GCE

Chemistry

Context study

Edexcel Advanced Subsidiary GCE in Chemistry

(8CH01)

Edexcel Advanced GCE in Chemistry (9CH01)

Green Chemistry

October 2007
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Contents

Introduction 1
Green chemistry 2
Carbon neutrality 2
Reducing greenhouse emissions 2
Carbon capture 3
Fuels and energy 3
Green chemistry and catalysts 5
The problem of waste 7
Web references 8
Introduction

This document is designed to help teachers to understand the contemporary context of green
chemistry. It should give 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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Green chemistry

Switch on the television, read the paper or listen to the radio, and it probably won’t be long
until you hear or see references to ‘green issues’ or ‘being greener’. Most people know that
using energy-saving light bulbs and recycling your rubbish are among ‘green’ activities, but
what is green chemistry?
Because of pressures on the environment, there is a move to make human activity more
sustainable — in other words to reduce or halt depletion of limited resources, and to reduce,
halt, or reverse pollution of air, sea and land. Some roles of the chemist involve developing
industrial processes based on renewable resources; finding catalysts that allow reactions to
proceed at lower temperatures or produce the equilibrium yield more quickly; preventing
pollution by using the side products of reactions and reducing waste; identifying hazardous
chemicals and finding alternatives; and monitoring what goes on in reactions and in the
environment.

Carbon neutrality
Burning hydrocarbon fuels produces carbon dioxide, which is a greenhouse gas and is believed
to contribute to global warming. If hydrogen is burnt as a fuel, the only product is water, so is
it ‘greener’ to burn hydrogen than hydrocarbons? The answer to this question depends on how
much energy is needed to produce each fuel. This is where the idea of carbon neutrality
comes in.
A fuel is carbon neutral if the amount of carbon dioxide absorbed when the raw material is
grown equals the amount of carbon dioxide produced when it is manufactured and then burnt.
Petroleum fuels come from micro-organisms that absorbed atmospheric carbon dioxide
millions of years ago, and they emit carbon dioxide when they are burnt. However, on a
sensible time frame, in other words within our life span, the carbon dioxide absorbed cannot
be set against the carbon dioxide produced.

Reducing greenhouse emissions

There are three ways to reduce carbon dioxide emissions.
1 Use renewable energy sources such as photovoltaic cells, wind and wave power and fuels
made from crops (bioethanol and biodiesel). All have significant disadvantages.
2 Increase the amount of electricity made from nuclear power. From fission in the short
term and from fusion in the long term. This also has certain disadvantages.
3 Conserve energy by being more energy efficient. Examples include using more fuel-
efficient cars, using energy-saving light bulbs, switching off lights and not leaving
television sets on stand-by.
Recycling metals such as aluminium can reduce greenhouse emissions by 95 per cent compared
with the production of new metal from ores. This reduction does not arise simply from the
reduction in fossil fuels used but includes the PFC (perfluorocarbon) gases, which are a by-
product of aluminium smelting by the Hall-Heroult process. PFCs are up to 900 times more
potent greenhouse gases than carbon dioxide. Recycling the metal removes this source of
atmospheric pollution completely, and it can be recycled with almost no loss of quality.

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Carbon capture
Alternatively, the impact of carbon dioxide produced in the combustion of fossil fuels could be
lessened by carbon capture. The waste gases from the power station can be cooled and
compressed. The carbon dioxide is liquefied and can be separated from the other gases
(mostly nitrogen and water vapour). This liquid carbon dioxide can then be pumped down old
gas wells where it evaporates and is trapped in the geological formations that previously held
the hydrocarbon gases.
Power stations burning fossil fuels will remain major contributors of carbon dioxide for the
indefinite future. Norway, a major exporter of natural gas, is planning to bury large amounts
of carbon dioxide one kilometre below the North Sea. The waste gas will be compressed and
injected into the porous rocks of the depleted Sleipner natural gas field. Other ideas include
the storage of liquefied carbon dioxide under the great pressures found in the deep ocean.
There remain serious concerns about the security of such measures and the consequences of
the rapid venting to the atmosphere of enormous volumes of carbon dioxide.

Figure 1 — Capture and storage of CO2 (Source: Carbon Capture and Storage)

Fuels and energy

Burning hydrogen produces no carbon dioxide, but to be a carbon-neutral fuel no carbon
dioxide should have been produced in its manufacture. Hydrogen is usually made by the
reaction of methane and steam, which produces hydrogen and carbon monoxide. The latter
can then be converted to more hydrogen and carbon dioxide by further reaction with steam.
This means that methane is used as a reactant, and also in combustion as a source of energy
to maintain the temperatures required. The carbon dioxide given off when hydrogen is
produced in this way should be counted in the comparison of CO2 absorbed and emitted by the
different fuels.

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In the USA and Brazil there has been a shift in agricultural production to give crops that can be
converted to ethanol as an alternative liquid fuel. Biofuels like bioethanol can be made from
crops such as sugar cane, sugar beet, or corn. If the crop was grown in the last few years, then
use of bioethanol comes close to being carbon neutral. Doubts have arisen owing to the energy
needed to produce these biofuels, for example in the distillation and transportation of the
products. Carbon dioxide would almost certainly be produced in the process of harvesting,
extracting sugar from the crop, converting it to ethanol and purifying the fuel, so there is a
carbon footprint when we use these.
Growing crops for biofuels may have other environmental impacts, as in Malaysia where
forests are cut down to provide land for the growing of oil palms, or where they would
produce a monoculture in a particular area. In overpopulated countries this is very
problematic as a solution to the greenhouse effect, as growing biofuels would replace food
crops. In the UK, extra oil seed rape, corn and sugar beet for conversion to biodiesel and
ethanol could be grown on land set aside under EU regulations.

Figure 2 — Sugar cane harvesting (Source: Wikipedia)

Energy can be produced from fuel cells and solar cells. In a fuel cell, fuel and oxygen react in
a cell without actually being burnt. Yet again, the process is not carbon neutral as carbon
dioxide will be produced during the manufacture of the cell itself and the fuel used in the
cell.
Solar panels are made from thin layers of silicon with an anti-reflective coating and strips of
metal leading to a circuit. The manufacturers design them with an expected life span of about
twenty years. To reduce atmospheric carbon dioxide, the CO2 produced during manufacture
must be less than the CO2 that would have been emitted by burning fuel to release the same
amount of energy as the solar panel.
If wind farms are used to produce energy, there is a carbon footprint caused by the energy
required to build them, the electricity transmission lines, that the fuel burnt by the stand-by
power stations for when the wind strength is too low to generate enough energy.

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Green chemistry and catalysts
Catalysts speed up reactions and are not used up in the process. They range from enzymes,
which work at body temperature, to transition metals and their compounds operating at
several hundred degrees celsius.
One use of enzymes is in detergents where proteases can be used to break down protein,
lipases to break down fats and even cellulases to break down matted fibres on the surface of
clothing. Enzyme detergents have to be used at relatively low temperatures, so they save
energy in use when compared to detergents used at high temperatures. Other applications for
enzymes have been developed such as breaking up oil spillages, breaking down toxic
substances like cyanide ions, and making test strips for glucose for diabetics.
Enzymes working in solution are homogeneous catalysts, and therefore are difficult to
separate so that they can be reused. Chemists can immobilise enzymes by trapping them on
inert materials such as clays or ion exchange resins, so that they can be filtered off and
reused. This can easily be shown with the enzyme lactase which breaks down the lactose in
milk to glucose and galactose. It is used to prepare milk for lactose-intolerant people, or to
make cows’ milk suitable for cats, who they cannot digest much lactose.
Our entire transport system depends on the use of catalysts, as the alkanes produced by
fractional distillation of crude oil are not suitable for direct use in petrol vehicles. Straight
chain alkanes explode prematurely and cause an effect called ‘knocking’, and large alkanes
burn too slowly. Alkanes from crude oil are cracked by one of two processes.
• Thermal cracking produces alkenes and smaller alkanes including some branched alkanes.
• Catalytic cracking takes place at a lower temperature and produces mostly branched chain
alkanes and some arenes.
The catalysts used can be bonded onto natural minerals called zeolites. These contain tiny
interconnecting pores and have a huge surface area per gram. Chemists can grow crystals of
zeolites with pores of precise dimensions and hence control the products of catalytic cracking.

Figure 3 — The micro-porous molecular structure of a zeolite, ZSM-5

(Source: Wikipedia)

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When the world’s oil supplies run out, an alternative fuel may be methanol, as it burns very
cleanly. Methanol can be manufactured from carbon monoxide and hydrogen with a metal
catalyst. The process works at pressure of around 100 atmospheres and a temperature of
lower than 300°C. However, the carbon monoxide is currently made from coal or methane, so
it is still dependent on fossil fuels.
Catalysts are also important in treating the fumes from car exhausts, which contain unburnt
hydrocarbons, carbon monoxide and oxides of nitrogen. A three-way catalyst is needed to
clean up this mixture and the annual MoT test on cars over three years old ensures it is
working.
Transition metals like iron are well known for reactions like the Haber process, but chemists
have discovered uses for many other scarcer metals. Ethanoic acid can be manufactured by
the reaction of methanol with carbon monoxide.
CH3OH + CO → CH3COOH
This process has an atom economy of 100 per cent. The atom economy of a reaction is the
percentage of reactant atoms in the desired product. In other words there are no unwanted
products in this reaction. It was first carried out using a cobalt-based catalyst at 700
atmospheres pressure and a temperature of 200°C, when it still produced 65 tonnes of by-
products per 100 tonnes of ethanoic acid. Chemists investigated other catalysts and the latest
process uses a rhodium and iridium based catalyst at a temperature of 180°C and pressure of
30 atmospheres. This gives 99 per cent selectivity for ethanoic acid, so money and energy are
saved in carrying out the process and purifying the product.
Chemists now know a great deal about how catalysts work, including:
• their electronic structure must allow a bond to form with the reactants
• the shape of their surface must allow the reactant to attach
• there must be a large number of active sites where the reactant can attach, and
• the bonding must be of appropriate strength for the product to detach from the catalyst
surface.
Metals are not necessarily used as elements — in ethanoic acid manufacture the catalyst is a
2-phosphanethylcyclopentadienyl complex.
Catalysts can be used to control the structure of polymers. Poly(ethene) has a low-density
form with few crystalline regions and a much stronger, more crystalline high-density form.
Organometallic catalysts cause polymers to grow out from the catalyst surface like hairs, and
chemists now have control over the structure and hence the properties of the catalysts they
are making.

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The problem of waste
Plastics were a miracle chemical of the twentieth century, but the fact that many are non-
biodegradable has caused problems with long-lasting rubbish in streets and in landfill sites.
Chemists have sought various solutions to the problem.
Biodegradable plastics are now being developed from lactic acid (2-hydroxypropanoic acid),
and 3-hydroxypropanoic acid which forms a polymer known as biopol. If certain monomers
containing carbonyl groups are incorporated into polymer chains, they degrade more easily in
sunlight. If a plastic is mixed with starch granules and disposed of by burying in soil, micro-
organisms break down the starch granules and the structure of the plastic object collapses.
Soluble polymers such as poly(ethenol), are used to make liquitabs (detergents in water
soluble packets) and laundry bags for use in hospitals, to avoid handling of contaminated
laundry. The use of bacteria to make polymers like poly(3-hydroxypropanoic acid) reduces our
dependence on crude oil as a source of monomers. At present it is still a very expensive
option.

Figure 4 — Biodegradable plastic cutlery

(Source: United States Department of Agriculture)

To keep our water supply pure, we need to prevent toxic waste entering drainage water.
Pesticides kill insects but can damage us and other organisms so they should be as specific as
possible, and not last for long in soil, to prevent contamination of ground water. Chemists
have made new pesticides by identifying the molecular structures of natural pesticides and
synthesising modified versions, by changing groups on the molecule. This can improve the
pesticide in use by changing its solubility or altering its stability in the environment.
Nowadays there are organisations that track the use of dangerous substances and develop
clean technology. There are degrees in Clean Technology and learners can study topics such as
using energy, water and raw materials efficiently and productively, creating less waste or
toxicity while delivering equal or superior performance, and improving customer profitability.
There is legislation on waste disposal, which regulates the pH, metal-ion content and organic
content of effluents. This legislation is of no use unless we can measure the concentrations of
possible contaminants, and again chemists have analytical methods, from spectroscopy to
chromatography, to detect minute quantities of a wide variety of substances.
So chemists can help to sustain the resources and environment on our planet; they have
techniques to detect when things go wrong, and the potential to repair some of the damage.

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Web references
http://news.bbc.co.uk/1/hi/sci/tech/portal/climate_change BBC Climate Change
www.carbonfootprint.com Carbon Footprint
www.catalysis-ed.org Ethanoic acid manufacture
www.co2capture.org.uk Carbon capture and storage
www.greener-industry.org Greener Industry
www.intelligent-energy.com Intelligent Energy
www.renewableenergyaccess.com Renewable Energy Access
www.world-aluminium.org/production The International Aluminium
Institute

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October 2007

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