardants containing some halogenoalkanes, such as CF
2
ClBr, are being
phased out.
Suggest a reason why the scientific community still supports the use of fire retardants containing
CF
3
CHF
2
. (4)

d. (i) In the Cativa process what effect, if any, would increasing the pressure have on the yield of
ethanoic acid? Justify your answer. (2)

(ii) Suggest TWO reasons why it might be difficult, or undesirable, to produce ethanoic acid in
industry by scaling up the laboratory process. (2)
Q21. Ethanoic acid is used industrially in the manufacture of polymers and glues and also in the
food industry as an acidity regulator.
It can be synthesized in the laboratory by the reaction of ethanol with excess sodium
dichromate(VI) solution, acidified with concentrated sulfuric acid. Ethanol is placed
in a suitable flask along with some anti-bumping beads. The concentrated sulfuric
acid is then added a drop at a time. The sodium dichromate(VI) solution is then added a drop at a
time causing the mixture to boil spontaneously. When the addition of the sodium dichromate(VI)
solution is complete, the mixture is heated under reflux for approximately 15 minutes. The
ethanoic acid formed can then be separated from the reaction mixture.
CH
3
CH
2
OH CH
3
COOH
(Conditions: Na
2
Cr
2
O
7,
H
2
SO
4
, heat, 1 atm)
Ethanoic acid can be produced industrially by the Cativa process. Methanol, which can be
obtained from wood, is reacted with carbon monoxide in the presence of an iridium catalyst.
CH
3
OH(g) + CO(g) CH
3
COOH(g)
(Conditions: Iridium catalyst, 2030 atm, 190C)
*e. An alternative industrial process for the production of ethanoic acid is the oxidation of butane
using a transition metal catalyst at 150C and 5560 atm.
2C
4
H
10
(l) + 5O
2
(g) 4CH
3
COOH(aq) + 2H
2
O(l)
Evaluate the greenness and sustainability of the two industrial processes.
Suggest TWO additional pieces of information that would help you make a more informed decision.
(6)
January 2010
(Source: adapted from an article from the NewScientist.com by Tom Simonite, March 2007)
d. Suggest ONE benefit of using a light activated catalyst for the new process.
(1)
*f. Benzene, which is needed for the new process of breaking down carbon dioxide, can be
made from coal. It is now usually made by catalytic treatment of one fraction of crude oil at
temperatures of around 500C and 20 atmospheres pressure.
Q 20. Fuel from the air?
A new catalyst that can break down carbon dioxide gas could allow us to use carbon from the
atmosphere as a fuel source in a similar way to plants.
Plants break the stable bonds in carbon dioxide during photosynthesis. In the natural process,
the carbon dioxide molecule is initially bonded to nitrogen atoms, making reactive compounds
called carbamates. Carbamates are derivatives of carbamic acid, NH
2
CO
2
H. These compounds
can then be broken down, allowing the carbon to be used in the synthesis of other plant products
such as sugars and proteins.
A new catalyst produced by scientists is a graphite-like compound made from flat layers of
carbon and nitrogen atoms arranged in hexagons. Carbon dioxide binds to the catalyst and takes
part in the following reaction, which occurs at 150C and at about three times atmospheric
pressure.

C
6
H
6
+ CO
2
C
6
H
5
OH + CO
benzene phenol

Carbon monoxide can then be used to make liquid fuels such as methanol.
The energy required for photosynthesis comes from light, and experiments are now going on to
develop a light activated catalyst which could break down carbon dioxide in a new process.

Suggest the benefits and disadvantages of breaking down carbon dioxide using benzene and the
catalyst as described in the passage. You should consider
the energy and resources needed
the effects on the atmosphere
whether it is a beneficial method for producing energy compared to direct use of fossil fuels.
(6)
January 2011
Q5. Which of the following is a greenhouse gas?
A Argon
B Nitrogen
C Oxygen
D Water vapour (1)

Q8. Which of the following best defines the meaning of the term anthropogenic change?
It is a change caused by
A nature.
B plants.
C animals.
D humans.
(1)
Q12. Which of the following statements is true?
A CFCs and nitrogen monoxide, NO, are involved in the depletion of the ozone layer.
B CFCs act as catalysts for the depletion of the ozone layer, while nitrogen monoxide, NO, does
not.
C CFCs and ozone are free radicals.
D CFCs and nitrogen monoxide, NO, are decomposed by UV radiation.
(1)

Q16. This question is about some reactions which can be used in the manufacture of hydrogen.

Reaction 1 uses two naturally occurring chemicals, water and natural gas. Steam is reacted with
methane to form carbon monoxide and hydrogen in an equilibrium reaction.

Reaction 1 CH
4
(g) + H
2
O(g) CO(g) + 3H2(g) H = +210 kJ mol
1


In reaction 2, carbon monoxide and steam are passed over copper at high temperature. This forms
carbon dioxide and hydrogen.

Reaction 2 CO(g) + H
2
O(g) CO
2
(g) + H
2
(g)

The carbon dioxide formed is removed by passing it through potassium carbonate solution in
reaction 3.

Reaction 3 K
2
CO
3
(aq) + CO
2
(g) + H
2
O(l) 2KHCO
3
(aq)

The potassium carbonate is regenerated by heating the potassium hydrogencarbonate solution in
reaction 4. The carbon dioxide gas produced is released into the atmosphere.

Reaction 4 2KHCO
3
(aq) K
2
CO
3
(aq) + CO
2
(g) + H
2
O(l)

b. (i) Discuss, with reasons, the conditions of temperature and pressure that would favour the
production of hydrogen in reaction 1. You should consider the effect of the conditions on both yield
and rate.
(7)
d. (i) State one economic advantage of reaction 4.
(1)

* (ii) Reaction 4 contributes to global warming. Identify the substance formed in this reaction which
is likely to be responsible and explain the processes that lead to an increase in global temperatures.

Suggest two effects an increase in global temperatures might have on the environment.
(4)














June 2009

*f. (i) Explain what is meant by a carbon neutral fuel (2)
* (ii) Suggest TWO reasons why these biofuels may not be carbon neutral and describe TWO effects
that large scale production of biofuels may have on society. Which of the three biofuels do you
think is the most sustainable? Justify your choice. (5)

Q23. As levels of fossil fuel resources are getting lower, society is increasingly looking at the use
of biofuels as alternatives to coal, oil and gas. Biofuels are derived from plants and examples
include bioethanol, biodiesel and Miscanthus, a plant more commonly known as elephant grass.
These fuels have the advantage of being renewable and the plants take in carbon dioxide as they
grow.

Bioethanol is produced from crops such as sugar cane or corn. The raw plant material is treated
to produce a sugary solution which is then fermented to produce ethanol, water and carbon
dioxide gas. The ethanol is removed by distillation. The resulting solution contains about 96 %
ethanol. The remaining water has to be removed by absorption using a suitable drying agent so
that the ethanol can burn efficiently. The bioethanol can then be burnt alone or mixed with
petrol in vehicle engines.

Biodiesel is formed by the hydrolysis of vegetable oils using sodium hydroxide
solution, followed by esterification with methanol and a sodium hydroxide catalyst. Biodiesel can
then be used on its own in diesel-engined vehicles or mixed with diesel derived from crude oil.
Plants which are used to produce the vegetable oils include rapeseed in the UK, soya bean in the
USA and palm oil in Asia.

Miscanthus, or elephant grass, is a quick growing, high-yield plant that grows up to four metres in
height. After harvesting, the grass is left to dry and then burnt in power stations designed to run
on solid fuels such as coal. In the United Kingdom, farms that produce elephant grass are
normally situated within 50 miles of such a power station.

In an experiment to simulate the production of bioethanol, a student produced a water/ethanol
mixture by fermentation of sucrose solution using yeast. It was then proposed to separate the
ethanol from water by carrying out a distillation on the mixture. The mixture would then be
dried using a suitable drying agent.
June 2010
Q15. The use of poly(ethene) packaging has been criticised mainly because:
A the complete combustion of poly(ethene) produces dangerous fumes.
B large amounts of oil are consumed in producing the monomer, ethene.
C poly(ethene) degrades to form toxic products.
D the catalyst used in the polymerization of ethene is expensive.
(1)

c. In the early 1900s, the CFC with the formula CCl
2
F
2
was identified as a refrigerant which was both
non-flammable and non-toxic.
(i) What does the term CFC stand for? (1)
(ii) Suggest ONE use for CFCs other than as a refrigerant. (1)

Q22. Halothane is a colourless and sweet-smelling liquid. It has a boiling temperature of 50C.
Halothane vapour was used as a general anaesthetic in hospitals during the mid to late 20th
Century. Patients inhaled the halothane vapour under medical supervision. However, halothane
was found to have some adverse side-effects and was therefore replaced by other
halogenoalkane anaesthetics.

Halothane has the structure



In an experiment, halothane was heated in a test tube with aqueous silver nitrate
and ethanol, using a water bath. Compound X and bromide ions were formed. The structure of
compound X is shown below.

Compound X
C
Cl
H
F
C F
F Br
C
Cl
H
F
C F
F OH
* (iii) In the stratosphere, CFCs are broken down by absorption of UV radiation to form chlorine free
radicals.
The following two reactions occur.
Cl

+ O
3
ClO

+ O
2
ClO

+ O Cl

+ O
2
Combine these two equations to give the overall equation for the reaction of ozone in the
stratosphere. State the role played by the chorine free radical in the overall reaction. Hence explain
why many scientists consider the effects of CFCs on ozone to be harmful. (5)

d. The compound of formula CH
2
F
2
has replaced several CFCs for commercial use. If molecules of
CH
2
F
2
reach the stratosphere, they do not break down to produce fluorine free radicals.
(i) Suggest why C-F bonds are not broken in the stratosphere. (1)
* (ii) The compound CH
2
F
2
acts as a greenhouse gas when it absorbs a particular type of radiation.
Name this type of radiation, and explain why a molecule of CH
2
F
2
is able to absorb this radiation.
(2)













ANSWERS TO QUICK QUESTIONS

Global warming and climate change

1. There is much more carbon dioxide in the atmosphere than the other gases and therefore
it has a bigger effect. Carbon dioxide is the greenhouse gas most often released by human
activities so we are very interested in its effects and how it might contribute to natural or
anthropogenic climate change.

2. By looking at climate data: natural climate change occurs in cycles and is very slow.
Anthropogenic climate change has happened very quickly and recently.

3. Any of: carbon dioxide, methane, dinitrogen oxide, CFCs (or specific example), water
vapour (2 marks for 3 correct, 1 mark for 2)
b. The Earth emits IR radiation/heat (1 mark) some of which is absorbed by greenhouse
gases (1 mark). The greenhouse gases re-emit IR radiation in all directions including towards
Earth (1 mark)
c. How much radiation one molecule of the gas absorbs (1 mark). How much of the gas
there is in the atmosphere (1 mark).

Carbon neutrality and carbon footprint

1a. Not renewable. Takes thousands of years to form. So not really carbon neutral
b.Feedstock may be renewable and carbon-neutral eg/ biomass, but the industrial process
requires energy, usually not from a carbon neutral source.
c.Carbon emissions here come from production of fertiliser, pesticides and tools for growing
the crops, processing and refining and transporting the crops, infrastructure. So not carbon
nautral.
d. Producing the solar panels takes energy and is probably not carbon neutral. The transport
and infrastructure are probably not carbon neutral.

Pick any of b-d and give a sensible reason. Other considerations: type of application energy
will be used for - eg. biofuel for some cars, solar power for calculators. Efficiency depending
on location eg/ solar power better somewhere more sunny than the UK!

2. a They are unreactive/chemically stable, non-toxic, non-flammable, volatile (3 marks for
any 3). Uses: fridge coolants, aerosol propellants, fire extinguishers, foaming plastics (3
marks for any 3)
b.Because they were destroying the ozone layer.
c. CCl
2
F
2
+ hv CClF
2
+ Cl ; Cl + O
3
ClO + O
2
; ClO + O
3
2O
2
+ Cl 3 marks for
recognisable equations, 3 marks for balancing and correct notation.
3. Give 2 marks if reasonable reasons given. Eg/ maybe the person trading their carbon
allowance wouldnt actually have emitted anyway (produces false saving). Doesnt promote
development of new green technologies etc. Is unfair because you shouldnt be able to buy
your way out of doing the right thing.

Reducing hazards and pollution in the chemical industry
1. Plants can be grown quickly and the same field can be used to grow crops every
year. That means the carbon dioxide released on burning/using the plants can be
quickly re-sequestered by growing more crops.
2. Insufficient interest or funding from government or companies, problems with the
technology (eg gas seeping out again), people may find other solutions, it might be
easier to just lower emissions. (any 2 or reasonable answer)
3. Because this process produces carbon dioxide which is also a greenhouse gas
(although it does not cause acid rain).
4. Costs rising, awareness of green issues, reputation of companies, low availability of
fossil fuels, better alternatives. (any 2 or reasonable alternative answer).

Increasing efficiency in the chemical industry
1. a. Drying column, distillation, separation tank (from catalyst)
b. use good catalyst to reduce temperature, recycle catalyst
c. burning waste gases, getting reactants and energy from sustainable source, use
less energy by using lower temperature (catalyst) (Each part, any 1 point =
1 mark)

2. Equation: Br
2
+ CH
3
-CH=CH
2
CH
3
-CHBr-CH
2
Br


=
= = = 100%
(1 mark for correct answer, 2 marks for correct working, either as above or by
writing out equation and noting that there is only one product (the desired one) so
atom economy must be 100%)

3. Any 4 of: use energy from sustainable energy sources, reduce total energy usage,
reduce waste products (have better atom economy), design better catalysts
(perform reactions at lower temperature), use microwaves, use heat exchangers,
recover catalysts, convert waste gases in flues into less harmful gases. (Or any other
suitable answer).
Answers to exam questions

January 2009

Q18c. (iv)
Halogenoalkanes such as CF
2
ClBr can release Cl free radicals
Cl free radicals react with O
3

Ozone layer depletes
Leading to greater levels of UV exposure
Greater risk of skin cancer

(Any 3 from above, in context and using correct terminology)

AND

CF
3
CHF
2
has strong C-F bonds so does not release F radicals

Q21. d. (i)
Increase yield (1)
As reaction moves to RHS as there are
fewer (gaseous) molecules (1)

(ii) Any two considered suggestions e.g.

Yield of lab process may be low
Cost of oxidising agent
Toxicity of oxidising agent
Disposal of Cr
3+

Control of temperature/rate in scaled up reaction could be difficult
The lab process has a lower atom economy
Energy costs to separate ethanoic acid from reaction mixture
Lab procedure is a batch process

e. Discussion of four aspects of processes

(e.g four from):

Cativa runs at lower Pressure
Hence less energy required (for compression)
Cativa has 100% atom economy
Methanol in cativa could be obtained from renewable sources
Cativa produces only one product so less separation required
Cativa runs at higher temp so greater energy requirements for heating

Each discussion point may made be made using reverse argument but only awarded once

plus 2 additional pieces of information

(e.g 2 from):

Life cycle cost of catalysts
Life cycle cost of capital equipment
Yield of reactions
Availability of renewable methanol.




January 2010

Q20. d. No heat energy required / low energy requirement / high temperatures not needed
/sunlight (which is renewable) could be used

Ignore generalisations such as greener, environmentally friendly smaller carbon
footprint cheaper or fossil fuels not used.

f. Score 1 mark up to 6 for each clearly made point:
1. Need energy to make benzene / catalyst/ hydrogen
2. High energy / temperature / pressure needed for the reaction (ALLOW stated T
or P)
3. Fossil fuel (oil or coal) used as source of energy, benzene or hydrogen
4. Hydrogen has to be manufactured
5. Hydrogen has to be stored
6. Fossil fuels non-renewable
7. Reduces CO2 in atmosphere / recycles CO2
8. CO2, is a greenhouse gas / causes global warming
9. CO toxic
10. Benzene toxic / carcinogenic
11. 100% atom economy in making methanol
12. Beneficial if phenol useful / not beneficial if phenol a waste product

Ignore generalisations such as greener, smaller carbon footprint or environmentally
friendly.




January 2011

Q5 = D
Q8 = D
Q12 = A

Q16. b (i): Any seven from:
1 A higher temperature would increase the yield/favour the forward reaction/produce more
hydrogen (1)
2 (as) the reaction is endothermic (1)
3 Increased temperature would increase the rate/speed of reaction /make the reaction go
faster (1)
4 (as) a greater proportion of /more molecules have sufficient /higher/activation energy
(to react) (1)
5 Decreased pressure increases the yield /favour the forward reaction /produce more
hydrogen(1)
6(as) the forward reaction is favoured with more (gaseous) molecules /mole (1)
7 Decreased pressure would decrease the rate of reaction (1)
8 (as) collision frequency decreases/less collisions (1)

Points may muddle into one another
Reverse statements allowed e.g. lower temperature decreases yield because reaction is
endothermic.
Contradictory statements in each pair lose both marks e.g. lower temperature increases
yield because reaction is endothermic.

d. (i) It regenerates /reforms potassium carbonate/reactant(s) (which reduces the cost of
the process)
OR
potassium carbonate can be re-used

Allow recycles potassium carbonate

(ii) 1 Carbon dioxide / CO2. Allow both water and carbon dioxide (1)
2 Traps longer wavelength radiation / traps radiation / IR emitted (from the earth)
OR Absorbs/traps heat /IR
OR Prevents loss of IR / heat (1)
3,4 Any two from:
Rising sea levels / flooding
Polar ice / ice caps /glacier(s) / glacial / habitat
ice melting
Changing (sea /air) currents, Changing weather patterns /more extreme weather / climate
change (2)

Other acceptable alternatives only if well justified e.g. more malaria because more
breeding areas for mosquitoes. But more malaria /desertification /forest fires alone is
insufficient

Three or more correct answers get 2 marks
Three or more answers, where some are wrong,
are marked 1 mark for each correct answer and 1
mark for each incorrect answer e.g.
Two correct and one wrong award 1 mark
Three correct and two wrong award 1 mark etc
One on list and one wrong award 1.
Ignore neutral statements



June 2009

Q23. f. (i) A fuel (derived from a plant) that takes in as much CO
2
(as it forms/grows) (1)
as is released during its production/combustion/when used (1)
OR
A fuel (such as hydrogen) that produces no CO
2
when burnt (1)
Nor in its production/processing (1)

(ii) 2 specific reasons e.g
energy used to heat/distil (ethanol water mixture after fermentation) may require burning
a fuel/energy
energy required to manufacture fertilisers (to grow plants for biofuels in good yield)
energy required to manufacture inseticides (to grow plants for biofuels in good yield)
energy required to transport fuel to the power plant
biofuels less effective at absorbing CO
2
than (rain)forests/trees
(2)

2 well reasoned effects on society e.g
use of food crops to produce biofuels reduces food supply
(use of land) for biofuels reduces biodiversity
use of land to grow biofuels leads to reduced food supply
leads to deforestation/leads to habitat loss
new jobs created to grow crops on new farmland
increased price of car/car service due to engine modifications
less CO
2
so less global warming
less SO
2
so less acid rain
less SO
2
so less respiratory illnesses e.g asthma
(2)

Choice of most sustainable biofuel with appropriate reasoning e.g
elephant grass as it requires little/no energy to process before it is burnt
elephant grass grows very quickly
elephant grass is a high yield crop
Any of the fuels can be burnt using existing technology
(1)



June 2010

Q15 = B

Q22 c (i) Chlorofluorocarbon (Accept ..flouro spelling)
(ii) Any one of the following / a statement equivalent to: aerosol / propellant / spray
cans
OR (degreasing) solvent
OR fire retardant
ALLOW fire extinguishers / putting out fires
ALLOW making expanded polystyrene / making plastics / making polymers
REJECT: pesticides / anaesthetics, just retardant, anti-freeze, air-conditioning, frying pans,
detergents

(iii) Mark independently
1
st
mark: O + O
3
2O
2
IGNORE any state symbols (1)
2
nd
mark: (chlorine free radical acts as a) catalyst (1)

Last 3 marks: any three from:
(the chlorine free radical) persists in the atmosphere / continues to attack / is regenerated
/ (starts) a chain reaction (1)

NOTE chain reaction may be described in terms of a chlorine radical breaking down many /
a large number of / a specified number of, eg 10,000, O
3
(molecules).
NOTE: As written, this response also earns the scoring point relating to ozone depletion.

less ozone / ozone decreases / causes hole(s) in ozone layer / breakdown of ozone (layer)
/ damages ozone layer / depletes ozone layer (1)
UV (reaching Earths surface) increases / less UV absorbed / (more) UV reaches Earths
surface (1)
causes (skin) cancer/mutation / DNA damage occurs (1)

IGNORE any references to global warming / Greenhouse Effect
If Cl and / or ClO left in equation OR 2O
3
3O
2

Just (UV) harmful

d. (i) The C-F bond is (very) strong
OR
C-F bond is (much) harder to break than the C-Cl bond
OR
UV/radiation does not have enough energy /does not have (high) enough frequency
REJECT Any mention of electronegativity OR mention of bond polarity scores

(ii) (long wavelength) IR /infrared radiation (1)
The molecule is polar OR (the molecule) changes its polarity OR polar bonds OR
vibrational energy/vibrations of the bonds / stretching or bending increases OR (IR causes)
bonds to vibrate (1)
Marks are stand alone
REJECT UC/ultraviolet, just molecule vibrates