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Lisette Vote
L. H. Vote GCE Green Chemistry Teachers Pack
Introduction
The purpose of this Teachers Pack is to provide teachers with a full resource on Green
Chemistry, covering all the specifications requirements for A-Level chemistry. Green
Chemistry is a new and/or enlarged topic in all the new specifications for teaching in
September 2008, following the new QCA GCE Chemistry Criteria. I reasoned that
many teachers themselves may not have had the opportunity to study environmental
chemistry as it is a relatively modern and current topic; and even if it was studied at
university, there may be some gaps in their knowledge, such as recycling and how it is
done; or they may not be up to date on the chemistry and issues as they stand today.
This resource would therefore allow them to fully understand the subject so they can
be very comfortable teaching it by knowing the background material, beyond what it
expressly required from the specifications. This would allow them, for example, to be
able to explain or answer pupils Green Chemistry-based questions on issues beyond
the syllabus. Furthermore, this pack would provide teachers with lesson plans and
resources, which would be useful when teaching a new and relatively unfamiliar
topic.
This resource therefore comes in two main sections: Firstly, a text-book allowing
teachers to become up-to-date on Green Chemistry today. This is based on the
required knowledge in all the A-Level Chemistry specifications (i.e. AQA, Edexcel
and OCR A and B), for both AS and A2, however in much more detail than the pupils
are required to know, in order to provide teachers with the confidence and background
knowledge required to teach these new topics well. The second main section is a
collection of lesson plans and resources on Green Chemistry-based topics. These
lesson plans can be used as just that, a plan for an entire lesson; or ideas and activities
can be used from them and attached to your other lessons where the chemistry might
link together with Green Chemistry. The plans also suggest resources to use, such as
animations, video clips, worksheets, links and PowerPoint presentations; all of which
I have attached to this resource.
The topics I have covered are, Atmospheric Chemistry, including the Ozone Hole; Air
Pollution, including smog, catalytic converters and acid rain; Global Warming,
including the notions of carbon neutral, carbon footprint, biofuels and examples of
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L. H. Vote GCE Green Chemistry Teachers Pack
them; and Recycling, including recycling, amongst other methods of disposal of
aluminium, iron, steel and polymers and issues associated with their disposal.
I hope you find this pack useful and practical; and that your pupils enjoyment and
understanding of Green Chemistry is increased.
February 2008
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L. H. Vote GCE Green Chemistry Teachers Pack
What is Green Chemistry?
Green Chemistry is based on and ties together a variety of strings of chemistry:
Organic, Inorganic, Physical, Environmental, Biochemistry and Analytical Chemistry.
Green Chemistry and Environmental Chemistry, while often confused are two
separate fields. Green Chemistry encourages environmentally conscious behaviour,
such as reducing and preventing pollution and the destruction of the planet. On the
other hand, Environmental Chemistry is simply the study of chemistry occurring in
the environment.
i
The following page lists the Twelve Principles of Green Chemistry, reproduced from
the Royal Society of Chemistry.
i
Green Chemistry, Wikipedia, site accessed March 2008
http://en.wikipedia.org/wiki/Green_chemistry
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The twelve principles of green chemistry
It is better to prevent waste than to treat or clean up waste after it is formed.
Synthetic methods should be designed to maximize the incorporation of all
materials used in the process into the final product.
Wherever practicable, synthetic methodologies should be designed to use
and generate substances that possess little or no toxicity to human health and
the environment.
Chemical products should be designed to preserve efficacy of function while
reducing toxicity.
The use of auxiliary substances (solvents, separation agents, etc.) should be
made unnecessary whenever possible and innocuous when used.
Energy requirements should be recognized for their environmental and
economic impacts and should be minimized. Synthetic methods should be
conducted at ambient temperature and pressure.
A raw material or feedstock should be renewable rather than depleting
whenever technically and economically practicable.
Unnecessary derivatization (blocking group, protection / deprotection,
temporary modification of physical / chemical processes) should be avoided
whenever possible.
Catalytic reagents (as selective as possible) are superior to stoichiometric
reagents.
Chemical products should be designed so that at the end of their function
they do not persist in the environment, and break down into innocuous
degradation products.
Analytical methodologies need to be further developed to allow for real-time,
in-process monitoring and control prior to the formation of hazardous
substances.
Substances and the form of a substance used in a chemical process should
be chosen so as to minimize the potential for chemical accidents, including
releases, explosions, and fires.
These principles have been reprinted with permission from Paul T. Anstas and J ohn
C. Warner Green Chemistry: Theory and Practice, New York: Oxford University
Press, 1998
L. H. Vote GCE Green Chemistry Teachers Pack
Table of Contents
1. Atmospheric Chemistry 1
1.1 Planetary Atmospheres 1
1.2 The Earths Atmosphere 2
1.3 Explanation for the Temperature Structure of the Atmosphere 3
1.4 Natural Catalytic Cycles: Problem with the Chapman mechanism 6
1.5 The Ozone Hole 8
1.5.1 Ozone Depletion 8
1.5.2 Why the Depletion is Dangerous 10
1.5.3 Explanation for the depletion 11
1.5.3.1 Polar Stratospheric Clouds 11
1.5.3.2 CFCs converting to Active Forms of Chlorine and Bromine 13
1.5.3.3 The Return of Sunlight: Ozone Destruction 13
1.5.3.4 Summary of Ozone Destruction 14
1.5.4 Current and Future Ozone Levels 15
1.5.5 CFC Substitutes 15
2. Air Pollution 19
2.1 Emitted Pollutants 20
2.2 Removal Processes of Compounds 21
2.3 Smog Formation 22
2.4 UK Emissions Today 25
2.5 Catalytic Converters 26
2.6 Acid Rain 27
3. Global Warming 30
3.1 Greenhouse Effect 30
3.2 Climate Change 30
3.3 Global Warming 31
3.3.1 Greenhouse Gases and How They Work 31
3.3.2 Evidence for Global Warming 31
3.3.3 Global Warming Potential 35
3.3.4 Carbon Neutral, Biofuels and Carbon Footprint 35
3.3.5 Controlling Global Warming and the Kyoto Protocol 37
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L. H. Vote GCE Green Chemistry Teachers Pack
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4. Recycling 40
4.1 Why Recycle 40
4.1.1 Household Waste 42
4.1.2 Aluminium and Steel 43
4.1.3 Plastics and Polymers 48
5. Lesson Plans and Resources 55
Lesson Plan: AS Module 1 Combustion of Alkanes: Air Pollution 56
Lesson Plan: AS Module 2 Extraction of Metals, Acid Rain and Recycling 58
Lesson Plan: AS Module 2 Ozone Destruction 59
Lesson Plan: AS Module 2 Global Warming 60
Lesson Plan: A2 Module 4 Disposal and Recycling of Polymers 61
Additional Green Chemistry Resources 62
References 63
L. H. Vote GCE Green Chemistry Teachers Pack
1. Atmospheric Chemistry
L. H. Vote GCE Green Chemistry Teachers Pack
1. Atmospheric Chemistry
1.1. Planetary Atmospheres
The Earths atmosphere is the only planet within the solar system which contains such
a large percentage of oxygen; it is an oxidising atmosphere; as can be seen in the table
below.
Table 1: Major atmospheric constituents of the Sun and the Planets within the Solar System and
their Surface Temperature
1
Planet/Star Most Abundant
Gas
2
nd
Most
Abundant Gas
3
rd
Most Abundant
Gas
Surface
Temperature (K)
Sun H
2
89% He 11% H
2
O 0.1% --
Venus CO
2
96.5% N
2
3.5% SO
2
0.015% 732
Earth N
2
78.1% O
2
20.9% Ar 0.93% 288
Mars CO
2
95.3% N
2
2.7% Ar 1.6% 223
Jupiter H
2
90% He 10% CH
4
0.24% 170
Saturn H
2
96% He 4% CH
4
0.2% 130
Uranus H
2
82% He 15% CH
4
2.3% 59.4
Neptune H
2
85% He 15% CH
4
1-2% 59.3
Titan N
2
82% Ar 12% CH
4
3% 95
Table 2: Mass of the Sun and the planets within the Solar System
2
Planet
/Star
Sun Mercury Venus Earth Mars Jupiter Saturn Uranus Neptune
Mass
(kg)
1.99
x10
30
3.30x10
23
4.87x10
24
5.97x1
0
24
6.42
x10
23
1.90
x10
27
5.68
x10
26
8.68
x10
25
1.02 x10
26
Mercury has a relatively low mass (see Table 2 above) hence a smaller
gravitational force, and therefore has almost no atmosphere. Its thin
atmosphere is comprised of 98% He and 2% H
2
.
1
Venus has largely CO
2
, which causes a runaway greenhouse effect and
hence its high surface temperature.
1
Mars atmosphere also consists chiefly of CO
2
but as it is of a lower mass than
Venus, its atmosphere is thinner as it has a weaker gravitational force. Thus,
there is not a very strong greenhouse effect.
1
The Outer Planets (Jupiter, Saturn, Uranus and Neptune) have a much lower
surface temperature due to their distance from the Sun. Their atmospheres are
predominately c. 90% H
2
and c. 10% He, and are reducing in nature as they do
not contain oxygen. There are low levels of a range of hydrocarbons in the
atmospheres, most likely to be caused by the photochemistry of CH
4
.
1
Titan is a satellite of Saturn and the only satellite to posses a massive
atmosphere; which here is of N
2
and some CH
4
. Titans atmosphere contains
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L. H. Vote GCE Green Chemistry Teachers Pack
photochemical smog: most likely to be due to the oxidation of hydrocarbons.
These aerosols cause the smog to appear as coloured clouds.
1
1.2. The Earths Atmosphere
The moon has c. 1/6 of the gravitational force than the Earth has, so it has virtually no
atmosphere. If the Earths atmosphere did not attenuate incoming solar radiation, the
temperature variation of the atmosphere would look like that of the moons
3
:
Figure 1: The temperature structure of the moons atmosphere and that of the Earths, if the
Earths atmosphere did not attenuate incoming solar radiation
3
The light from the sun heats up the Moons surface, which radiates heat upwards, so
the surface heats the atmospheric layers directly above it. Therefore, there is a high
temperature at the surface, which falls away rapidly as the distance from the surface
increases, as heat transfer is less effective.
1
However, the temperature structure of the
Earth has an S shape:
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L. H. Vote GCE Green Chemistry Teachers Pack
Figure 2: Temperature variation with altitude of Earth's atmosphere
4
1.3. Explanation of the Temperature Structure of the Atmosphere
Troposphere decrease in temperature
From the surface to the Tropopause, the temperature decreases, this is due to the same
reason for the temperature structure of the moon (the Sun heats the Earths surface,
which re-radiates heat back up, heating the layers above it, with decreasing intensity
as the altitude increases).
Stratosphere increase in temperature
At 10-15 km the temperature begins to increase throughout the stratosphere.
1
This can
be explained by the absorption of solar radiation:
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L. H. Vote GCE Green Chemistry Teachers Pack
Figure 3: The solar flux at various altitudes in the Earth's atmosphere
5
As can be seen from Figure 3, the dangerous high energy radiation (wavelengths less
than 200 nm, i.e. the lower UVC region) is removed at the top of the atmosphere. This
is done through photochemistry with O
2
, O
2
+
, N
+
, N
2
+
, O, O
+
, and NO
+
.
1
The (also
harmful and it is vital for life that it is removed) UVB region, between ~200-300
nm, begins to be absorbed at about 50km, and is removed by the time the solar
radiation impinges on the Earths surface
1
. This is due to O
2
and especially O
3
(ozone) being the species that absorb UVB radiation
1
, acting as a UV filter.
Therefore it is clear that ozone is vital to protect humans and the ecosystem from
harmful UVB radiation.
Ozone is generated via the Chapman Mechanism (discovered in the 1930s by Sidney
Chapman)
3
:
2 3
2 3
3 2
2
2O O O
H - O O h O
M O M O O
O O h O
+
+ +
+ + +
+ +
Where M is a non-reactive body which can absorb excess energy
The most interesting step is the 3
rd
one. It is extremely exothermic (90 kJ mol
-1
)
1
so
ozone is liberating a lot of heat in photolysis, causing the temperature to increase in
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L. H. Vote GCE Green Chemistry Teachers Pack
the stratosphere. Ozones generation reaches a maximum in the Stratosphere because
it is a balance between number of photons and the concentration of O
2
molecules
1
:
At higher altitudes: There is a high number of photons (fewer have been absorbed
by the atmosphere), but the atmosphere is thinner, so the pressure low, therefore
there is a low concentration of O
2
molecules too low to create high enough
levels of O
3
.
At lower altitudes: Despite the fact there is a higher pressure, hence higher
concentration of O
2
, the number of photons is too low as the layers of atmosphere
above it have attenuated the incoming radiation this slows the rate of the first
step in the Chapman mechanism.
In the stratosphere, there is warm air sitting on top of cold air, so it is hard for the cold
air to move through it: the air remains stuck in these distinct layers, which is termed
zonally symmetric
1
.
Mesosphere decrease in temperature
Again, the air begins to cool here as the altitude increases, as the pressure decreases
and hence the concentration of M and O
2
molecules decrease, so there is very little to
kick-start
1
the Chapman cycle, and generation of ozone is extremely low.
Thermosphere increase in temperature
This begins at about 90 km, at this point the atmosphere is so thin and collisions
between particles are extremely infrequent. This means that most of the particles dont
get the chance to equilibrate once they have absorbed the high energy incoming solar
radiation, and therefore their translational temperatures become very high
1
.
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L. H. Vote GCE Green Chemistry Teachers Pack
1.4. Natural Catalytic Cycles: Problem with the Chapman mechanism
The Chapman mechanism predicted the right ozone generation mechanism but over-
predicted the production of O
3
by a factor of about 5.
1
This is because the last step in
the cycle:
is slow and there exist catalysts, X, which are species in parts of the atmosphere
which participate in the following cycle to speed up the destruction of ozone. This is
called natural catalytic cycles
1
:
2 3
O 2 O O +
Species of X are:
3
2 2 3
2
2 3
O O O O :
O X O XO
O XO O X
+ +
+ +
+ +
Net
NO 30-40km e.g.
NO
2 2 3
2 2
2 2 3
O O O O :
O NO O NO
O NO O
+ +
+ +
+ +
Net
Cl and Br maximum at 45km
HO above 45 km
H above 60 km
Sources of catalysts:
The catalysts are formed via the reactions outlined below. They involve a natural
source gas
1
reacting with another molecule or undergoing photolysis (i.e. the
compound is broken down by sunlight photons).
Despite the fact that these species catalyse the destruction of ozone, these reactions
dont go on indefinitely, which would destroy the ozone layer. Fortunately,
termination reactions occur and this produces stable (inactive) reservoir
compounds
1
from the active radicals. These reservoir compounds are often the source
gases themselves
1
.
Source of NO
X
:
Firstly, ozone undergoes photolysis to form oxygen and an excited oxygen
radical
1
:
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L. H. Vote GCE Green Chemistry Teachers Pack
) ( O D) O( h O
g
1
2
1
3
+ +
The source gas, N
2
O is produced by soil, which goes on to react with the oxygen
radical to form NO
1
:
M HNO M HO NO
2NO O N D) O(
3 2
2
1
+ + +
+
n Step: Terminatio
Source of Cl:
1
3 4
3 3
CH HCl CH Cl
Cl CH h Cl CH
+ +
+ +
n Step: Terminatio
Fortunately, the amount of CH
3
Cl emitted into the atmosphere is very low.
However if this amount increases, it would present a problem as this is a very
efficient process (see Table 3).
Source of HO
X
:
1
2 2 2 2 2
2 2 2
3 4
1
2
1
O O H HO HO
O O H HO HO
CH OH CH D) O(
OH OH O H D) O(
+ +
+ +
+ +
+ +
n Step: Terminatio
Table 3: Rates of catalytic cycles
X K
220
/ cm
3
molecule
-1
s
-1
k
b
/k
a
H 1.7 x10
-11
25000
HO 2.2 x10
-14
32
NO 3.5 x10
-15
5
Cl 8.7 x10
-12
12794
O 6.8 x10
-16
1
NB: k
b
/k
a
b 2 3
a 2 2 3
O XO O X
O O O O
k
k
+ +
+ +
Rate loss of ozone:
d[O
3
]/dt=- k
a
[O][O
3
]-k
b
[X][O
3
]
The rates are equal when:
k
a
[O][O
3
]/k
b
[X][O
3
]=1
a b
k k / ] [ = O]/[X
Natural Chapman cycle
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L. H. Vote GCE Green Chemistry Teachers Pack
It can be seen from the above table that one only needs to add c.1 millionth of the
amount of H into the system compared to O for it to have the same effect as the
natural Chapman cycle.
1.5. The Ozone Hole
1.5.1. Ozone Depletion
In the 1970s, the British Antarctic Survey recorded an enormous decrease in ozone in
the Stratosphere over the Antarctic
6
. At first they believed their equipment to be
faulty as they were astonished by this finding
7
.This continued to decrease year on
year
8
, as shown by Figure 4.
Figure 4: Average Ozone Depletion for
October over the Antarctic
6
Figure 5: Average Area of the Ozone Hole
1980-2006
8
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L. H. Vote GCE Green Chemistry Teachers Pack
Figure 6: Graph to show the changes in Ozone Partial Pressure over the South Pole from 1967-
2001
3
As can be seen from Figure 6, since about the mid-1970s there has been a remarkable
decrease in ozone partial pressures. There has also been an observed diminution over
mid-latitudes and in the Arctic
3
. Every spring in the Antarctic (i.e. October), the
average ozone levels drop and ozone depletion reaches a maximum at the end of
November. The ozone hole develops seasonally over 6-8 weeks in the stratosphere,
completely destroying ozone in some places. This seasonal change can be seen from
the figure overleaf:
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L. H. Vote GCE Green Chemistry Teachers Pack
Figure 7: Graph showing the variation in Ozone Partial Pressure at various altitudes in the
summer (October) and winter (July) of 2001 over the Antarctic
9
As can be seen from the July bulge around 15km, this is where the ozone is usually at
its maximum in the stratosphere. In the winter, the ozone level is almost 0 at this
altitude, showing severe depletion.
1.5.2. Why the depletion is dangerous
Low levels or lack of ozone in the stratosphere causes detrimental impacts of humans,
the ecosystem, and the economy at large. This is primarily due to the fact that reduced
levels of ozone means that less of the dangerous, high energy UV-B radiation will be
absorbed (see Figure 3), and so more will impinge upon the earths surface.
Approximately, a 1% decrease of ozone leads to a 2% increase of UV radiation
reaching the earths surface
3
.
Humans: Increased levels of dangerous high-energy UVB radiation
17
impinging
upon the earths surface can cause melanoma and non-melanoma skin cancer
17
,
eye disorders and cataracts and suppression of the immune system in people of all
races possibly leading to an increase in diseases and infections. According to
Tolba et al:
The percentage increases [of skin cancer] will not be one-to-one: a sustained
ten per cent reduction in ozone would result in a 26 per cent increase in non-
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L. H. Vote GCE Green Chemistry Teachers Pack
melanoma skin cancer. All other things remaining constant, this would mean
an increase in excess of 300,000 cases a year, world-wide.
17
Plants: Roughly half of the worlds plants are sensitive to UV-B light, and their
leaves shrink and the plant grows less when there is an increase in UV-B light
impinging on the earths surface. Economically, this is also problematic as it can
cause reduce food yields and plants also can change their chemical composition
with increased UV-B exposure, which can affect their quality and nutrient levels.
17
Aquatic ecosystems: Phytoplankton experience a similar detrimental impact of
excess UV-B radiation that terrestrial plants do. This could affect species further
up the food chain and have a detrimental impact on the productivity of fisheries
17
,
amongst others. In addition, there could be nitrogen deficiency in rice paddies as:
Increased exposure to UV-B radiation could lead to decreased nitrogen
assimilation by prokaryotic micro-organisms
17
Air quality: Increased levels of surface UV radiation can change the levels of
reactive compounds in the troposphere, such as acids, hydrogen peroxide and
ozone where levels of NO
x
are high.
17
Materials damage: Photo-oxidation
3
can occur to many materials (wood, plastics
and rubber
17
), which is when the materials become oxidized through the action of
UV light. Thus, increased UV light can cause increased damage to these materials.
1.5.3. Explanation for the depletion
1.5.3.1. Polar Stratospheric Clouds
In the Polar Regions in the winter, the temperatures drop so low that a polar vortex
forms. This is when sunlight does not shine upon the region, and it is so dark and cold
that air descends and creates a strong downwards vortex motion
1
, or circumpolar
winds in the mid to low stratosphere
6
. This isolates the air within the vortex from the
rest of the globe, and no material can get out and material can only enter at 40 km:
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L. H. Vote GCE Green Chemistry Teachers Pack
Figure 8: Depiction of the Polar Vortex during the winter over the South Pole
10
In these conditions: no sunlight, and very cold temperatures below -80
0
C polar
stratospheric clouds (PSC) can form, these clouds remain there as the vortex isolates
the air so it remains cold. These contain high levels of nitric acid (HNO
3
) and ice-
water.
11
Figure 9: Depiction of how CFCs enter the atmosphere
6
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L. H. Vote GCE Green Chemistry Teachers Pack
1.5.3.2. CFCs converting to Active Forms of Chlorine and Bromine
CFCs were first created in 1928 as a non-toxic, non-flammable refrigerant, and then
many other uses for them were discovered
7
, due to their low reactivity and volatility.
As can be seen from the figure above, CFCs are emitted into the atmosphere by
factories and homes (such as through the use of CFCs in aerosols, refrigerants, in air-
conditioning and as solvents). The UV light in the upper atmosphere can easily break
the C-Cl bonds in CFCs and converts the compounds into the main reservoir species
of chlorine HCl and ClONO
2
, as they have a long lifetime, and move down into the
polar vortex. The PSCs provide a surface on which heterogeneous reactions can occur
to convert these two species, and their bromine equivalents, into active forms of
chlorine
11
:
3 2 5 2
3 5 2
2 2
3 2 2
2 3 2
HNO 2 O H O N
ClONO HNO HCl O N
Cl O H HOCl HCl
HOCl HNO O H ClONO
Cl HNO ClONO HCl
+
+ +
+ +
+ +
+ +
These heterogeneous reactions allow for the reservoir compounds of catalysts for
ozone destruction to rapidly convert chlorine and bromine to their active forms.
1.5.3.3. The Return of Sunlight: Ozone Destruction
Remembering this occurs in the winter, as the cold temperatures that occur allow the
formation of the PSCs; when the sunlight returns in the spring (October for the South
Pole), the molecular chlorine readily undergoes photolysis:
Cl Cl Cl
2
+ + h
This could now go on to catalyse the destruction of ozone through the cycle:
20km) (c. altitude at this slow too is it - O Cl O ClO
: cycle in the step final the do vortex to in the atoms O enough not are ere However th
O ClO O Cl
2
2 3
+ +
+ +
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L. H. Vote GCE Green Chemistry Teachers Pack
Instead, the cold temperatures encourage the formation of dimers of ClO, which
drives the following cycle:
n Destructio Ozone - 2O 2O : Net
) O 2(ClO ) O 2(Cl
O Cl Cl h ClOOCl
M ClOOCl M ClO ClO
2 3
2 3
2
+ +
+ + +
+ + +
This cycle is thought to be the predominant cycle for ozone destruction, accounting
for 70% of destruction in the South Pole.
1.5.3.4. Summary of Ozone Destruction
The greater the amount of CFCs released into the atmosphere, the greater the amount
of chlorine available as CFCs break with a high energy source:
i.e. light at 200 nm: CFCl
3
+ hv CFCl
2
.
+ Cl
.
This free chlorine then goes on to catalytically destroy ozone. The following figure
depicts how ClO is rapidly created from CFCs in the polar vortex in the winter (i.e. in
the absence of sunlight), and how this destroys ozone in the presence of sunlight (i.e.
in the spring), and ClO levels continue to increase.
Figure 10: Graphs to show a comparison in the variations of ClO and Ozone in the Antarctic
vortex in the winter (28/08/87) and the spring (16/09/87) of 1987
12
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L. H. Vote GCE Green Chemistry Teachers Pack
These same factors also cause destruction over the arctic, although because of warmer
temperatures, the loss isnt as great. In addition, the PSCs dont occur as strongly in
the northern hemisphere because the land-ocean distribution is different (the mountain
ranges stir the atmosphere up
11
) and more favourable for their formation in the
southern hemisphere, and in the Arctic the polar vortex disperses earlier in the
spring
11
.
1.5.4. Current and Future Ozone Levels
Currently, the ozone hole is one and a half times the size of the United Sates (see
Figure 11), and is still getting larger. However, levels of CFCs are decreasing. This is
due to legislations controlling the use of CFCs: the Vienna Convention
17
which did
not prevent the use of bromofluoroalkanes
13
, and therefore the Montreal Protocol
14
that were implemented in 1985
17
and 1989
14
respectively. These legislations were
supported by chemists. The Montreal Protocol aimed to reduce stratospheric halon
levels to the levels they were at before the ozone hole by 2060
11
.
The Montreal Protocol was written so that schedules for the phasing out of
halofluorocarbons could be revised depending on the current scientific and
technological advances
15
. Thus, most recently, in September 2007 a Montreal Summit
was held whereby c.200 countries (including the US and China which had previously
been opposed to the protocol) signed a treaty to accelerate the complete ban of the use
of hydrocarbons by 2020, and developing countries were given until 2030. China
currently has CFC levels equivalent to those that were present in the 60s and 70s in
the UK
3
.
With the use of halofluorocarbons being phased out, all CFCs are currently banned
except for medicinal use only
13
. In the US, the use of CFC, HCFC or HFC gases
requires the technician to pass licensing examinations set by the Environment
Protection Agency.
13
1.5.5. CFC Substitutes
Scientists have developed and are currently developing alternatives to CFCs, to meet
the legislations requirement. CFCs have a variety of uses, primarily as cleaning
agents, fire extinguishing agents, foam, and refrigerants
15
.
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L. H. Vote GCE Green Chemistry Teachers Pack
The CFC substitutes developed include:
HFC-134a, a chlorine free compound used as a refrigerant with an Ozone
Depletion Potential (ODP see overleaf) of zero
16
.
PhostrEx, the fire suppression agent used in light jets, was developed to be
free of CFCs and is now being sold to other airplane manufacturers
13
.
HCFC: the H atom increases the reactivity of the compound, so less is
required for its use. In addition, 95% of the compound is destroyed the
troposphere and never reaches the stratosphere
11
, for example CF
3
CH
2
F.
Other chlorine-free compounds have been developed as well, and their use
is in rapid growth, especially fluorinated and partially fluorinated
hydrocarbons
15
, such as CF
2
C
12
. This requires replacing the chlorine with
fluorine. These compounds do not destroy the ozone layer (doesnt react
with O
3
) but unfortunately have a high Global Warming Potential (GWP)
and so contribute to climate change.
Therefore, compounds that are developed today not only have to be chlorine-free but
also have to abide by the Kyoto protocol by having a low GWP
15
.
Using models, we are able to estimate this future decrease of atmospheric chlorine
level (see Figure 12) and a complete drop by about 2070
1
. The ozone hole itself is
hoped to level off by 2019 and eventually start to decrease by 2050
3
.
Figure 11: The ozone hole with the area of the United States superimposed
3
- 16 -
L. H. Vote GCE Green Chemistry Teachers Pack
Figure 12: Past and predicted levels of atmospheric chlorine
3
Although this legislation appears to be taking effect, the lifetime of CFCs is very long
and particularly CF
3
Br is very potent at destroying ozone (see Table 4: bromine has
10 times the ODP of chlorine). In addition, unlike Cl, Br wont react with methane
1
:
reaction no CH Br
CH HCl CH Cl
4
3 4
+
+ +
Therefore it is unable to form a reservoir compound and difficult to get rid of bromine
once it has entered the atmosphere
1
. Therefore it could take quite some time before
the anthropogenic sources (i.e. derived from human activity) of Cl and Br are
removed from the atmosphere.
Table 4: Halocarbon abundances, lifetimes and Ozone Depletion Potentials
Halocarbon Abundance
17
(pptv)
Lifetime
1
(years)
Ozone Depletion Potential
1
(=Ozone destroyed by unit mass halocarbon/Ozone
destroyed by unit mass of CFCl
3
)
CFCl
3
280 55 1.0
CF
2
Cl
2
484 100 0.8
CF
3
Br
2 65 10.0
CH
3
CCl
3
158 50 0.1
- 17 -
L. H. Vote GCE Green Chemistry Teachers Pack
Finally, it can be seen that global warming did not cause the ozone hole; however
there are links between the two processes
11
:
CFCs are greenhouse gases
The stratosphere is actually cooling due to global warming, so more PSCs
can be formed, increasing the amount of reactions for ozone depletion.
- 18 -
L. H. Vote GCE Green Chemistry Teachers Pack
2. Air Pollution
L. H. Vote GCE Green Chemistry Teachers Pack
2. Air Pollution
Figure 13: Diagram to show the range of chemicals emitted by natural and anthropogenic
activity, as well as depositions, transport and photochemistry
18
The industrial revolution in the 17
th
century instigated the development of urban
conurbations and also caused a rapid increase in anthropogenic emissions causing air
pollution
19
. This lead to heavy, stagnant combustion smog
19
(so named as it is a
portmanteau of smoke and fog
20
) over cities such as London and caused a variety of
serious heath problems including pulmonary disease and heart failure
19
. The smog
contained a mixture of Primary Pollutants emitted directly from the combustion
source, especially soot particles and sulphur dioxide (SO
2
). Reductions in these
emissions were made leading to a reduction in combustion smog occurances
19
.
In the last century, increasing emissions of oxides of nitrogen and sulphur due to
industrial and domestic combustion have lead to acid rain
19
.
NOx
VOC
&
s
4
CH
NOx
VOC
&
s
ry
n
D
Depositio
Wet deposition
h
Stratosphere
Troposphere
ea S
VOCs
al
ns
m
e
&
X
s,
&
- Natur
emissio
Flow of ozone fro
stratospher
DMS
CH
3
Termites, cow
domestic emissions
domestic ruminants
Industrial Activity
- 19 -
L. H. Vote GCE Green Chemistry Teachers Pack
Since the post-war era of the 1950s, both the population and use of motorized vehicles
has rapidly increased. These emissions caused a hazy photochemical smog
19
. This also
causes adverse health problems, such as eye irritations, sore throats, asthma and
respiratory diseases
19
. It was found that the component of photochemical smog (and
cause of these ailments) were Secondary Pollutants, made from Primary Pollutants.
The main components are ozone and PAN (peroxyacetylnitrate - CH
3
C(O)O
2
NO
2
)
and are formed from the action of primary pollutants (from car exhausts etc) such as
reactive VOCs and nitrogen oxides, with sunshine
19
. Every major city in the world
now experiences photochemical smog
19
. From the figure above, it can be seen that the
troposphere today has a complex array of emissions and processes.
2.1. Emitted Pollutants
1
VOCs are volatile organic compounds; these contain a large variety of different
organic compounds both emitted from anthropogenic and natural sources. They
absorb IR radiation, as does methane (CH
4
), and so contribute to global warming
and they are therefore greenhouse gases.
o VOCs from anthropogenic sources are mainly from the burning of fuels (such
as in industry, for energy supplies and through the usage of cars). Alkanes are
used as fuels and their combustion can be complete or incomplete, so some
light, unburned hydrocarbons are emitted during combustion, such as through
car exhausts. Incomplete combustion causes emission of CO and complete
combustion emits CO
2
. Additionally, the light hydrocarbons in fuel evaporate
when refuelling or storing, and others during combustion. A source of light
alkanes is due natural gas leakage and a source of alkenes is biomass burning.
o Natural sources of VOCs are from vegetation (plants, trees, fungi and algae),
which they emit as pheromones (to ward off predators, to attract insects), to
regulate their temperature or even as antifreeze. The VOCs include
hydrocarbons, CO
2
from respiration and CO.
NOx includes NO and NO
2
, this is formed due to high temperatures in combustion
(especially in the combustion of fossil fuels) where nitrogen and oxygen react: N
2
+ O
2
+ heat NO
x
. In addition, there are some natural sources of nitrogen, such
as ammonia from fertiliser and manure
23
. This causes the formation of smog and
acid rain.
- 20 -
L. H. Vote GCE Green Chemistry Teachers Pack
SO
2
and particulates are also released through anthropogenic processes, as
combustion of hydrocarbons releases soot and ash and combustion of
hydrocarbons containing sulphur releases sulphur dioxide. These are emitted
through car exhausts, and as pollution from industry. In addition sulphur can be
emitted from natural sources, such as volcanoes, the action of bacteria in soils and
lightning
23
. These can both contribute to smog and SO
2
contributes to acid rain.
2.2. Removal Processes of Compounds
1
Wet deposition involves the incorporation of species into aqueous media such as
mist, rain, sea, and snow. This therefore has to involve soluble species such as the
following inorganic compounds: HNO
3
, H
2
SO
4
, HCl, HONO and SO
2
. VOCs
usually are hydrophobic and therefore insoluble and rarely are lost through wet
deposition.
Dry deposition is removal of species through their adsorption onto air mass.
When air mass comes into contact with water, earth or vegetation the emitted
species can either physisorp (through Van der Waals forces) or chemisorp
(through a chemical reaction). The rate of this determined by the flux through the
atmospheric boundary layer (1 km form the Earths surface
3
) the rate of
adsorptions. Generally the species are polar and therefore inorganic such as
HNO
3
, NO
2
, HCl, HONO, O
3
and SO
2
. Only very polar VOCs are lost through
this process.
Chemical removal is the removal of VOCs through oxidation. This is mainly
done by the OH radical, but also ozone, NO
3
radicals and even direct photolysis.
This is why the troposphere is said to be oxidising. Through oxidation, it reacts
with the species and eventually H
2
O and CO
2
get out water is then rained out (a
subcategory of wet deposition) and CO
2
is a greenhouse gas.
o The OH radical is created via the mechanism:
+ +
+ +
< + +
OH OH O H D) O(
molecule N or O an is M re whe M P) O( M D) O(
330nm ~ at h O D) O( h O
2
1
2 2
3 1
2
1
3
This occurs in the troposphere: a small amount of ozone is found in the
troposphere and therefore only a small amount of excited atomic oxygen
- 21 -
L. H. Vote GCE Green Chemistry Teachers Pack
(O(
1
D)) is created by photolysis. However, as the troposphere sits below the
stratosphere, the air in it is at a higher pressure. This leads to a balance
between concentrations of water vapour and M. At these high pressures the
excited O(
1
D) is rapidly quenched by M, however the troposphere also has 10-
50,000 times higher water vapour concentrations than in the stratosphere so a
small amount of O(
1
D) reacts with water to form OH radicals.
o The OH radical reacts with VOCs (RH) via the reaction:
O H R RH OH
2
+ +
The rates of reaction (and hence lifetime of RH) increases with increasing
number of Hs as there is a greater chance of collision with . However,
with a polar atom in the molecule, such as Cl in CH
3
Cl, the reaction is a lot
faster as the Cl is electronegative, inducing a dipole in the molecule and
leaving the Hs a lot more positive so they are more reactive. With alkenes, an
addition reaction occurs:
OH
2 2 2 2
CH (OH) CH M CH CH OH + = +
+ +
+ +
+ + +
+ +
With NOx:
produced is O
O CO 2O CO : Net
M O M O P) O(
O P) O( NO h NO
OH NO NO HO
M HO M O H
CO H OH CO
3
3 2 2
3 2
3
2
3
2
2 2
2 2
2
+ +
+ + +
+ + +
+ +
+ + +
+ +
Figure 14
3
overleaf shows the complete cycle of how ozone is formed and destroyed
via the action of NOx and sunlight. In urban areas the concentration of NOx and
VOCs are always high, however one doesnt see smog on a daily basis as intense
sunlight is required to create the OH radicals and photolyse NO
2
(therefore producing
O
3
), so clear, still, hot days are ideal for smog formation
1
.
- 23 -
L. H. Vote GCE Green Chemistry Teachers Pack
Figure 14: Diagram to depict the cycle of formation and destruction of ozone, determined by
NOx
Image courtesy of: T. G. Harrison and D. E. Shallcross, Teacher Update 1 Atmospheric Chemistry, University of Bristol,
Bristol, 21
st
June 2006.
The graph below (Figure 15) shows how production of ozone - hence smog - varies
with NOx concentration. As NOxs are produced from anthropogenic sources (car
exhausts and industry), their concentration is higher in urban areas than rural:
Figure 15: Graph to show the variation of ozone production (hence photochemical smog) with
NOx concentration
1
- 24 -
L. H. Vote GCE Green Chemistry Teachers Pack
At low NOx concentrations, there is more ozone than NOx, so ozone is destroyed
by CO. This typically occurs in a marine environment
1
.
At zero net production of ozone (the compensation point
1
), the amount of
destruction equals the amount of ozone production.
Above the compensation point there is a linear increase in the production of ozone
with increasing NOx concentrations (as explained by the mechanism above).
This reaches a maximum, and at very high NOx concentrations, there is
retardation of ozone production as radical termination reactions occur
1
:
M HNO M OH NO
3 2
+ + +
(M is an unreactive species in the air which can absorb excess energy from the
reactants)
So we see lower levels of smog with extremely high concentrations of NOx.
Ozone only lasts on the surface for a few hours, so one can monitor the changes in
ozone levels throughout the day. For example, on a sunny day when NOx levels peak
early in the early morning rush hour, ozone levels increase for a few hours afterwards
and then drop in the evening. However, ozone rises slightly into the troposphere and
remains there for a few months which is an unwanted effect as ozone is a greenhouse
gas
3
.
2.4. UK Emissions Today
CO and SO
2
levels have decreased since the 1970s
3
o This is because society has made an effort in cleaning up these pollutants,
through legislations such as the Clean Air Act (introduced in 1956). This act
created zones where smokeless fuels had to be burnt, moved power stations to
rural areas (to reduce urban smog), and required industries and factories to
have tall chimneys to disperse air pollution
21
. Since then, power stations and
factories are required to have filters and catalytic converters in their chimneys.
NOx and VOC levels have stayed almost constant, as although cars emissions
have been cleaned up (through the use and improvement of catalytic converters),
the volume of cars has increased
3
- 25 -
L. H. Vote GCE Green Chemistry Teachers Pack
Society has increased their awareness of pollution and its causes since the
industrial revolution. There are continuing efforts to find greener fuels to reduce
these emissions.
Infrared spectroscopy can be used to monitor air pollution through the use of
mobile Fourier transform spectrometers as the major components (CO, CO
2
, SO
2
,
NO
2
and VOCs) can be detected.
2.5. Catalytic Converters
A catalytic converter treats the exhaust of a car before it enters the atmosphere to
remove sources of air pollution.
The main components of car emissions are N
2
gas (due to the fact that the majority of
air in N
2
gas, so this passes through the cars engine), CO
2
and H
2
O (both products of
combustion). As combustion is not always complete, trace amounts of CO, VOCs
(unburned fuel that has evaporated), and NOxs. Besides carbon dioxides Global
Warming Potential, the trace gases are most harmful and causes of air pollution.
A catalytic converter is usually 3-way: it has a reduction catalyst, an
oxidation catalyst and a control system (which monitors the exhaust and
feeds back information to fuel injection system)
22
.
The reduction catalyst is the first stage and uses a ceramic (usually)
honeycomb structure coated with platinum and rhodium
22
. It reduces NOx
emissions by
22
:
o Adsorbing NO and NO
2
at the catalyst surface
o The NOx then undergoes a chemical reaction whereby it bonds with the
nitrogen, hence breaking the N-O bond so oxygen is free and bonds with
other oxygen atoms to form O
2
. The N then reacts with other N atoms on
the catalysts surface and so forms N
2
. This is then desorbed from the
catalysts surface as free N
2
gas.
The oxidation catalyst is the second stage and uses a platinum and palladium
catalyst coated again onto a ceramic honeycomb structure
22
. It oxidises
unburned hydrocarbons (VOCs) and CO
22
by lowering the activation energy
for combustion of these reactants with the remaining oxygen supply in the
exhaust.
o The catalyst adsorbs CO and the VOCs onto the catalyst surface
- 26 -
L. H. Vote GCE Green Chemistry Teachers Pack
o Free O
2
in the exhaust gas passes over the catalyst and the catalyst
therefore aids the oxidation of the CO and VOCs causing a chemical
reaction to form CO
2
.
o This CO
2
doesnt adsorb as well onto the catalyst so is released into the
exhaust.
2.6. Acid Rain
Acid rain is caused by NOx and SO
2
converting to nitric acid and sulphuric acid
23
.
Rain is normally slightly acidic anyway, having a pH of 5.5
23
due to the fact that
some acids are dissolved in it from natural sources of nitrogen and sulphur as well
as carbon dioxide. However precipitation in polluted areas or downwind from
polluted air is more acidic than usual due to increased levels of NOx and SO
2
.
These pollutants are emitted into the atmosphere through combustion of
hydrocarbons or hydrocarbons containing sulphur (the released H
2
S reacts with
oxygen during the combustion process:
2 2 2 2
2SO O 2H 3O S 2H + + )
24
.
Acid) (Nitric HNO OH NO
: Formation Acid Nitric
SO H HSO
Hydrolysis HSO H O H SO
in water dissolves dioxide Sulphur O H SO O H SO
: Chemistry Phase Aqueous - Formation Acid Sulphuric
Acid) (Sulphuric SO H O H SO
SO HO O HOSO
HOSO OH SO
: Chemistry Phase Gas - Formation Acid Sulphuric
3 2
2
3 3
3 2 2
2 2 (l) 2 (g) 2
4 2 2 3
3 2 2 2
2 2
+
+
+
+
+
+ +
+
+
+
25
Thus, both are oxidised by the reactive hydroxyl radical (see Section 2.2 for how
is created). In the presence of water vapour, the sulphur trioxide (SO
3
) is
rapidly converted to sulphuric acid
OH
25
. In clouds, liquid droplets of water react
much more rapidly with sulphur dioxide
25
.
These acids are both dissolved into water, precipitated down to earth, and the
pollutants may be deposited through dry deposition closer to their source onto
- 27 -
L. H. Vote GCE Green Chemistry Teachers Pack
vegetation and soils, where the above reactions occur to create acids
23
. If it is
dissolved into clouds, the acids may travel a long way, even hundreds of
kilometres before it falls
23
therefore pollution recognises no boundaries and acid
rain caused by UK emissions are known to have fallen in Norway and devastated
the forests. In fact, the UK accounts for at least 16% of Norways acid rain
26
.
Effects of Acid Rain
of rivers and lakes and so can destroy the ecosystems,
vegetation and organisms within them. pHs below 5 will stop fish eggs from
ria in the soil
27
.
diseases such as cancer, bronchitis, emphysema and
g
/
m
3
Day
11
P
H
O
T
OC
O
P
Y
P
Monitoring air pollution page 3 of 3
Air quality bands for three pollutants
Air Pollution Low Moderate High Very High
NO
x
/ ppb,
hourly average Less than 150 150299 300399 400+
Ozone / ppb
hourly average Less than 50 5989 90179 180
PM10 / g/m
3
Less than 50 5074 7599 100+
3. At the start of 1999, how would you describe the levels of a) NO
x
, b) Ozone,
c) PM10 recorded in Leeds and Narberth?
a)
____________________________________________________________________
____________________________________________________________________
b)
____________________________________________________________________
____________________________________________________________________
c)
____________________________________________________________________
____________________________________________________________________
4. Do you find any of these results surprising? Explain your answer.
____________________________________________________________________
____________________________________________________________________
____________________________________________________________________
____________________________________________________________________
L. H. Vote GCE Green Chemistry Teachers Pack
Lesson Plan 2 and
Resources:
AS Module 2
Extraction of Metals, Acid
Rain and Recycling
L. H. Vote GCE Green Chemistry Teachers Pack
AS Module 2 Extraction of Metals, Acid Rain and Recycling
Objective
To be able to state some advantages and disadvantages of recycling
scrap metals vs. extraction of metals
To be able to explain why it is more environmentally friendly to use
scrap iron to extract copper from aqueous solutions vs. carbon
reduction of copper oxide
To be able to describe which pollutants + hence acids cause acid rain
To be able to describe the environmental effects of acid rain
To be able to list the uses of polypropene and know that it is recycled.
Aim
To discuss the environmental and economic
advantages and disadvantages of recycling metals
compared to extraction of metals, and why using
scrap iron to extract copper is advantageous.
To explain how sulphides are converted to oxides
and how this can contribute to acid rain
To understand the environmental problems of acid
rain
To explain the uses of polypropene and that it is
recycled.
Links to AQA specification
AS Module 2: 3.2.7. Extraction of Metals
AS Module 2: 3.2.9. Polymerisation of Alkenes
Overall Picture
To hold a brainstorming session on the pros and
cons of recycling metals vs. extraction of metals.
To remind them of sulphur dioxide causing acid
rain, showing them the animation and PowerPoint
presentation.
To do a practical demonstrating the effects of acid
on limestone
To do a worksheet on Acid Rain
To explain the uses of polypropene, a recyclable
polymer.
Resources to be used
Animation on acid rain:
http://www.dfes.gov.uk/psp/resources/Secondary/Science/
Year_9/Acid_rain/Acid_rain_animation.swf
PowerPoint Presentation on Acid Rain: cause and effects
Worksheet on acid rain:
http://chemistry.slss.ie/downloads/ch_ol_clozeacidrain.pd
Health and Safety Risk Assessment
f
Britannica Online video on Acid Rain:
http://www.youtube.com/watch?v=RP-
Wear protective lab coats and goggles
Take car when pouring the acid, using latex gloves
if possible
Place the chalk into the beaker using tongs
sU8i2edo&feature=related
Starter Activity
Hold a class brainstorming session, writing responses on a table on the board, on the environmental and economic advantages
and disadvantages of recycling metals compared to extraction of metals, and why using scrap iron to extract copper is
advantageous. Refer to Table 6 in Section 4.1.2 for a comprehensive table.
Main Activity
Remind the class of SO
2
and NOx being pollutants that cause acid rain, asking how they are formed (the combustion of
hydrocarbons).
Explain that metals are usually found in ores as oxides or sulphides and when they are extracted SO
2
is released, another
anthropogenic way of contributing to acid rain.
Show the animation on acid rain and the PowerPoint presentation, having the students make notes. If time, watch the Britannica
Online video 2 minutes.
Optional Practical activity in small groups or individually :
From: http://www.reachoutmichigan.org/funexperiments/agesubject/lessons/tnrcc/acidrainlesson.html
1. Explain that acids react chemically with limestone and that chalk is limestone
2. Fill a beaker 1/3 full with vinegar or H
2
SO
4
3. Add a piece of chalk to the glass
4. Have the students write what they see happening
5. Discuss their observations and inferences. Discuss the slow deterioration of statues and buildings due to the weak acid rain
that falls on some statues and buildings. If the stone is limestone or has limestone in it, the deterioration is more rapid.
Ask the students to do the worksheet on acid rain, where the students can fill in the gaps.
To list the uses of polypropene (refer to the end of 4.1.3), and that it is a recyclable polymer.
Plenary
Ask the students to name one advantage and one disadvantage on the recycling of scrap iron
Ask the students which pollutants contribute to acid rain, which acids they form and how they are formed
Ask the class to list 3 problems caused by acid rain
Ask the class to name 3 uses of polypropene
- 58 -
Acid Rain
Lisette Vote
Acid rain is caused by NOx
and SO
2
converting to nitric acid (HNO
3
) and
sulphuric acid (H
2
SO
4
)
Acid) (Nitric HNO OH NO
: Formation Acid Nitric
SO H HSO
Hydrolysis HSO H O H SO
in water dissolves dioxide Sulphur O H SO O H SO
: Chemistry Phase Aqueous - Formation Acid Sulphuric
Acid) (Sulphuric SO H O H SO
SO HO O HOSO
HOSO OH SO
: Chemistry Phase Gas - Formation Acid Sulphuric
3 2
2
3 3
3 2 2
2 2 (l) 2 (g) 2
4 2 2 3
3 2 2 2
2 2
+
+
+
+
+
+ +
+
Butprecipitation in polluted areas or downwind
from polluted air is more acidic
than usual due to
increased levels
of NOx
and SO
2
These pollutants are emitted into the
atmosphere through:
Combustion of hydrocarbons
Combustion of hydrocarbons containing sulphur
Extraction of metals from their metal sulphide form
NO) and NO (i.e. NOx ) combustion (from heat N O
2 2 2
+ +
2 2 2 2
2SO O 2H 3O S 2H + +
2
2 2
SO 3Pb 2PbO PbS
SO PbS PbO O
2
3
2PbS
+ +
+ + +
These acids are both:
Dissolved into water in clouds & precipitated down
to earth
This means the clouds could travel a long way (100s of km!)
before it falls
UK emissions are known to have fallen in Norway and
devastated the forests. In fact, the UK accounts for at least
16% of Norways acid rain
The pollutants may be deposited through dry
deposition
onto vegetation and soils, where they
create acids directly
Problems of Acid Rain
The increased acidity of rivers and lakes
and so
can destroy the ecosystems, vegetation and
organisms within them.
pHs below 5 will stop fish eggs from hatching and
below that can kills
even adult fish.
So as acidity increases, the biodiversity
of lakes
decreases.
Acid rain has made certain fish and species of
insects extinct.
Acid rain can slow
the growth of
vegetation and
forests.
Changes to the soil
pH can harm plants
and denature
enzymes and
bacteria in the soil.
There is an increase in the rate of people
obtaining lung diseases
such as:
Cancer
Bronchitis
Emphysema
Asthma
This is thought to be caused by the inhalation
of small particulate matter (PM10s); including
sulphur
so acid rain may be a contributing
factor to these human health problems.
Limestone is easily dissolved by acids:
So buildings and monuments have
become easily eroded
O H CO CaSO SO H CaCO
2 2 4 4 2 3
+ + +
Acid Rain
The following words are omitted from the passage below:
sulfur dioxide, volcanoes, limestone, power plants, fossil fuels, acid rain, pH,
oxidized, rain
Write down in the spaces given below the appropriate missing word corresponding to
each of the numbers 1 to 9.
Unpolluted rainwater is slightly acidic. It has a (1) of approximately 5.5 due to
carbon dioxide in the atmosphere. Emissions of acidic gases lead to a lowering of pH,
with the formation of acid rain. The main causes of acid rain are the oxides of
nitrogen and the oxides of sulfur. (2) damages soil, causes the poisoning of
fish, attacks trees and erodes buildings.
Oxides of nitrogen
Oxides of nitrogen are released from car exhausts and _____ (3) ___where the high
temperatures bring about the oxidation of atmospheric nitrogen. They are also formed
in some biological processes and by lightning discharges. Nitrogen monoxide, NO, is
quickly (4) in air to nitrogen dioxide, NO
2
. Nitrogen dioxide dissolves in
water and reacts to form a mixture of HNO
2
and HNO
3
. When this occurs in the
atmosphere the result is acid rain.
Oxides of sulfur
Oxides of sulfur are mainly formed by the combustion of fossil fuels, particularly
coal. They can also be released by (5) and by the decay of organic matter.
When (6) are burned the sulfur in them forms sulfur dioxide, SO
2
, which is
a dangerous pollutant. Sulfur dioxide dissolves in water to form sulfurous acid,
H
2
SO
3
. In the atmosphere, sulfur dioxide is oxidised to sulfur trioxide, SO
3
. Sulfur
trioxide dissolves in rainwater to form sulfuric acid, H
2
SO
4
. Thus the release of SO
2
into the atmosphere is likely to result in (7) containing H
2
SO
3
and H
2
SO
4
.
Scrubbing waste gases
Limestone is used to reduce sulfur dioxide emissions from coal-fired power stations.
Coal is mixed with finely ground (8) . The high temperatures in the furnace
cause the limestone to decompose: CaCO
3
CaO + CO
2
The calcium oxide reacts with much of the (9) , preventing its release:
CaO + SO
2
CaSO
3
1________________ 2________________ 3 ________________
4________________ 5________________ 6________________
7________________ 8________________ 9________________
L. H. Vote GCE Green Chemistry Teachers Pack
Lesson Plan 3 and
Resources:
AS Module 2
Ozone Destruction
L. H. Vote GCE Green Chemistry Teachers Pack
AS Module 2 Ozone Destruction
Aim
Resources to be used
PowerPoint Presentation: The Effects of Ozone Depletion
Useful website that can be used to help explain ozone
destruction: The Ozone Hole Tour
6
http://www.atm.ch.cam.ac.uk/tour/
Cl
.
Generation animation:
http://aes.gsfc.nasa.gov/vis/a000000/a001600/a001603/mo
leculeA.mov
Worksheet on Atmospheric Chemistry
Health and Safety Risk Assessment
Care must be taken when using a computer. Avoid
straining eyes and low light.
To understand the benefit of ozone in the
stratosphere
To understand why CFCs form Cl atoms in the
stratosphere and how it causes the destruction of
ozone
To know of the legislation banning the use of CFCs
and of an example of one of the chlorine-free
alternatives developed by chemists
Objective
To be able explain why ozone is beneficial in the stratosphere, listing
some adverse effects of increased UVB exposure
To be able to provide the mechanism of Cl catalysed ozone
destruction
To be able to explain why CFCs are a source of this Cl atom
To be able to state that CFCs are now banned by the Montreal
Protocol and Chlorine-free alternatives have been developed by
chemists
Overall Picture
Discussion of what ozone is and why it is
beneficial, making use of the PowerPoint
presentation.
An explanation of how Cl radicals catalyse the
destruction of ozone. The notes in this resource and
the Ozone Hole Tour website are useful resources
An explanation of how CFCs are a source of the Cl
radicals using the animation.
Worksheet on atmospheric chemistry
An explanation of the solution: legislation banning
CFCs and alternatives develo
Links to AQA specification
AS Module 2: 3.2.8. Synthesis of chloroalkanes
ped.
Starter Activity Idea taken from: http://www.floridatechnet.org/GED/LessonPlans/Science/ScienceLesson5.pdf
Ask what is the ozone? Discussion should centre on how the ozone is a layer around the earth and is important in keeping out
the harmful, high energy UVB radiation from the sun. Ask what is meant by damage to the ozone? Answers should include such
things as holes in the layer itself or the thinning of the layer, by CFCs. You may wish to bring in a product to demonstrate the
types of materials that are viewed as damaging to the ozone such as an aerosol can or a product that contains/formerly contained
chlorofluorocarbons.
Main Activity Please refer to sections 1.2 and 1.5 for notes.
Explain the benefit of ozone in the upper atmosphere in that it attenuates harmful UVB radiation, briefly list some of the effects of
ozone depletion (see PowerPoint presentation).
Explain why chlorine atoms catalyse the decomposition of ozone: Use the Ozone Hole Tour resource to help explain.
2 3
O ClO O Cl + +
n Destructio Ozone - 2O 2O : Net
) O 2(ClO ) O 2(Cl
O Cl Cl h ClOOCl
M ClOOCl M ClO ClO
2 3
2 3
2
+ +
+ + +
+ + +
Explain that these chlorine atoms are formed in the upper atmosphere (stratosphere) when energy from UV radiation causes C-Cl
bond to break in CFCs: light at 200 nm: CFCl
3
+ hv CFCl
2
.
+ Cl
.
Use the above animation (and, if you wish, the Ozone
Hole Tour resource to help explain).
Ask the students to complete the attached worksheet on Atmospheric Chemistry
Explain the aims of the Montreal protocol and Vienna Convention (see section 1.5.4) to ban the use of CFCs, and that this was
supported by chemists. We have now developed alternative-chlorine free compounds, examples of which are in section 1.5.5.
Plenary
Ask the students to explain why ozone is beneficial
Ask the students to state which substance catalyses the destruction of ozone and each student to come to the board to write a line
for the mechanism of its destruction
Ask the student to state what the Montreal protocol does and to provide the name of an alternative to CFCs.
- 59 -
Ozone Depletion:
Why it is Dangerous
Lisette Vote
Humans
Increased levels of dangerous high-energy UVB
radiation impinging upon the earths surface can
cause:
Melanoma and non-melanoma skin cancer
A 10% reduction in ozone results in a 26%
increase in non-melanoma skin cancer
Eye disorders and Cataracts
Suppression of the immune system in people of
all races
possibly leading to an increase in diseases and
infections
Plants
Roughly half of the worlds plants are sensitive to
UV-B light
Their leaves shrink and the plant grows less when
exposed to an increase in UV-B light
Economically, this is also problematic as:
It can cause reduce food yields
Plants also can change their chemical composition
with increased UV-B exposure, which can affect
their quality and nutrient levels
Aquatic Ecosystems
Phytoplankton
experience a similar
detrimental impact
of excess UV-B
radiation that terrestrial plants do.
This could:
Affect species further up the food chain
Have a detrimental impact on the
productivity of fisheries, amongst
others
Air Quality
Increased levels of surface UV radiation
can increase the levels of reactive
compounds in the troposphere (lower
atmosphere), such as:
hydrogen peroxide
acids
ozone where levels of NOx are high
causing smog
Materials Damage
Photo-oxidation
can occur to many
materials, e.g.:
Wood
Plastics
Rubber
This is which is when the materials become
oxidized & damaged
through the action of UV
light
Atmospheric Chemistry
The following words are omitted from the passage below:
oxides, increase, nitrogen, oxygen, ultraviolet, ozone, reactive,
chlorofluorocarbons, chlorine
Write down in the spaces given below the appropriate missing word corresponding to
each of the numbers 1 to 9.
The atmosphere is a thin layer of gas extending about 100 km above the earths
surface. It becomes less dense the higher you go. The main gases in the atmosphere
are (1) (78% by volume), oxygen (21% by volume) and argon 1%. The
remainder of the gases are present in much smaller concentrations and include carbon
dioxide, methane, water vapour and the (2) of nitrogen. All these gases are
present in an unpolluted environment. Human activities however (3)________ the
concentrations of some gases and add other gases including chlorofluorocarbons to
the atmosphere.
In the upper atmosphere oxygen molecules break down into oxygen atoms. These
oxygen atoms react with (4) molecules to form ozone.
Certain atmospheric gases absorb ultraviolet radiation strongly. One of the most
important of these is (5)_____, O
3
. Ozone is broken down on reaction with (6)_____
radiation to form an oxygen molecule and an oxygen atom.
Ozone is a very (7) gas. It reacts very quickly with other substances and gets
destroyed in the process. Chlorofluorocarbons are believed to be the main cause of
damage to the ozone layer.(8) break down in the atmosphere releasing chlorine
atoms. These (9)____ atoms react with and break down ozone, thus reducing the
amount of ozone in the atmosphere. There has been an increase in skin cancer and eye
cataracts as a result of the damage to the ozone layer.
1________________ 2________________ 3 ________________
4________________ 5________________ 6________________
7________________ 8________________ 9________________
L. H. Vote GCE Green Chemistry Teachers Pack
Lesson Plan 4 and
Resources:
AS Module 2
Global Warming
L. H. Vote GCE Green Chemistry Teachers Pack
AS Module 2 Global Warming
Aim Objective
To understand the terms carbon neutral and biofuels and how it is
applied to methanol and bioethanol.
To understand how methanol and bioethanol are produces
Understand to what extent bioethanol is carbon neutral
To be able to explain the link between IR radiation absorption by the
bonds in greenhouse gases and global warming
Explain the terms carbon neutral and biofuel
Understand how methanol and ethanol can
produced as carbon neutral biofuels
To discuss to what extent bioethanol is carbon
neutral
To explain the link between IR radiation absorption
by the bonds in greenhouse gases and global
warming
Overall Picture Links to AQA specification
AS Module 2: 3.2.3. Importance of equilibria in industrial processes
AS Module 2: 3.2.10. Ethanol production
AS Module 2: 3.2.11. Infra-red spectroscopy
To discuss what carbon natural means
To use a PowerPoint presentation to explain the
production of methanol for use as a carbon-neutral
fuel
Explain what a bio-fuel is and how bioethanol is
made
Show the video documentary about biodiesel to lead
into a discussion why bioethanol might not be
completely carbon neutral
Explain the link between IR radiation absorption by
the bonds in greenhouse gases and global warming
The students complete the global warming
worksheet
Resources to be used
PowerPoint presentation: Carbon Neutral Methanol
Production
Video Documentary about biodiesel:
http://www.soton.ac.uk/chemistry/IDECAT/
Courtesy of: Dr. David Read, University of Southampton,
Southampton, U.K.
Worksheet on Global Warming:
http://chemistry.slss.ie/downloads/ch_ol_clozegreenhouse
Health and Safety Risk Assessment
Care must be taken when using a computer. Avoid
straining eyes and low light.
.pdf
Starter Activity Please refer to section 3.3.4 for notes
Ask the class to name 3 greenhouse gases. Ask what it means to be a greenhouse gas (contributes to global warming). Explain
what is meant by carbon neutral to the class. Then ask them to come up with ideas in groups or as a class processes that could be
considered carbon neutral.
Main Activity
Explain (can be done using PowerPoint presentation) how methanol can be a carbon neutral fuel by being made by reaction of CO
with H
2
, explain how use of carbon neutral alcohols as fuels is an important and essential application.
Use this to lead on to explain what a biofuel is (see section 3.3.4) and how ethanol, produced by fermentation of growing crops is a
carbon-neutral biofuel
Show the video about biodiesel (analogous process to bioethanol)
Set up a class discussion as to why, through this process, it is debatable whether it is carbon neutral. (see section 3.3.4)
Explain how IR radiation excites the bonds C=O, C-H and O-H in CO
2
, methane and water vapour respectively causing them to
vibrate more vigorously and then re-emit the energy in all directions as heat, thereby heating up the atmosphere (see section 3.3.1).
This is why they are considered to be greenhouse gases and why they contribute to global warming; which refers to the recorded
increase of the mean surface temperature of the Earth, which is thought to be due to an increase in the concentration greenhouse
gases in the atmosphere due to human activity
31
.
Ask the students to complete the worksheet on Global Warming.
Plenary
Ask the students what carbon neutral means
Ask them to name one carbon neutral fuel and why
Ask the students why bioethanol might not be perfectly carbon neutral
Ask the students why CO
2
, H
21
O, and CH
4
are greenhouse gases in term of IR radiation.
- 60 -
Carbon Neutral Methanol
Production
Lisette Vote
Production of Methanol (CH
3
OH)
OH CH 2H CO
4 2 2
3
C 250 atm, 100 50
O Al ZnO, Cu,
2
2 2 4
0
3 2
+
+ + H CO O CH
Natural gas (methane) is combusted as a fuel to
produce energy, if it combusts incompletely
with a limited supply of oxygen
it forms
carbon monoxide, CO.
This can then react with hydrogen using a
catalyst to form methanol
Carbon Neutral
This is a carbon neutral process because
any CO produced when combusting
natural gas can be reclaimed to produce
methanol
When the methanol is combusted as a
fuel, the CO
2
released has the same
amount of carbon that was reclaimed
from CO.
So there are no net carbon emissions
into the atmosphere
Greenhouse Effect and Global Warming
The following words are omitted from the passage below:
greenhouse, rubbish dumps, global warming, water vapour, combustion,
warmer, forests, CFCs
Write down in the spaces given below the appropriate missing word corresponding to
each of the numbers 1 to 8.
Some gases found in the atmosphere absorb infrared radiation, thus preventing it from
escaping into space. The effect of this is to make the earth (1) . This greenhouse
effect keeps the earth at a comfortable temperature.
Problems arise when growing amounts of certain gases in the lower atmosphere
increase the greenhouse effect. There is evidence that the earth is getting hotter, i.e.
that (2)____ _ ____ is taking place. The effects of global warming on climate
have been predicted. These include warmer weather, changes in rainfall distribution,
rising sea levels, increased flooding and loss of land.
The most important (3)____ gases are water vapour, carbon dioxide, methane, and
chlorofluorocarbons. Water vapour makes the largest contribution to the greenhouse
effect because of its abundance. Global warming causes the amount of (4) in
the lower atmosphere to increase. The amount of carbon dioxide in the lower
atmosphere has been increasing for the past 150 years. The (5)_____ of fossil fuels
such as coal and oil is regarded as being the principal factor leading to this increase.
The destruction of the worlds (6) makes the problem worse because it reduces
the amount of photosynthesis taking place.
The concentration of methane in the lower atmosphere is rising. It is produced in
(7)____ ___ compost heaps, marshes , slurry pits, coal mines, and in the
digestive tracts of animals. Bacteria operating in anaerobic conditions on materials
such as carbohydrates are responsible. Chlorofluorocarbons, (8) , also absorb
infrared radiation. The fact that they have a large greenhouse factor makes their
release into the lower atmosphere undesirable.
1________________ 2________________ 3 ________________
4________________ 5________________ 6________________
7________________ 8________________
L. H. Vote GCE Green Chemistry Teachers Pack
Lesson Plan 5 and
Resources:
A2 Module 4
Disposal and Recycling of
Polymers
L. H. Vote GCE Green Chemistry Teachers Pack
A2 Module 4 Disposal and Recycling of Polymers
Aim
Links to AQA specification
A2 Module 4: 3.4.9. Biodegradability and disposal of polymers
To understand that polyalkenes are chemically
inert and therefore non-biodegradable
To understand that polyesters and polyamides can
be broken down by hydrolysis and are therefore
biodegradable
To appreciate the advantages and disadvantages of
different methods of disposal of polymers
including recycling
Objective
To be able to state why polyalkenes cannot biodegrade
To be able to state which polymers can biodegrade and how this is
done
To be able to state at least 2 advantages and disadvantages for each
method of disposal of polymers, including recycling
Resources to be used
Video of polyester hydrolysis: http://www.coolschool.ca/lor/BI12/unit2/U02L01/Hydrolysis-maltosemovie.htm
Video of polyamide hydrolysis: http://www.coolschool.ca/lor/BI12/unit2/U02L01/Hydrolysis-depeptidemovie.htm
Worksheet: Pros and Cons of Disposal of Polymers
Slide show of the process of recycling polymers:
http://www.americanchemistry.com/s_plastics/hands_on_plastics/activities/hdpe_slideshow/slide1.html
Health and Safety Risk Assessment Overall Picture
To come up with the different methods of disposal of polymers
To explain that polyalkenes are non-biodegradable, but polyesters and
polyamides are degradable: show the hydrolysis videos.
To discuss the pros and cons of the different methods of polymer
disposal, creating a table (see worksheet) as a class (possible for this
to be a homework assignment)
Optional: Practical on the hydrolysis of glycogen to glucose over
time.
If doing the practical, wear lab coat and goggles
Take care when handling HCl and K
2
HPO
4
, use
latex protective gloves
Keep test tubes in a test tube rack
Have excess acid/base at hand to neutralise any
spillages
If heating with a Bunsen burner, place away from
overhead shelving and cluttered equipment and
combustible materials, do not leave open flame
unattended and shut off gas when not in use. Use
tongs to hold the test tube to the flame.
Starter Activity Please refer to section 4.1.3 for notes
To brainstorm as a class, writing on the board their answers different methods of disposal of polymers
Main Activity
Explain that due to the unreactive alkane backbone of polyalkenes (e.g. polyethene), polyalkenes are chemically inert. This causes
them to be non-biodegradable, and can take up to 500 years to start to degrade.
Explain polyesters and polyamides can be broken down by hydrolysis and are therefore biodegradable, showing the videos
Discuss as a class the advantages and disadvantages as a class for the different methods of disposal of polymers, including
recycling, writing answers on the board and in the matrix on the attached worksheet (Pros and Cons of Disposal of Polymers).
Alternatively, it can be written on an A3 sheet which can be photocopied and distributed to the students as it is being discussed.
Table 7 is a comprehensive table of this. You can show the slide show of the process of recycling polymers (see link above).
Optional Practical Activity: Hydrolysis of glycogen to glucose monomers (Adapted From: http://staff.science.nus.edu.sg/~dbsyhh/lab3.htm)
1. Prepare a series of seven test tubes, labeled 0 through 30 minutes in 5-minute intervals.
2. Pipette 2.5 ml of 1.0 M K
2
HPO
4
into each tube (quenches the reaction)
3. In a separate tube, add 2.5 ml of glycogen (8 mg/ml) to 2.5 ml of 4.0 M hydrochloric acid and mix.
4. Immediately withdraw 0.5 ml of the glycogen-acid mixture and transfer it to the tube marked 0 minutes.
5. Place the remainder of the glycogen-acid solution in a vigorously boiling water bath, using a foil cap to cover the top of the
tube.
6. Remove 0.5 ml samples of 5-minute intervals for 30 minutes and transfer them to the appropriately labeled tubes containing
1.0 M K
2
HPO
4
7. Test each of the samples for increasing levels of glucose with Benedicts Test (a solution of copper sulphate, sodium
hydroxide, and tartaric acid) and heat.
8. Write down observations of how the colour increases in depth/intensity as more glucose is formed
Plenary
Ask the students to name the different methods of disposal of polymers
Ask the students to name 2 advantages and 2 disadvantages of recycling polymers
Say which type of polymers can be biodegraded and what is the name of the reaction type for this reaction (i.e. hydrolysis)
Ask why polyalkenes cannot biodegrade
- 61 -
Environmental Economic Social
Reuse
Advantages
Disadvantages
Mechanical
Recycling to
Lower Grade
Products &
Chemical
Recycling to
Monomers
Advantages
Disadvantages
Degradation
Advantages
Environmental Economic Social
Disadvantages
Incineration
Advantages
Disadvantages
Landfill
Advantages
Disadvantages
L. H. Vote GCE Green Chemistry Teachers Pack
Additional Green
Chemistry Resources
L. H. Vote GCE Green Chemistry Teachers Pack
Additional Green Chemistry Resources
The following pages contain extra resources on Green Chemistry, reproduced from
the Royal Society of Chemistry.
Contents:
1. The Twelve Principles of Green Chemistry
2. Plastics from renewable raw materials and bio-degradable plastics
a. Rubber & Experiment: Vulcanisation of natural rubber
b. Lactic Acid - Production of a plastic from 2-hydroxypropanoic acid
(lactic acid)
c. Experiment: production of a film using starch
Video Documentary about biodiesel can be found at:
http://www.soton.ac.uk/chemistry/IDECAT/
AQA specification link: A2 Module 4: 3.4.5. Carboxylic acids and esters and
Acylation
Courtesy of: Dr. David Read, University of Southampton, Southampton, U.K.
- 62 -
The twelve principles of green chemistry
It is better to prevent waste than to treat or clean up waste after it is formed.
Synthetic methods should be designed to maximize the incorporation of all
materials used in the process into the final product.
Wherever practicable, synthetic methodologies should be designed to use
and generate substances that possess little or no toxicity to human health and
the environment.
Chemical products should be designed to preserve efficacy of function while
reducing toxicity.
The use of auxiliary substances (solvents, separation agents, etc.) should be
made unnecessary whenever possible and innocuous when used.
Energy requirements should be recognized for their environmental and
economic impacts and should be minimized. Synthetic methods should be
conducted at ambient temperature and pressure.
A raw material or feedstock should be renewable rather than depleting
whenever technically and economically practicable.
Unnecessary derivatization (blocking group, protection / deprotection,
temporary modification of physical / chemical processes) should be avoided
whenever possible.
Catalytic reagents (as selective as possible) are superior to stoichiometric
reagents.
Chemical products should be designed so that at the end of their function
they do not persist in the environment, and break down into innocuous
degradation products.
Analytical methodologies need to be further developed to allow for real-time,
in-process monitoring and control prior to the formation of hazardous
substances.
Substances and the form of a substance used in a chemical process should
be chosen so as to minimize the potential for chemical accidents, including
releases, explosions, and fires.
These principles have been reprinted with permission from Paul T. Anstas and J ohn
C. Warner Green Chemistry: Theory and Practice, New York: Oxford University
Press, 1998
Plastics from renewable raw materials and bio-
degradable plastics
Adapted from RSC material by Horn, Bader and Buchholz
Plastics are an indispensable part of modern society. They are used in many different
areas, in daily use, in technical applications and even in medicine. It is often forgotten that
many modern developments would have been impossible without the use of plastics.
Plastics may have many advantages, but they are also the subject of environmental and
political debate. The use of fossil raw materials, such as oil, and the dangers which can
occur as a result of its extraction and transport have been criticized, as well as the
disposal and recycling of plastics. The fact that some of the problems could be reduced by
using renewable raw materials for the production of plastics has been overlooked.
Particularly in recent times the interest generated by such products has increased, or
rather, increased again. They are the subject of this section.
What are renewable raw materials?
Renewable raw materials are natural substances
1
which are used by mankind for
purposes other than nutrition or foodstuffs. [i]. They can be agricultural, forestry, animal or
microbial products. Examples of renewable raw materials which are used industrially are
cellulose, starch, sugar, oils and fats. The philosophy of the renewable management of
raw materials is that only amounts which do not upset the natural biological equilibrium are
extracted, and thus no disruption of the biosphere results.
The variety of renewable raw materials and their different chemical structures leads to a
wide range of applications. Table 1 shows some examples.
Renewable raw
material
Origin Chemical / technical
product
Application (example)
Cellulose Wood, cotton Cellulose ethanoate
(acetate),
cellulose ether
Sheets, films, filtration
condensate,
construction materials
Vegetable oils eg rape Rape seed oil
Rape seed oil methyl
ester
Lubricant
Fuel
Sugar (saccharose) Sugar cane, sugar
beet
Saccharose derivates
Plastics
Starch Wheat, potatoes,
corn, starch
Physically or
chemically modified
starch (eg
hydroxypropylstarch)
alkylpolyglycoside
Pregelatinized starch,
binders, adhesives,
finishing agents, plastics
Surfactants, detergents
Flax Fibre flax (Flax) Flax fibre Fibre-reinforced materials
Latex Rubber tree Rubber Car tyres
Wool
Sheep, goats etc Clothes, insulating
materials
Table 1 Examples of the application of renewable raw materials
1
These do not include mineral oil, natural gas and coal, which are natural substances, but which
were formed a long time ago.
The use of renewable raw materials to satisfy human needs has been happening for
thousands of years. The technique of boiling soap from plant oils and wood ash was used
by the Sumerians (2500 BC). The Egyptians had already discovered the method of dyeing
using henna, a powder from the leaves of the henna shrub, in the 14th century BC, as had
the people of Asia Minor in the 13th century BC, using alizarin from the madder plant.
The accumulation and decomposition of biomass are in equilibrium: 120 thousand million
tonnes of carbon a year are bound by photosynthesis, while 60 thousand million tonnes
are respired by plants in the dark and only 60 thousand million tonnes are converted to
biomass in plants. These in turn are released into the atmosphere as carbon dioxide in
winter as a result of decay processes. This is how the annual balance is worked out. This
balance can be disrupted by natural disasters and by mankind. Around 2 thousand million
tonnes of carbon dioxide are released into the atmosphere by deforestation and soil
destruction, and five thousand million tonnes by the combustion of fossil fuels.
The total biomass of the earth amounts to 1841 thousand million tonnes, or 3.6 kg m
-2
of
surface area,
according to estimates. Phototrophic plants, which use photosynthesis to
produce energy, make up 99% of this figure. However, mankind uses only 3% of the
biomass produced naturally (170 thousand million tonnes), by cultivation, harvesting and
processing. This amounts to 2 thousand million tonnes of wood, 1.8 thousand million
tonnes of grain and 2 thousand million tonnes of other natural substances (eg sugar cane,
turnips, oily fruits).
This can be compared with a worldwide consumption of 7 thousand million tonnes of oil
equivalent (mineral oil, natural gas, coal) for the production of energy. Only 7% is
reprocessed by the chemical industry. In 1991, the German chemical industry covered
1.8% (10%) of its raw materials demand with renewable raw materials, and the trend is
rising [ii]. In the meantime, 10% of packaging chips are made from starch, and the
proportion of biodegradable lubricants is over 30%.
Renewable raw materials have the big advantage over fossil raw materials that the
sunlight required for their growth is available in unlimited amounts, and that the carbon
dioxide released by their combustion corresponds to the amount bound by the plant during
its growth. The chemical industry makes use of this advantage, as well as the ability of
nature to synthesize new products. Thus, for example, soap can be made from vegetable
oils in one step by an alkali ester cleavage. The basic molecular structure of the surfactant
is already present and does not need to be developed via several reactions, as for
example in the oxidation of alkanes to fatty acids.
However, even the cultivation and processing of renewable raw materials can cause
environmental pollution, for example through the over-use of fertilizers and pesticides.
Furthermore, the energy expenditure required for cultivation, harvesting and processing
should not be forgotten. There are also products which are based on renewable raw
materials which are not easily degradable or even toxic. As with any chemical product, this
has to be carefully examined and taken into account.
[i] S. Mann, Nachwachsende Rohstoffe, Ulmer Verlag, Stuttgart 1998
[ii] M. Eggersdorfer, Perspektiven nachwachsender Rohstoffe in Energiewirtschaft und
Chemie, Spektrum der Wissenschaft 1994 Nr. 6 S. 96-102
Plastics from renewable raw materials
Plastics based on renewable raw materials are not a novelty. The first plastics which were
used in large amounts were modified natural products. Examples include rubber based on
natural rubber (1839), celluloid from cellulose (1865) and galalith which comes from casein
in milk. (1897). Natural rubber is still an important product today. In the first third of the 20
th
century, polymers based on renewable raw materials were dominant. Then gradually
plastics based on fossil raw materials began to take over, due to their ready availability
and the fact that they created completely new possibilities in the world of chemistry.
Today the interest in plastics based on renewable raw materials has increased
considerably. The aim here is to move away from petroleum-based plastics towards
renewable raw materials, whilst at the same time trying to synthesize new products with
special, desirable properties. For example, sugars are used as the alcohol components in
the production of polyurethanes, and scientists are trying to better exploit raw materials,
such as cellulose, which are available in large amounts. Products which are biologically
degradable, ie which can easily be disposed of after use, are also gaining considerable
interest. Only a few examples of the many possibilities will be illustrated here. We will start
with the classic example, rubber, and extend the range from plastics based on cellulose,
starch and 2-hydroxypropanoic acid (lactic acid) to polyurethanes made using castor oil.
Rubber
Rubber can be produced either synthetically, or from natural latex (or from mixtures of the
two). Natural rubber is, today, an alternative to synthetic products, a fact which is
highlighted by its proportion of only 30% of global rubber production.
Natural rubber is extracted from latex, the sap from the rubber tree (Hevea brasiliensis),
which oozes out of the bark when the tree is damaged. Coagulation then produces solid
natural rubber which is elastic and can be stretched considerably. If natural rubber is
kneaded with sulphur and heated to around 400 K, rubber is then formed (vulcanisation)
(Figure 2). These properties depend on the one hand on the sulfur content as well as on
other additives, eg fillers such as soot and zinc oxide in the production of tyres.
n
+S
8
S
x
S
x
S
x
S
x
S
x
n
Rubber
Natural rubber (polyisoprene)
Figure 2 Vulcanisation of natural rubber (poly(isoprene)) with sulfur to rubber
Experiment: vulcanisation of natural rubber
In the following experiment we will be working with the natural latex concentrate Kagetex
FA [i]. The rubber dispersion is stabilized with ammonia (0.7 %) and has a dryness ratio of
61.5 %. Three types of rubber with different sulfur contents are produced [ii].
Each group of students will need
Eye protection
Three aluminium dishes
A glass rod
A mortar and pestle
Access to an oven or drying cabinet
Natural latex concentrate liquid (eg Kagetex FA)
Sulfur (flammable)
Safety
Wear eye protection
Sulfur is flammable and its dust may be irritating to the eyes and respiratory
system.
Method
Different mixtures with varying amounts of sulfur are set up as shown in Table 2.
Mixture Mass of latex /
g
Mass of sulfur / g Relative
concentration of
sulfur
1 2.0 0.1 5
2 2.0 0.5 25
3 2.0 1.0 50
Table 2 Mixtures for the experiment on vulcanisation of rubber
The sulfur is ground in the mortar and mixed with the latex in an aluminium dish. The
different mixtures are then left in the drying cabinet at 140
0
C.
Disposal
The rubber waste can be disposed of with the household waste.
Observation
Elastic products are formed. The lower the sulfur content, the more elastic and soft the
rubber is.
Evaluation
The degree of hardness of the rubber depends on the sulfur content. The sulfur reacts with
the double bonds in the poly(isoprene) strands. Loose bonds are formed between the
chains (vulcanisation). The more sulfur is added to the natural rubber, the higher the
degree of intermolecular cross-linking and thus the hardness of the rubber produced.
[i] Kautschuk-Gesellschaft mbH, Frankfurt: http://www.kautschukgesellschaft.de
[ii] H. J . Bader (Hrsg.), Kunststoffe, Recycling, Alltagschemie, Band 12 der Reihe:
W. Glckner, W. J ansen, R. G. Weienhorn (Hrsg.), Handbuch der experimentellen Chemie -
Sekundarbereich II, Aulis-Verlag, Kln 1997
Production of a plastic from 2-hydroxypropanoic acid (lactic acid)
Each group of students will need
Eye protection
Test tubes
Test tube rack
Bunsen burner
Acrylic glass plate (approximately 15 cm 15 cm)
Boiling stone
Microspatula
Tin(II) chloride (irritant)
2-hydroxypropanoic acid (lactic acid)
Cobalt chloride paper (dried)
Safety
Wear eye protection
Tin(II) chloride is irritating to eyes and skin, and is dangerous with oxidising agents
such as nitrates and peroxides
Method
5 cm
3
of 2-hydroxypropanoic acid (lactic acid) are added to a microspatula load of tin(II)
chloride crystals and a boiling chip in a test tube and heated for 10 minutes whilst stirring
vigorously. The vapours emitted are tested with cobalt chloride paper. If an orange-brown
colour occurs in the test tube, the hot solution is poured onto the acrylic glass plate.
Disposal
Plastic waste can be disposed of with other household waste.
Observation
The solution applied to the acrylic glass plate solidifies and forms a yellow-brown slightly
sticky mass. The cobalt chloride paper changes colour from blue to pink.
Evaluation
Cobalt chloride paper is used to test for water which, as a result of the temperature,
escapes as steam from the test tube. The blue dry cobalt(II) chloride forms a pink-coloured
hexahydrate when combined with water.
The reaction is an esterification in which the 2-hydroxypropanoic acid (lactic acid) is
converted to oligomers with loss of water. In general one molecule of alcohol reacts with
one molecule of acid with loss of water to form an ester. The 2-hydroxypropanoic acid
used is bifunctional. It consists of one hydroxyl and one carboxyl group which form an
intermolecular bond.
The esterification is catalyzed by acid. The proton required for the first step of the
esterification (protonation of the carboxyl group) is formed by the hydrolysis of tin(II)
chloride with precipitation of a basic salt.
Poly(lactic acid)
2-hydroxypropanoic acid
(lactic acid)
n
nH
2
O
-nH
2
O
SnCl
2
+H
2
O Sn(OH)Cl +Cl
-
+H
+
Experiment: production of a film using starch
Part a: extraction of starch
Each group of students will need
Eye protection
Grater
Tea strainer
Mortar and pestle
Two 400 cm
3
beakers
Potatoes
Distilled or deionized water
Safety
Wear eye protection
Method
100 g of peeled and washed potatoes are ground with a grater. The mush is slurried with
100 cm
3
of water and poured through a tea strainer. This process is repeated twice. The
beaker is left for five minutes until the starch is precipitated on the bottom of the beaker.
The remaining water is decanted off. Another 150 cm
3
of water are added, stirred briefly
and decanted again. This process is repeated again with 100 cm
3
of water.
Disposal
The potato and starch waste can be added to compost or disposed of with other
household waste.
Observation
A white powder can be extracted from the potatoes.
Evaluation
The starch in potatoes can be extracted via a number of separation and purification steps.
It is known as natural starch and is treated with cold water during the extraction process
because starch does not dissolve in cold water.
Part b: production of a film
Each group of students will need
Eye protection
One 50 cm
3
round flask
One reflux condenser
One 25 cm
3
measuring cylinder
Three 3 cm
3
pipettes
Magnetic stirrer with hot plate
Oil bath
Acrylic glass plate
Drying cabinet
Thermometer
Spatula
Natural potato starch (from Part (a) or a chemicals supplier)
Propane-1, 2, 3-triol (glycerol) solution 50 %
Hydrochloric acid 0.1 mol dm
-3
Sodium hydroxide 0.1 mol dm
-3
(irritant)
Food dye (liquid)
Safety
Wear eye protection
Method
Add 25 cm
3
of water to 2.5 g of potato starch, 3 cm
3
hydrochloric acid and 2 cm
3
proppane-
1, 2, 3-triol (glycerol) solution. If you use the moist starch from Part (a), 4 g of potato
starch are required. Heat for 15 minutes under reflux. The reaction is stopped by adding
sodium hydroxide. The mixture can be dyed by adding 1 to 2 cm
3
of food dye. The hot,
viscous mass is poured uniformly onto the acrylic glass plate and dried for two days at
room temperature or for approximately 90 minutes at 100 C in a drying cabinet. If the
moist starch from Part (a) is used, the amounts should be adjusted to 4 g of starch.
Disposal
Waste can be added to compost or disposed of with other household waste. Neutralized
liquid waste can be poured down the drain.
Observation
The initially highly viscous but later thin solution can be cast into a film. The clear film can
then be removed form the glass plate.
Evaluation
Starch forms a film when it is dried from an aqueous solution. The reason for this is the
intramolecular and intermolecular hydrogen bonds, in particular those between the long
chains of the amylose molecules. However, the branched amylopectin, which makes up
the larger part of the starch molecule, inhibits film formation. The reaction with diluted
hydrochloric acid partially breaks down the amylopectin. This leads to improved film
formation, but the product is brittle. For this reason propane-1, 2, 3-triol (glycerol) is added.
Propane-1, 2, 3-triol retains water as a result of its hygroscopic properties. The bound
water inhibits the formation of crystalline and brittle areas within the molecule. Thus water
acts as a softener here as does propane-1, 2, 3-triol. The later is capable of slipping
between the starch molecules and thus making the plastic softer.
L. H. Vote GCE Green Chemistry Teachers Pack
References
L. H. Vote GCE Green Chemistry Teachers Pack
- 63 -
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