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Edexcel Advanced Subsidiary GCE in Chemistry (8CH01)


Edexcel Advanced GCE in Chemistry (9CH01)
The Atmosphere

Issue 2
July 2008
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Prepared by Sarah Harrison
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© Edexcel Limited 2008
Contents

Introduction 1
The atmosphere 2
Regions of the atmosphere 2
Greenhouse gases 3
Carbon dioxide 4
CFCs and HCFCs 5
Methane 6
Nitrogen oxides (NOX) 8
Ozone 8
Water vapour 10
Other gases 11
Their effect on the environment 12
Resources 13
Introduction

This document is designed to help teachers to understand the contemporary context of the
atmosphere. It gives teachers information on this context and on how to research it further if
they wish. This document could also be given to students as introductory material.

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The atmosphere

Regions of the atmosphere


The atmosphere is divided into four regions.
• The troposphere — This is the lowest layer (up to 10 km from the Earth’s surface) and
contains about 80 per cent of the total mass of air and almost all the water vapour. The
temperature decreases linearly with distance from the Earth.
• The stratosphere — This is the next layer and goes up to 50 km above the Earth. The
temperature rises as the distance from the Earth increases, reaching about 10 °C at
50 km.
• The mesosphere — This is above the stratosphere and here the temperature decreases
with increasing altitude.
• The ionosphere (or thermosphere) — This is the outermost layer, stretching up to 500 km
from the Earth’s surface. This has a high temperature which is caused by the
bombardment of the few air molecules by particles from the Sun.

Figure 1 — The Earth’s atmosphere, as seen from space (Source: NASA)

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Greenhouse gases

The Sun is constantly radiating energy and the gases in our atmosphere absorb some of this
radiation, which then heats the Earth. Some of this energy is radiated back into space, and if
the amount absorbed equalled the amount radiated the Earth would remain at a steady
temperature. However, some gases in the atmosphere trap radiation, preventing it from being
radiated into space, and these are known as greenhouse gases. The effect of trapping the
Sun’s radiation is called the greenhouse effect.
The natural greenhouse effect is a very good thing for life on Earth. Without it, the average
temperature of the planet would be about -20°C and there would be little liquid water at any
time, water that is essential for life. The problem is with the enhanced greenhouse effect.
Many, but not all, climate scientists believe that the addition of greenhouse gases to the
atmosphere is largely responsible for global warming. This remains a contentious issue. The
gases responsible are produced both naturally and as a result of human activity (anthropogenic
activity).
The greenhouse effect is concerned with the troposphere. The majority of the radiation from
the Sun is in the range of wavelengths from 100 to 5000 nm, but nearly all of it is in the visible
range of 400 to 700 nm. Some of this radiation is reflected back into space by snow and
icefields but most of this radiation is absorbed by the Earth’s surface, and some is absorbed by
clouds. The Earth radiates energy back into space, but this radiation is in the infrared region
of the spectrum, with a wavelength of over 4000 nm.
Clouds trap some of this radiation and some is absorbed by molecules in the air. Only
molecules with polar bonds can absorb infrared radiation. To do this the molecule must
change its dipole moment during the vibration or bending of a bond in the molecule.
Evidence from ancient ice cores drilled in the Antarctic and from rocks around the world
indicates that the Earth has been much warmer in the past.

Figure 1 — An Antarctic ice core (Source: USGS)

Average global temperatures in the Cretaceous period, when chalk rock was being formed,
were significantly higher than today. Clearly these temperature variations must have had a
natural cause. A number of gases are able to absorb radiation within the infrared region of the
spectrum. These include the greenhouse gases such as carbon dioxide, water vapour, methane
and ozone.

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Carbon dioxide
From natural sources
Carbon dioxide is released in vast amounts as a result of volcanic activity. There have been
many periods of intense vulcanism in the Earth’s history, each likely to have been
accompanied by major releases of carbon dioxide. Hydrothermal activity on the ocean floor
also releases carbon dioxide. Evidence has been found of a lake of liquid carbon dioxide in an
ocean trench near Taiwan. This finding has implications for the removal and storage of carbon
dioxide produced in thermal power stations. Natural volcanic lakes can sometimes explode,
releasing toxic mixtures of gases, the major component being carbon dioxide as happened
many times in West Africa.
In recent geological time, the level of carbon dioxide was fairly constant at around 280 ppm.
Animals and plants converted carbohydrates into carbon dioxide (respiration) and plants also
converted carbon dioxide into carbohydrates (photosynthesis). The two processes balanced. In
earlier geological time, vegetation and marine organisms were submerged and changed into
coal and oil.
The atmospheres of other planets often contain carbon dioxide. It is the major component of
the atmosphere of Venus, whose surface pressure is about 90 times that of Earth. The carbon
dioxide on Venus has raised the surface temperature to 450°C, an effect described as a
runaway greenhouse effect.
From anthropogenic sources
When carbon-based fuels are burned, carbon dioxide is released. New coal-fired power
stations are being opened every month, especially in the industrialising Far East. The growth
in the use of petrol- and diesel-powered vehicles is also a major factor in adding carbon
dioxide to the atmosphere.

Figure 2 – Amount of CO2 generated per capita, per country, 2006 (Source: Wikipedia)

After the industrial revolution, large and increasing amounts of these fossil fuels were burnt,
and the carbon dioxide that had been trapped for billions of years was released. This has
caused the carbon dioxide level to rise. Currently air contains about 380 ppm of carbon
dioxide compared with 320 ppm 40 years ago.
The major source of carbon dioxide emissions caused by burning fossil fuels is electricity
production.

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home
and
office
heating
10%

electricity
35%
industry
25%

cars and lorries


30%

Figure 3 — Sources of anthropogenic carbon dioxide emissions

Chemistry of CO2
In carbon dioxide the C=O bonds are polar, but the molecule is linear so the dipoles cancel and
the molecule has zero dipole moment. A change in dipole moment from zero happens with the
asymmetrical stretching of the bonds and the bending mode.

Figure 4 — Infrared active bending and stretching vibrations of carbon dioxide

This means that carbon dioxide is able to absorb infrared radiation and so is a greenhouse gas.
It is an undoubted fact that the percentage of carbon dioxide in the air is increasing and that
this will cause more infrared radiation to be absorbed. The discussion is whether this man-
made increase in carbon dioxide levels is the major cause of climate change or one that is less
important than natural changes, such as variations in Sun activity or changes in the Earth’s
orbit around the Sun.

CFCs and HCFCs


From natural sources
CFCs and HCFCs are not found naturally.
From anthropogenic sources
When it was realised that CFCs in fridges and aerosols were depleting atmospheric ozone,
alternatives were sought. CFCs are being replaced in refrigerants by similar compounds that
contain a hydrogen atom. These are given the generic name of HCFCs. One such is HCFC-22
which has the formula CHClF2. The presence of the hydrogen atom causes the molecule to be
oxidised at lower altitudes. Thus it does not diffuse into the stratosphere, where it would
cause ozone depletion.

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CFCs and HCFCs are also powerful greenhouse gases and they contribute significantly to the
warming of the atmosphere. One problem, the destruction of atmospheric ozone, has been
replaced by another. An interesting side effect is that ozone also absorbs radiation, and so the
depletion of ozone in the stratosphere by CFCs causes a cooling in that region.
The amount of waste HFCs in the atmosphere is increasing by 20 per cent each year. There is
a certain irony in that the use of hydrocarbons, ammonia or carbon dioxide as refrigerants or
in air conditioning would eliminate this particular problem with HFCs. The impacts on the
greenhouse effect would be much less than continuing to vent HFCs.

Figure 5 — The hole in the ozone layer, over Antarctica,


as imaged in 2006 at its largest size (Source: Wikipedia)

Chemistry of CFCs and HCFCs


Chlorofluorocarbons (CFCs) have been widely used as refrigerants, aerosol propellants,
solvents and blowing agents for making expanded plastics. Radiation breaks down CFCs in the
upper atmosphere to produce chlorine radicals, and these radicals cause ozone breakdown and
prevent ozone formation by several different reactions. This is explained in detail in the
Chemistry of ozone section.
Chemists have made it a priority to find alternatives to CFCs so that ozone depletion does not
continue.

Methane
From natural sources
Methane is also a significant greenhouse gas and has many potential sources. The bacterial
decay of cellulose in vegetation in marshy conditions releases marsh gas, which is mostly
methane and carbon dioxide. Methane is also vented naturally from oil seepages such as at
Kirkuk in the Middle East. Methane is found as a crystalline hydrate where ice crystals contain
about 12 per cent of the gas. Enormous deposits of hydrates exist in the permafrost of Siberia
as well as in some ocean sediments. Any significant warming of the Earth will release large
amounts of methane as the ice crystals melt.

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From anthropogenic sources
Agriculture is responsible for the addition of some greenhouse gases to the atmosphere.
Methane is produced in the digestive tract of ruminant animals such as cows and sheep, and is
released from flooded paddy fields when rice is cultivated. When new land is cleared for
agriculture by the primitive slash-and-burn technique, the combustion of the forests both
releases carbon dioxide and reduces its uptake by photosynthesis. The rotting of farm waste,
both animal waste and discarded plant material, also releases methane and carbon dioxide.
This has been utilised on a small scale to prepare biogas for local use. It is a useful fuel but
the admixture of carbon dioxide reduces its calorific value. A similar gas mixture is produced
and released from landfill sites filled with domestic waste.
The energy industries are major contributors to the release of greenhouse gases. Since the
beginning of the industrial revolution, large quantities of coal have been extracted for use as
fuel. Methane is released naturally from coal mines where it was known as fire-damp, the
cause of serious explosions. Leakage of natural gas, mostly methane, from gas and petroleum
wells is also a significant contributor to the greenhouse gases in the atmosphere.

Figure 6 — Amount of methane on the Earth’s surface and in the stratosphere


(Source: Wikipedia)

Chemistry of methane
Methane, like carbon dioxide, is a non-polar molecule, but the bonds are polar, and so certain
vibrations will produce a dipole moment enabling it to absorb infrared radiation.

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Nitrogen oxides (NOX)
From natural sources
Lightning flashes release enough energy to combine nitrogen and oxygen, giving nitrogen
oxides. These oxides then generate ozone in the atmosphere.
From anthropogenic sources
The oxides of nitrogen, N2O, NO and NO2 are also greenhouse gases. They are produced by the
reaction of nitrogen and oxygen in the high temperatures of vehicle engines and aircraft and
in the breakdown of organic and inorganic fertilizers.
Oxides of nitrogen also act as catalysts in the oxidation of sulphur dioxide, and contribute to
acid rain formation.
Chemistry of NOX
The oxides of nitrogen play a significant role in the destruction of ozone. This is discussed in
the Chemistry of ozone section. This effect is less significant than the effect of CFCs.

Ozone
From natural sources
Ozone is a potent greenhouse gas produced directly from oxygen in the higher levels of the
atmosphere. Ozone is also produced as a result of electrical storms. Lightning flashes release
enough energy to combine nitrogen and oxygen, giving nitrogen oxides. Theses oxides in turn
generate ozone in the atmosphere.
From anthropogenic sources
At low levels in the atmosphere, ozone is a pollutant; it is produced when exhaust fumes
containing oxides of nitrogen are involved in a series of photo-catalysed reactions with
unburnt hydrocarbons, oxygen and water vapour. The result is a photochemical smog.

Figure 7 — Smog in New York (Source: Wikipedia)

Chemistry of ozone
Ozone is generally studied in relation to its depletion by CFCs in the atmosphere and
consequent increase in ultraviolet radiation at ground level. At high levels in the atmosphere,
ultraviolet (UV) radiation breaks down oxygen molecules and ozone forms.

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The overall equation is:
3O2 → 2O3

Along with oxygen, this ozone is important in protecting us from the damaging effects of UV
radiation. Oxygen is changed into ozone by action of UV light. Oxygen, O2, absorbs UV
radiation at wavelengths below 240 nm to produce oxygen atoms (free radicals).

O2(g) UV 2O(g)

These free radicals react with more O2 molecules to form ozone in an exothermic reaction
(which is why the stratosphere is hotter than the top of the troposphere).

O(g) + O2(g) → O3(g) ΔH = - 600 kJ mol-1(approx)

Ozone molecules absorb UV radiation of wavelengths between 200 to 300 nm and are
decomposed by it.

O3(g) UV O2(g) + O(g)

Under natural conditions an equilibrium is set up and organisms on Earth are protected from
much of the UV radiation, as both O2 and O3 molecules absorb these harmful rays.
The two main causes of anthropogenic depletion of ozone are CFCs and NOX, specifically nitric
oxide, NO. Both work in complex chain reactions. This means that a single free radical from
CFCs or from NOX will destroy millions of ozone molecules.

Nitric oxide, NO, is produced at high altitudes by the jet engines in aircraft. The following
sequence of reactions takes place.

NO(g) + O3(g) → NO2(g) + O2(g)

The NO2 molecules react with oxygen free radicals produced from the decomposition of ozone
(or the photolysis of O2 molecules).

O3(g) UV O2(g) + O(g)

NO2(g) + O(g) → NO(g) + O2(g)

The overall process, combining these three reactions, is:

2O3(g) → 3O2(g)

where the NO is acting as a catalyst.


CFCs are decomposed by UV light of wavelength between 175 and 220 nm and form chlorine
radicals, Cl.

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CF2Cl2(g) UV CF2Cl(g) + Cl(g)

A similar set of reactions then takes place:

Cl(g) + O3(g) → ClO(g) + O2(g)

O3(g) UV O2(g) + O(g)

ClO(g) + O(g) → Cl(g) + O2(g)


Overall:
2O3(g) → 3O2(g)

Water vapour
From natural sources
Water vapour is part of the natural water cycle on Earth and is essential to life. It is naturally
produced when bodies of water are heated by the Sun and evaporate. This water vapour then
forms clouds, which can be effected by gases and particles in the atmosphere. This can lead
to effects such as global dimming or global brightening.
From anthropogenic sources
An increase in jet aircraft has led to an increase in contrails (condensation trails) produced by
them. These are formed when water vapour condenses at high altitudes.

Figure 8 — Contrails from a jet aircraft (Source: Wikipedia)

These contrails affect cloud formation, but are not classified as air pollution. They are
important as any change in global cloud cover can contribute to long-term changes in the
Earth’s climate.

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Power stations, and other chemical plants, are also a major contributor of water vapour to the
atmosphere. The steam used to drive the turbines and generate the electricity is cooled in
cooling towers. These release huge clouds of water vapour into the atmosphere, which will
affect the global cloud cover, and the Earth’s climate.

Figure 9 — Water vapour being released from cooling towers at Drax power station,
North Yorkshire (Source: Wikipedia)

Chemistry of water vapour


The most important greenhouse gas is water vapour. Oxygen is more electronegative than
hydrogen and so the O-H bonds are polar. The H2O molecule is V-shaped and so the two
dipoles do not cancel and the molecule is also polar. This means that it has a dipole moment.
Any vibration or bending of bonds in the molecule will cause a change in the magnitude of the
overall polarity (dipole moment), so water vapour will absorb infrared radiation.
Deserts are bitterly cold at night, because the air contains very little moisture and so most of
the heat radiated from the Earth’s surface is not absorbed. It is estimated that about 95 per
cent of the global greenhouse effect is caused by atmospheric water vapour. A water molecule
will absorb infrared radiation and the molecule is promoted to a higher vibrational energy
level. These excited molecules lose this extra energy either by collision, causing the air
temperature to rise, or by emitting radiation of the same frequency. Some of this radiation is
goes into space and some back to Earth.

Other gases
Other gases produced by industry pollute the atmosphere, but chemists work to reduce this
pollution. A simple example is the sulphur dioxide produced in power stations, which can be
absorbed by calcium carbonate to make calcium sulphate. This can then be used to make
plasterboard for building.
There are some other chemicals whose impact on the atmosphere is enormously greater than
that of either methane or carbon dioxide, molecule for molecule. These are known as the
PIGGS: potent industrial greenhouse gases. They already account for 3 per cent of the
enhanced greenhouse effect and this seems likely to rise. Sulfur hexafluoride (SF6) is
estimated to have an effect that is 25 000 times more than an equivalent amount of carbon
dioxide. It is used in the manufacture of reactive magnesium metal.

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Figure 10 — Sulfur hexafluoride (SF6) (Source: Wikipedia)

Their effect on the environment


Carbon dioxide, methane and oxides of nitrogen (NOX) all contribute, to some extent, to
global warming. Methane molecules are more efficient at absorbing infrared radiation than
carbon dioxide. NOX and CFCs are even more powerful.
The greenhouse factor of a gas is a comparison with carbon dioxide, which has a greenhouse
factor of one. On this scale, the greenhouse factors of methane, nitrogen(I) oxide, and
trichlorofluoromethane (CCl3F) are 30, 160 and 21 000 respectively. This means that one
molecule of methane has the same effect as 30 molecules of carbon dioxide. Processes that
reduce greenhouse gas production are therefore important in reducing global warming.
The contribution of these four greenhouse gases to global warming is shown in the pie chart
below. The contribution of water vapour has been excluded, as its concentration remains
virtually constant from year to year.

HCFCs and
CFCs
20%
CO2
CH 4 55%
15%

NOX
10%

Figure 11 — Contribution to global warming by various greenhouse gases


(excluding water vapour)

The relative effect of these gases to man-made global warming is determined by two factors.
One is their ability to absorb infrared radiation and the other is their half-life in the
atmosphere. The combination is called the Global Warming Potential (GWP). The calculation
of a GWP is based on the radiative efficiency (infrared-absorbing ability) of the gas relative to
the radiative efficiency of the reference gas (carbon dioxide), as well as the removal process
(or decay rate) for the gas relative to the reference gas over a specified time horizon (usually
100 years). The table below shows the GWP for each of the major greenhouse gases.

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Greenhouse gas GWP

Carbon dioxide, CO2 1

Methane, CH4 20

Nitrous oxide, N2O 300

CFC-12, CCl2F2 6500

HCFC-22, CHClF2 1300

Table 1 — GWP for each of the major greenhouse gases

The IPCC (International Panel on Climate Change) gives the error on these values as ± 35 per
cent, which indicates just how unreliable the predictions are of long-term climatic changes.

Resources
Contrail Education — http://asd-www.larc.nasa.gov/GLOBE/science.html
IPCC — http://www.ipcc.ch

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July 2008

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