Module 1 Production of Materials

Production of Materials
1.1 Energy and Raw Materials from Fossil Fuels

1.1.1 Identify the industrial source of ethylene from the cracking of some of the fractions
from the refining of petroleum

Petroleum is a mixture of crude oil and natural gas.

Fractional distillation is a process used to separate crude oil into fractions according to their boiling
point ranges. Each fraction contains hydrocarbons of similar molecular weight, and lighter fractions
rise higher in the column.

Boiling point of a substance is directly related to the strength of the intermolecular forces
between molecules. Hydrocarbons exhibit only dispersion forces, which increase in strength when
there are more electrons present in a molecule. Thus, longer chained hydrocarbons possess
stronger dispersion forces, resulting in their higher boiling points.

A large amount of long-chain molecules are obtained by the process of fractional distillation, however
the high demand for ethylene in industry makes it economically favourable to break these down.

Cracking is the decomposition of large hydrocarbon molecules into small chain molecules, to increase
the output of high-demand products. There are two forms of cracking thermal and catalytic.

Catalytic cracking: 500 C

The heavy fractions are heated to 500 C in the presence of a heterogeneous surface catalyst
composed of zeolites crystalline aluminosilicates (compounds of aluminium, silicon and oxygen
as well as metal ions) with a high internal surface area due to its porous structure, which allows
the reaction to occur at a faster rate. While thermal cracking provides a better yield of ethylene,
catalytic cracking occurs at a lower temperature and thus provides substantial energy savings.

() ( ) ()

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Thermal cracking: 700-1000 C, 70

Long pyrolysis coils are used to heat hydrocarbon feedstocks and steam to around 700-1000 C
within a furnace, at just above normal atmospheric pressure. The high temperatures cause the
long-chain hydrocarbons to split, forming free radicals (highly reactive atoms with unpaired
electrons) that continue to decompose until the radicals react with each other, forming small
alkenes (eg. ethylene) and a by-product of hydrogen gas.

( ) ( ) ( ) ( )

Safety issues: Fire is the major risk as there is potential for leaks of flammable hydrocarbon
vapours from this closed process. Steam build-up has the potential to cause explosions if the
structural integrity of the equipment is not monitored and maintained. Some hazardous gases
(eg. , ) are produced and ventilation is essential to avoid poisoning if leaks occur.

1.1.2 Identify that ethylene, because of the high reactivity of its double bond, is readily
transformed into many useful products

Alkenes are unsaturated hydrocarbons as they contain double or triple bonds, while alkanes are
saturated hydrocarbons as they contain all single bonds. Their physical properties (eg. melting point
and solubility) are due to intermolecular forces and thus are similar. However, their chemical
properties are very different due to the high electron density of the alkene double bond, making
alkenes much more reactive than alkanes.

Ethylene has a highly reactive double bond (a site of high electron cloud
density) which allows it to undergo polymerisation. The double bond breaks
open to form two single bonds.

Alkene reactions:

Halogenation: Alkenes readily react with electronegative elements (eg. , , ) as they

are attracted to the high electron density of the double bond, resulting in electron transfers:

( ) ( ) ()

Hydrogenation: Addition reaction in which hydrogen molecules add onto an unsaturated

molecule, in the presence of a catalyst such as platinum:

( ) ( ) ( )

Hydration: Addition reaction in which water adds onto an unsaturated molecule to produce
an alcohol, in the presence of a dilute acid catalyst:

( ) () ()

Alkenes undergo addition reactions, where a small molecule adds across the double or triple bond of
another molecule to form a saturated hydrocarbon.

Alkanes undergo substitution reactions, where the hydrogen atoms in a hydrocarbon are replaced
by other atoms.
() () () ()

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1.1.3 Identify that ethylene serves as a monomer from which polymers are made

Ethylene is the starting material in the initial manufacturing process of many essential monomers,
which in turn form commercially significant polymers. The polymerisation of ethylene itself to form
polyethylene is also an important reaction.

Vinyl chloride (chloroethene) used in the production of polyvinyl chloride (PVC).

Styrene (phenylethene or ethenyl benzene) used in the production of polystyrene (PS).

1.1.4 Identify polyethylene as an addition polymer and explain the meaning of this term

Polymerisation is the process where many sub-units known as monomers, join together in a head to
tail like arrangement to form a large chain molecule known as a polymer. Ethylene is able to undergo
this process to form polyethylene.

Polyethylene is known as an addition polymer. Addition polymerisation is where alkene monomer

units add together side by side to form a polymer, without the loss of any atoms. The nature of
addition polymerisation requires double bon sites within monomers, as the double bond decomposes
to enable each monomer to attach itself to another.

( ) ( ) [ ]

( ) ( )

1.1.5 Outline the steps in the production of polyethylene as an example of a commercially

and industrially important polymer

1.1.6 Analyse information from secondary sources such as computer simulations, molecular
model kits or multimedia resources to model the polymerisation process

There are three main stages in the polymerisation of polyethylene:

Initiation:

The initiator molecule (organic peroxide) decomposes to form reactive free radicals, highly
reactive molecules which contain unpaired electrons.

These then activate the monomers by breaking their double bond to form an ethylene free radical.

Propagation:

The monomer radicals react with each other to join in a head to tail like arrangement, growing
into a large chain polymer. This process continues with the polymer chain length increasing.

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Termination:

When two free radical ethylene chains combine, a complete polyethylene molecule is formed and
the process stops.

( ) ( ) ( )

Alternatively, an inhibitor is added to halt the formation of free radicals. This can be done at any
time, so the size and molecular weight of the polymer chains can be regulated.

There are two main forms of polyethylene that are formed in industry high density polyethylene
(HDPE) and low density polyethylene (LDPE). These are dependent on the method used:

Ziegler-Natta process (HDPE): 60 C, 1

Ethylene is passed through a liquid alkane solution at 60 C and a few atmospheres. The catalyst
used for this process is a heterogeneous surface catalyst composed of a mixture of tin (II) chloride
and triethylaluminium. The polymer that is formed is high density polyethylene.

The Gas Phase process (LDPE): 300 C, 1000-3000

This process uses extremely high pressures and temperatures along with an organic peroxide
initiator (eg. benzoyl peroxide). This process forms low density polyethylene.

1.1.7 Identify vinyl chloride and styrene as commercially significant monomers by both their
systematic and common names

1.1.8 Describe uses of polymers made from the above monomers in terms of their properties

Polyethylene:

Polyethylene is commercially manufactured from the monomer ethylene. There are two major
forms of polyethylene:

High density polyethylene: Uniform high density crystalline structure as it is linear with
minimal side branches. The dispersion forces between chains tightly hold them together,
resulting in a strong and rigid polymer with a high melting point. The high density of its
crystalline regions extensively scatter and refract light, causing the polymer to appear
translucent or white. Thus, due to its strong, rigid and aesthetic properties, it is primarily used
in durable items such as housewares containers, rubbish bins and agricultural pipes.

Low density polyethylene: Non-uniform low density polymer due to its extensive chain
branching, which inhibits the chains from closely packing together. This results in weak
dispersion forces between polymer chains, causing the plastic to be soft and flexible with a
low melting point. It is primarily used in cling wrap, plastic bags and squeeze bottles.

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Polyvinyl chloride:

Polyvinyl chloride is commercially manufactured from the monomer vinyl chloride (systematic
name: chloroethene). The presence of large chlorine atoms along the polymer chain causes chain
stiffening, and the stronger intermolecular forces due to the larger chlorine atom results in a very
stiff material. Thus, PVC is a hard, inflexible and brittle polymer which is impermeable to water and
is extensively used in underground piping and electrical conduits.

PVC decomposes in the presence of UV light due to the formation of chlorine radicals, but the
addition of UV stabilisers (titanium chloride) prevents this reaction. Softer PVC can be produced
by adding a plasticiser, which decreases the dispersion forces between the polymer chains and
hence makes it more flexible.

Vinyl chloride Polyvinyl chloride

Polystyrene:

Polystyrene is a clear crystalline polymer commercially manufactured from the monomer styrene
(systematic name: phenylethene or ethenyl benzene). The nature of compaction of polystyrene
due to its large benzene ring results in a rigid and stiff polymer with a high melting point due to
chain stiffening and the increased dispersion forces. It also has thermal and electrical insulation
properties, as the large amount of benzene rings allows it to absorb energy, and has a high
refractive index. Hence, these properties make it suitable for use in car battery cases and CD cases.

Expanded polyethylene is produced by blowing gas through molten polystyrene and allowing it to
cool. Styrofoam is lightweight, as well as a good heat insulator and shock absorber due to the gas
trapped inside the spongy beads that allow temperature to be retained. It is also very formable as
it is a thermoplastic. It is used extensively for protective packaging and insulation.

Styrene Polystyrene

1.1.9 Identify data, plan and perform a first-hand investigation to compare the reactivities of
appropriate alkenes with the corresponding alkanes in bromine water

Aim: To compare the reactivity of cyclohexane and cyclohexene bromine water.

Equipment: Two test tubes, cyclohexane, cyclohexene, 0.01 bromine water, fume cupboard.

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Method:
1. 5 of cyclohexane was added to one test tube and 5 of cyclohexene was added to the
other test tube, clearly labelling the separate text tubes.
2. 2 of bromine water was added to each and the test tubes were shaken to the same extent.
3. The test tubes were left to settle, and then observed.
Results: It was observed that the cyclohexene immediately decolourised the bromine water from
yellow to colourless, while the cyclohexane remained yellow. This showed which hydrocarbon
decolourised the bromine water, allowing them to be distinguished from each other. The
cyclohexene reacted with the bromine water, forming 1,2-dibromocyclohexane (bromination).

() ( ) ()

Discussion: The experiment requires an environment of subdued light, as cyclohexane will

undergo a substitution reaction with bromine water in the presence of UV light, causing the
decolourisation of the cyclohexane-bromine water solution. This would make the experiment
invalid if it were to occur.

() ( ) () ( )

Cyclohexene and cyclohexane were used as they are clear, colourless liquids at room
temperature, and bromine water is an aqueous brown solution making the colour change
clearly visible. They are also stable, less toxic and have a longer shelf-life than hexene/hexane.
Risk assessment:
Safety goggles were worn to protect from splashing of any solutions.
Organic hydrocarbons (cyclohexene and cyclohexane) are highly volatile and flammable so
they were kept away from heat sources or flames at all times. They also release moderately
toxic vapour, so only small quantities were used and a fume cupboard was used to perform
the experiment. Experimental time was kept to a minimum.
Bromine water is highly toxic if ingested and is slightly corrosive.

1.1.10 Analyse information from secondary sources such as computer simulations, molecular
model kids or multimedia resources to model the polymerisation process

Models create a 3D representation of a chemical process, leading to greater understanding of

polymerisation. The models simplify and provide an analogical approach which allows an increased
conceptual understanding of the process.

However, the model is only a basic representation and simplifies a very complex chemical process. The
model only provided a very limited section of a polyethylene molecule, as it would be unfeasible to
have the amount of equipment to represent a single polymer chain of hundreds to thousands of
monomers.

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1.2 Materials from Biomass

1.2.1 Discuss the need for alternative sources of the compounds presently obtained from the
petrochemical industry

The petrochemical industry is one of the largest industries in the world. Its function varies from the
production of plastics to the refining of petroleum. The raw materials used to make petrochemical
compounds (eg. ethylene) are chiefly obtained from crude oil (petroleum). The rate of crude oil
consumption far outstrips the rate of supply in converting organic matter into oil, resulting in
petroleum being a non-renewable resource.

Crude oil supplies and natural gas reserves will thus eventually be exhausted in the foreseeable future.
There is a growing pressure to find and develop an alternative economically and environmentally
viable source of raw materials to obtain the compounds used in the petrochemical industry. Several
decades of rising world oil prices due to depleting resources and climate change has resulted in
growing investment in research towards the future implementation of economically viable sources.

These alternative sources include:

Ethanol is the main alternative source of ethylene, as it can be produced by fermentation of

starch and sugars, and can be easily converted to ethylene.
Cellulose (a major component of renewable biomass) is a major source of carbon compounds
as it contains the basic carbon chain structures needed to build compounds presently
obtained from petrochemicals, and is relatively abundant.
Biopolymers, produced using enzymes and bacteria, could also be a replacement for plastics.

1.2.2 Explain what is meant by a condensation polymer

1.2.3 Describe the reaction involved when a condensation polymer is formed

A condensation polymer is formed when monomers with functional groups react together to form
long polymer chains, with the elimination of a small molecule (eg. water).

Natural polymers include cellulose, starch, protein and DNA.

Manufactured polymer fabrics include silk, polyester and nylon.

1.2.5 Describe the structure of cellulose and identify it as an example of a condensation

polymer found as a major component of biomass

Cellulose is a naturally occurring condensation polymer formed from the monomer glucose. It is the
most abundant polymer on Earth and is a major component of biomass, a carbon-based renewable
resource produced by living organisms. Cellulose has a straight, flat and rigid carbon structure.

The formation of cellulose by the condensation polymerisation of -glucose monomers:

( ) ( ) ( ) ()

The beta glucose monomers combine together to form beta-maltose dimers as the attached to C1
combines with the of C4 on the next glucose molecule, to form a -1,4 glycosidic bond with the
elimination of water. The maltose dimers continue to condense together to form a cellulose chain.

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Properties of cellulose:
Linear structure as the bulky groups on alternate sides of adjoining glucose units.
Long and rigid cellulose fibres as the groups form strong hydrogen bonds which account
for the strength of wood as a building material.
Insoluble in water due to the reduced availability of groups, as they are involved in
hydrogen bonding between chains. The structure of cellulose exposes few groups to water
molecules, lowering the intermolecular interactions between the two substances.

Alpha glucose Beta glucose

1.2.2 Identify that cellulose contains the basic carbon-chain structures needed to build
petrochemicals and discuss its potential as a raw material

As each glucose unit contains a carbon chain and hydrogen atoms, cellulose contains the basic
building blocks of all hydrocarbons used in the petrochemical industry.

To convert cellulose into ethylene, it must first be broken down into glucose units. The glucose is then
fermented into ethanol, which is subsequently dehydrated to form ethylene. However, the
decomposition of cellulose into glucose is a major obstacle. This is because the long linear chains of
cellulose form very compact fibres, meaning complex energy intensive processes must be used to
break the glucose-glucose links. There are two main processes:

Cellulase digestion: Sodium hydroxide is used to open cellulose fibres, which are then
digested using microflora bacteria containing cellulase enzymes, producing glucose solution.
Acid hydrolysis: Heating of cellulose materials with concentrated sulfuric acid solution to
decompose cellulose into glucose, which is then neutralised to produce a solution of glucose.

These processes are currently not commercially viable, as cellulase digestion is a very slow biological
process and the hydrolysis of cellulose requires large amounts of energy. Scientific research continues
to develop more efficient and low-cost ways of using cellulose as a raw material. Despite the potential
presented by cellulose, an economically viable method of using cellulose as a raw material for
petrochemicals is not yet available.

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1.2.6 Use available evidence to gather and present data from secondary sources and analyse
progress in the recent development and use of a named biopolymer.

Biopolymers are naturally occurring polymers found in living organisms. They are biodegradable,
unlike plastics formed in the petrochemical industry, able to be broken down into their constituent
monomers and re-enter the environment.

Biopolymer: Biopol PHB (poly-3-hydroxybutyrate)

PHB is a condensation biopolymer that has been developed to replace polypropylene, a synthetic
and non-renewable polymer created from propylene. It is a stiff and brittle biopolymer that is rapidly
degraded by bacteria to form carbon dioxide, however has low impact strength which can be a
disadvantage in many applications.

Production:

This polymer is produced industrially by the bacteria Alcaligenes eutrophus. The method of
industrial production is as follow:
1. The bacteria are first grown in tanks of a high valeric acid environment (nutrients) until a
large population of bacteria is present.
2. The supply of nutrients is then changed to be deficient in nitrogen. This stops the bacteria
from multiplying, but forces them to form PHB as an alternative food source.
3. The PHB is then isolated from the bacteria, through the thermal decomposition of the
bacteria which leaves pure PHB.

Uses in relation to properties:

Replacement for polypropylene: PHB has very similar properties to polypropylene, a

polymer used in bottles and plastic bags. It has a high tensile strength due to the presence of
hydrogen bonding between chains and is resistant to water and acids.
Medical industry: It also has the potential to be used in medical applications due to its
biocompatibility (not rejected by the bodys immune system) and biodegradability. It is hence
used in stitches and body scaffolding, as these stitches will decompose naturally without the
need for removal and also result in fewer allergic reactions.
Disposable items: Used to make disposable items (eg. bottles, razors) as it is biodegradable
and non-toxic. However, this is uncommon due to the high cost of production.

Recent developments:

Gene splicing has been investigated as a means of transferring the PHB production capabilities of
Alcaligenes eutrophus to other bacteria such as the common Escherichia coli, as these are much
cheaper and easier to grow.

Evaluation:

Biopol is currently much more expensive than petrochemical plastics, but the growing demand for
its biodegradability and biocompatibility has increased research towards genetically modifying
bacteria to control the plastic they form. The renewability of biopolymers is a major factor towards
alleviating the worlds dependence on fossil fuels as it is a viable future replacement.

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1.3 Ethanol - Use and Manufacture

1.3.1 Describe the dehydration of ethanol to ethylene and identify the need for a catalyst in
this process and the catalyst used

The dehydration of ethanol involves the removal of a water molecule from ethanol, forming ethylene:

() ( ) ()

Concentrated sulfuric acid is used as a catalyst and a dehydrating agent due to its high affinity for
water. It provides an alternate chemical pathway with lower activation energy.

1.3.2 Describe the addition of water to ethylene resulting in the production of ethanol and
identify the need for a catalyst in this process and the catalyst used

The hydration of ethanol involves the addition of a water molecule to ethylene, forming ethanol:

( ) () ()

Dilute sulfuric acid is used as a catalyst, which opens the double bond and allows water to attach.
Water itself is not reactive enough to break the ethylene double bond.

1.3.3 Describe and account for uses of ethanol as solvent for polar and non-polar substances

Non-polar Polar hydroxyl

alkyl chain group

Ethanol is considered to be a universal solvent, as it is able to dissolve both polar and non-polar
substances. This is due to the presence of two distinct parts within the ethanol molecule an alkyl
chain and a hydroxyl group.

The polar hydroxyl group can form dispersion, dipole-dipole interactions and hydrogen bonds with
other polar molecules. As such, ethanol can dissolve polar molecules (eg. water).

The alkyl end can form dispersion forces with other non-polar molecules, and hence ethanol is able
to dissolve non-polar molecules (eg. iodine, pentane).

Uses of ethanol:

The major uses of ethanol are as a motor fuel supplement and as a solvent.
Solvent in cosmetics (eg. perfumes), medicinal preparations (eg. antiseptics), cleaning agents,
food colourings and flavourings.

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1.3.4 Present information from secondary sources by writing a balanced equation for the
fermentation of glucose to ethanol

Fermentation is the process in which glucose is broken down to ethanol and carbon dioxide by the
action of enzymes present in yeast.

( ) ( ) ( )

1.3.5 Describe conditions under which fermentation of sugars is promoted

For optimal fermentation to occur, there are conditions under which fermentation is promoted:

Temperature of 37C as this is favourable for the yeast to live.

Anaerobic conditions (exclusion of air), as if oxygen is present, the yeast will use the sugars
and oxidise them to carbon dioxide and water.
Presence of yeast, as it contains enzymes (biological catalysts).
Suitable grain or fruit (high content of starch or simple sugars) mashed with water.
Ethanol concentration is kept below 15%, as alcohol concentrations above this level kill the
yeast and prevent further fermentation.
Low to neutral as this prevents pathogens from growing.

1.3.6 Summarise the chemistry of the fermentation process

1. Simple sugars derived from plant material are mixed with yeast.
2. The zymase, maltase and invertase enzymes in the mixture catalyse a complex series of
biochemical reactions in which the starch or sucrose are converted to glucose and fructose:

( ) () ( ) ( )

3. The enzymes then convert glucose or fructose into ethanol and carbon dioxide:

( ) ( ) ( )

4. Fermentation ceases when the available sugars are metabolised. Yeast can produce ethanol
concentrations of up to 15%, after which the yeast cannot function and die. Fractional
distillation is required to obtain higher ethanol concentrations (95% azeotrope). To
completely remove water from azeotrope, mixture must pass through a dehydrating material.

1.3.7 Process information from secondary sources to summarise the processes involved in the
industrial production of ethanol from sugar cane

In the production of sucrose from sugarcane, a by-product is the leftover syrup from sugar milling
known as molasses. This can be used as the source of simple sugars for fermentation, as it contains a
high percentage of sucrose. The molasses is used to produce ethanol by hydrolysis and fermentation,
through the use of the yeast enzyme invertase which breaks sucrose down to form glucose.

There are some problems associated with the fermentation process:

When used industrially, fermentation requires large amounts of arable land to grow the crops
required to produce glucose. This results in a high level of deforestation.
Inefficient process, producing only 15% ethanol as higher concentrations will kill the yeast.

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1.3.5 Outline the use of ethanol as fuel and explain why it can be called a renewable resource

Ethanol is a renewable fuel as it can be manufactured from carbohydrates such as glucose that are
produced by the production of photosynthesis by living organisms (biomass).

( ) () ( ) ( )

Ethanol is readily able to undergo combustion, so it can be used as a fuel.

() ( ) ( ) ( )

1.3.9 Assess the potential of ethanol as an alternative fuel and discuss the advantages and
disadvantages of its use

As supplies of petroleum dwindle, the development of renewable fuels becomes an important area of
research. Ethanol has been promoted as a fuel for motor cars to supplement or replace petrol, giving
it the potential to lengthen the lifetime of the non-renewable petrochemical industry.

Advantages of using ethanol as a fuel:

It is a renewable resource that is derived from biomass, reducing the worlds dependence
non-renewable fossil fuel.
Undergoes complete combustion more readily than fossil fuels, as it has an oxygen atom
within its molecule which ensures that less oxygen is needed for complete combustion. This
increases the octane rating of the fuel, reducing engine knocking from premature and
uncontrolled combustion. Hence, ethanol is a cleaner burning fuel with reduced greenhouse
gas emissions.
It is a liquid, making it an easily transportable fuel.

Disadvantages of using ethanol as a fuel:

Large areas of agricultural land would need to be devoted to growing suitable crops in order
to produce sufficient ethanol to meet demand, leading to environmental problems such as
deforestation, soil salinity and fertiliser runoff.
Ethanol has a lower heat of combustion than petrol, so does not release as much energy
upon complete combustion. This means that cars require more ethanol fuel for the same
mileage as a lower amount of petrol, making it more expensive.
Costly engine modifications are required to run on ethanol mixtures beyond 20% as a higher
engine compression ratio is required.

Currently, ethanol has potential as an alternative fuel and a future replacement for fossil fuels,
reducing the worlds consumption of petrol and prolonging the supply of non-renewable crude oil.
However, further research into developing more efficient methods of ethanol production is required
before it can become an economically viable proposition.

Note: Ethanol has been proposed as a fuel based on the fact that it is greenhouse neutral (ie. the
produced when burned is balanced by the used in photosynthesis to produce crops to be
later converted to ethanol). However, significant energy input is required for the production of
fertilisers and the distillation process, coming from the combustion of fossil fuels which release carbon
dioxide. Nevertheless, the combustion of ethanol does have a lower greenhouse impact than petrol.

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1.3.10 Process information from secondary sources to summarise the use of ethanol as an
alternative car fuel, evaluating the success of current usage

At present, ethanol is predominantly used in fuel blends to supplement petrol supplies. Petrol
containing levels of ethanol up to 10% can be used in all cars without engine modifications.

Brazil: The worlds largest producer of ethanol, implementing a biofuels program in 1975 by
adopting ethanol as its primary fuel. Sugar cane has been used as a source of sugar for alcoholic
fermentation. The cellulose waste (bagasse) is also used to generate ethanol. However, Brazil has
struggled with the higher cost of ethanol production in comparison with petrol, and subsidies are
needed before it is economically viable.

USA and Canada: A biofuels program has been adopted, granting initiative tax concessions to
ethanol producers. Ethanol is used in a fuel called gasohol (10% ethanol, 90% gasoline).

Australia: Ethanol is generally considered an uneconomic proposition due to the high costs of
production. Furthermore, there is a lack of arable land within Australia to grow sufficient sugar
cane crops to make ethanol an important contributor to liquid fuel demands. However, subsidies
and tax concessions have been set up to encourage the production of ethanol to be used as a fuel
additive, such as the increasing use of E10 (10% ethanol).

1.3.11 Define the molar heat of combustion of a compound and calculate the value for ethanol
from first-hand data

The molar heat of combustion of a substance is the heat liberated when one mole of the substance
undergoes complete combustion with oxygen at standard temperature and pressure, with the final
products being carbon dioxide gas and liquid water.

The heat released by the substance can be calculated by using the formula:

change in heat ( ) mass of system ( )

change in temperature ( ) specific heat capacity of
substance ( )

To calculate the molar heat of combustion we need to find enthalpy ( ). Enthalpy is the amount of
heat absorbed in the reaction per mole of the reactant, and is measured in .

1.3.12 Solve problems, plan and perform a first-hand investigation to carry out the
fermentation of glucose and monitor mass changes

Aim: To ferment a sucrose solution and monitor the mass changes involved.
Equipment: balance, Buchner flask with delivery tube and stopper, conical flasks, hydrometer,
sucrose, yeast, limewater ( ) ( ) .
Method:
1. Place the fermentation mixture of 6.5 sucrose, 2 dried yeast and 100 of warm water
into a 500 Buchner flask and swirl until thoroughly mixed. Weigh the flask.

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2. Measure 60 of limewater into two conical flasks and weigh one is for the collection of
carbon dioxide from the fermentation process, and the other is a control.
3. Place the sidearm of the Buchner flask into one of the limewater flasks.
4. Record appearance of fermentation mixture and limewater.
Results: The yeast flask became milky, foamy and smelt of alcohol, proving that ethanol was
produced. The limewater turned cloudy, proving that carbon dioxide gas was produced.
( ) ( ) ( ) ( ) ()

As the mass of the yeast flask steadily decreased each day (due to the inevitably escaping),
the limewater flask also gained approximately the same mass.
Risk Assessment: Safety glasses were worn throughout this experiment.

1.3.13 Identify data sources, choose resources and perform a first-hand investigation to
determine and compare heats of combustion of three liquid alkanols per gram and per mole

Aim: To determine and compare the heats of combustion of ethanol, methanol and butanol.
Equipment: Spirit burners containing ethanol, methanol and butanol, copper calorimeter, balance,
thermometer, matches.
Method:
1. Set up apparatus as drawn below:

2. Add 200 of water to the can. Place a thermometer in the water and record initial temp.
3. Weigh the spirit burner with its initial content.
4. Heat the water with the spirit burner until the temperature has risen by 10 C, and then
extinguish the flame. Reweigh the burner immediately and record final mass.
5. Repeat twice for each alkanol.
Results: In order of increasing : methanol, ethanol, butanol
Discussion: As molecular mass increases, more bonds need to be created for products. Since bond
formation releases energy, this leads to an increase in molar heat of combustion.
The experimental value of may have been less than the theoretical value because:
Molar heat of combustion is calculated under standard temperature and pressure. The soot
that formed indicated that the combustion was incomplete, and hence maximum energy was
not released.
Heat was lost from the can to the surrounding air, which would reduce accuracy. This could be
minimised by using a draught shield to reduce heat loss to surroundings.
Risk Assessment: Alkanols are flammable so the bulk supply was kept well away from the burner
and matches.

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1.4 Energy from Redox Reactions

1.4.1 Explain the displacement of metals from solution in terms of transfer of electrons

A displacement reaction is where a metal converts the ion of another metal into a neutral atom.

Active metals will displace less active metal ions from solution. The more active metal atom loses one or
more electrons and becomes a positive ion. The electrons lost are transferred to the ions of the less
active metal, resulting in them becoming metal atoms.

For example, zinc metal will displace copper ions from solution:

( ) ( ) oxidation (zinc loses electrons)

( ) ( ) reduction (copper gains electrons)
( ) ( ) ( ) ( ) redox reaction
The electrons lost by atoms undergoing oxidation are used to reduce ions to atoms.
Hence, no oxidation reaction can occur independent of a reduction reaction.

Oxidation is the loss of electrons, whereas reduction is the gain of electrons. These two reactions
must occur simultaneously, being known as a redox reaction.

1.4.2 Identify the relationship between displacement of metal ions in solution by other
metals to the relative activity of metals

A metal higher up in in the standard reduction potentials series is more reactive and will displace a
metal ion lower down from solution.

Spontaneous redox reaction will occur if the reductant is higher in the table of standard
reduction potentials than the oxidant.
The further apart the ions are (the greater the difference in activity between the two metals),
the more vigorous the displacement reaction, and thus more energy released.
Reactions between acids and metals are exothermic. The higher the metal in the activity
series, the greater the heat liberated in its reaction with an acid.

1.4.3 Account for changes in the oxidation state of species in terms of their loss or gain of
electrons

The oxidation state is a number given to an atom to indicate the number of electrons it has lost of
gained. This allows an understanding of the electron transfers of the system if it increases, then
oxidation has occurred and if it decreases, then reduction has occurred.

Rules for oxidation states:

1. The oxidation state of atoms and molecules in elemental form is always zero.
2. For monatomic ions, the oxidation state is the charge of the ion.
3. Neutral molecules have oxidation number zero.
4. The oxidation state of an element within a compound is its charge on the periodic table, and
the sum of all oxidation states of a compound (or polyatomic ion) is the charge of the ion.
5. Oxygen always has an oxidation number of number (except in peroxides and ).
6. Hydrogen always has an oxidation number (except in metal hydrides where it is ).

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 Module 1 Production of Materials

1.3.5 Describe and explain galvanic cells in terms of oxidation/reduction reactions

A galvanic cell (electrochemical cell) is a device that allows electricity to be generated from a
spontaneous redox reaction.

In a galvanic cell, there are two conducting terminals called electrodes one is the anode, and the
other is the cathode. Electrons flow from the negative anode of the oxidation half-cell to the positive
cathode of the reduction half-cell through an external circuit, occurring due to the presence of
electrolytes. This flow of electrons produces electricity, and the salt bridge completes the circuit.

The two active chemicals must not come into contact, as this would cause a direct reaction
and no electricity would be produced. The role of the electrolyte in cells is to keep the active
chemicals apart while allowing migration of ions through the cell.

1.4.5 Outline the construction of galvanic cells and trace the direction of electron flow

1.4.6 Define the terms anode, cathode, electrode and electrolyte to describe galvanic cells

electron flow external circuit

V

+
anions salt cations
anode cathode
bridge
(oxidation) (reduction

anolyte catholyte

Electrodes: The metallic conducting plates of a galvanic cell, involved in the redox reaction.
The anode is the negative electrode where the oxidation half-equation occurs. The cathode is
the positive electrode where the reduction half-equation occurs.
Electrolytes: Substance which in solution or molten conducts electricity as it releases ions.
The electrolyte solution must not form a precipitate with the other ions in solution, as this will
hinder the electrical conductivity (hence nitrates are typically used).
Salt bridge: The salt bridge serves two purposes in a galvanic cell.
Facilitates the migration of ions from one half-cell to the other to complete the circuit.
Maintains electrical neutrality as anions flow to the anode to neutralise the positive
charge developed by formation of cations, while cations flow to the cathode to neutralise
the relative negative charge accumulating due to reduction and removal of cations.

As galvanic cell reactions proceed, usually the mass of the anode decreases, while deposits of
metal form on the cathode. The anolyte colour becomes darker and the catholyte colour fades.

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 Module 1 Production of Materials

There are a variety of galvanic cells, each with different types of electrodes:

Electrodes that consist of metal dipped into a solution, containing the ion of the metal.
Electrodes that are an inert conductor (eg. platinum wire, graphite rod) dipped into a solution
of both an oxidised and reduced form of one element (eg. solution of both , ):
Oxidation: ( ) ( )

Reduction: ( ) ( )

Electrodes of a gas bubbling into a solution containing the oxidised or reduced form of the
gas, with an inert conductor dipping into the solution (eg. gas). The half-equations are:
Oxidation: ( ) ( )

Reduction: ( ) ( )

1.4.7 Solve problems and analyse information to calculate the potential requirement of
named electrochemical processes using tables of standard potentials and half-equations

Standard reduction potential ( ) is a measure of the relative tendency of a substance to undergo

reduction compared to the standard hydrogen electrode (0 ).

Standard cell potential is the sum of standard reduction potential and standard oxidation potential:

These are measured under standard laboratory conditions (25 C, 100 ,1 and 100% pure
electrodes) any change in these conditions will alter the voltage generated by the cell.

Positive cell potential indicates a spontaneous redox reaction will occur in forward direction.
The potential of a cell decreases as the reaction proceeds because the reactant is used up, so
it produces less current. Thus, batteries go flat when one of the reactants is all used up. No
further chemical reaction is possible so no more current is produced.

1.4.8 Gather and present information on the structure and chemistry of a lead-acid cell and
evaluate it in comparison to a button cell in terms of chemistry, cost and practicality, impact on
society and environmental impact

Lead-acid cell:

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 Module 1 Production of Materials

In a lead-acid cell, six cells (each ) are arranged in series to produce a battery. The positive
anode is a porous lead sheet, and the cathode is a lead sheet coated in compressed lead (IV) oxide.
These plates are joined together to maximise the area of contact between electrode and electrolyte of
sulfuric acid, which allow the cell to deliver a large current. Thin perforated fibreglass sheets separate
each electrode.

Rechargeable by the application of an external current. This is possible because the product of
the reaction ( ) is insoluble and stays in contact with the electrodes.
The battery is used during start-up to provide the energy for a cars starter motor. It is
gradually recharged during driving using electrical energy from the cars alternator.

Chemistry:

Anode ( sheet): ( ) ( )

Cathode ( powder on lead sheet): ( ) ( ) ()

Electrolyte:
Voltage: 12

Cost and practicality:

The batteries are relatively expensive due to the lead content. They are reliable and have a long-
lifetime of many years even in extreme temperatures; however this is limited by
disintegration from the electrode surface, lead corrosion or internal short-cutting. The battery can
also be recharged externally from a car by using a suitable transformer care must be taken as
rapid charging can cause explosive hydrogen gas to form. These batteries are heavy and bulky,
and have the lowest energy density of most rechargeable batteries, limiting their practicality.

Impact on society:

This battery allowed development of starters in vehicles, as it provides high currents over short
periods. It is also a useful storage battery for remote locations as it can be recharged by
connecting to solar panels or electric generators. It is also useful for emergency lighting.

Environmental impact:

Lead-acid batteries are recycled to retrieve the lead, as it is a heavy metal pollutant that is toxic to
organisms in the environment and causes anaemia in humans. The electrolyte is highly acidic and
corrosive, and can cause severe damage if spilled. Sealed lead-acid cells prevent acid cells prevent
acid fumes from causing corrosion.

Vanadium redox cell:

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 Module 1 Production of Materials

The silver oxide button cell is a small cell with an extremely high energy to weight ratio. In this cell,
zinc and silver oxide serve as the anode and cathode respectively. An alkaline substance ( ) serves
as the electrolyte.

Chemistry:

Anode ( ): ( ) ( ) ( )

Cathode ( ): ( ) () ( )

Electrolyte:
Voltage: 1.5

Cost and practicality:

The silver oxide button cell is widely used in cameras and watches, due to its light and small size
but relatively high output. Its ability to produce a very steady output is also ideal for medical
equipment such a pacemakers and hearing aids. It is not rechargeable, but is relatively cheap.

Impact on society:

This battery allowed the miniaturisation of electronic devices, such as hearing aids, increasing
portability of such devices. The high reliability of the cell has also had a large impact upon the
medical industry, as the lifespans of various medical devices such as pacemakers have been
extended. This impact has prolonged and improved the quality of life for some within the society.

Environmental impact:

The cell is not recyclable when the battery is exhausted and discarded, the toxic zinc heavy metal
and the alkaline pollutant within the cell are released into the environment.

1.4.9 Perform a first-hand investigation to identify the conditions under which a galvanic cell
is produced

1.4.10 Perform a first-hand investigation and gather first-hand information to measure the
difference in potential of different combinations of metals in an electrolyte solution

Aim: To measure the voltage when various combinations of metals are used in a galvanic cell.
Equipment: 100 beakers, filter paper as salt bridges, electrical leads with clips, voltmeter,
emery paper, zinc, copper, ion and magnesium metal and their electrolytes.
Method:
1. Clean the metal strips with the emery paper.
2. Place the solutions of zinc nitrate, copper sulphate, iron sulphate and magnesium sulphate
into separate beakers. Add the same metal to the beaker containing the related ion solution.
3. Form a galvanic cell by connecting the zinc and copper half cells with
strips of filter paper soaked in in solution (salt bridge).
4. Use the connecting wires to connect the metals to the voltmeter. The potential difference was
recorded, noting which electrode is positive.
5. Repeat with the other half cells, using different combinations.
Results: was found to be the strongest reductant and was the strongest oxidant.

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 Module 1 Production of Materials

1.5 Nuclear Chemistry

1.5.1 Distinguish between stable and radioactive isotopes and describe the conditions under
which a nucleus is unstable

A radioactive isotope (radioisotope) has an unstable nucleus

which spontaneously emits radiation ( , or ) and undergoes
a spontaneous transmutation.

An isotope is unstable (radioactive) if:

Atomic number is greater than 83 ( ): These

isotopes undergo nuclear fission to form smaller, more
stable nuclei.

Ratio of neutrons to protons (n:p ratio) lies outside

the zone of stability.
20: stable ratio is 1:1
50: stable ratio is 1.3:1
80: stable ratio is 1.5:1

The half-life of a radioisotope is the time required for half the atoms in a given sample to undergo
radioactive decay. The amount of radioisotope remaining can be calculated by:

( )

amount of radioisotope remaining

original amount of radioisotope
time half life

There are three types of radioactive decay alpha, beta and gamma.

Alpha emission:

The nucleus emits an alpha particle, which is essentially a helium nucleus ( ). Alpha particles
have an atomic mass of 4 and a charge of +2, and hence are ejected from unstable nuclei to
remove a surplus of protons and neutrons. An example is:

Alpha particles have the lowest penetrating power of all radiation, stopped by a sheet of paper.
However, they have the highest ionising ability as they have the highest charge.

Beta emission:

Beta particles are electrons ( ) that are released from neutron rich nuclei. Since the nucleus
contains an excess of neutrons, the nucleus will act to remove this by the decay of neutrons into a
proton and an electron. An example is:

Beta particles have moderate penetrating power, stopped by 0.5cm of aluminium, and have a
moderate ionising ability.

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 Module 1 Production of Materials

Gamma emission:

Gamma rays ( ) are high-energy electromagnetic rays. The emission of these rays are a means of
shedding excess energy as the nucleus changes from a high level to a lower level energy state
through the rearrangement of nuclear particles. It usually accompanies alpha and beta emission,
and only occurs in isolation of these when a metastable nucleus decays:

Gamma rays are extremely penetrating, only being stopped by 10cm of lead, and have a low
ionising ability as they carry no charge.

Ionising ability is the ability of a particle to strip electrons from another atom. It is directly related to
the charge of the particle, as a higher charge will give an atom a larger tendency to interact with other
charges either by attraction or repulsion. Thus, alpha radiation with a charge of +2 has a higher
ionising ability than gamma radiation which has no charge.

Penetrating power is the ability of a particle to travel through substances of varying thickness and is
dependent on its tendency to interact with the medium it is travelling through. A greater amount of
interaction will translate as a reduced penetration, as the particles motion is disturbed to a greater
degree. The progress of radiation can also be hindered by physical collisions, more likely to occur for
radiation with high masses. Hence, the higher the mass of radiation, the lower its penetrating power.

Radiation Identity Charge Mass Penetrating power Ionising ability

Alpha ( ) Helium nucleus +2 4 Low (sheet of paper) High
Beta ( ) Electron 1 1/2000 Moderate (aluminium) Moderate
Electromagnetic
Gamma ( ) 0 0 High (10cm of lead) Low
radiation

1.5.2 Describe how transuranic elements are produced

Transuranic elements are artificially produced elements with atomic numbers greater than that of
uranium ( 92). Uranium has the largest value of the naturally occurring elements.

Transuranic elements are produced by bombardment of nuclei with neutrons or other nuclei, in
nuclear reactors or particle accelerators.

Fission reactions (neutron bombardment):

Nuclear fission is the process in which neutrons bombard atoms and cause them to split. This
occurs in a nuclear reactor, a structure in which controlled nuclear fission occurs through neutron
bombardment. An example is the synthesis of neptunium and plutonium from uranium-238.

Fusion reactions (high-speed particle bombardment):

The production of larger transuranic elements is achieved by the bombardment of heavy nuclei
with high-speed particles (eg. ions) produced in particle accelerators, such as linear accelerators
and cyclotrons.

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 Module 1 Production of Materials

Linear accelerator: Particles are accelerated in a straight line along the axes of a series of
cylinders made alternatively positive and negative, so particles are continuously pushed and
pulled forward by the different charges.
Cyclotrons: Accelerate positive particles by passing them through alternative positive and
negative fields, but use an additional magnetic field to constrain the particles to a spiral path
which make the machine more compact.

Californium-246 is formed by bombarding uranium-238 with carbon in a linear accelerator.

( )

1.5.3 Describe how commercial radioisotopes are produced

Commercial radioisotopes are produced in nuclear reactors or particle accelerators.

Nuclear reactors:

Neutron bombardment is ideal as a projectile, as they have no electric charge and thus raises no
issues in overcoming electrostatic repulsion with the target nucleus. Nuclear reactors are also
significantly cheaper than particle accelerators. An example of a commercial radioisotope is
technetium-99m which is produced by the neutron bombardment of molybdenum-98 at a reactor
run by ANSTO at Lucas Heights.

Particle accelerators:

Particle accelerators accelerate light positive particles to high speeds, which are then collided with
heavy nuclei. Fluorine-18 is a medical radioisotope made in the Royal Prince Alfred cyclotron by
bombarding nitrogen-14 with helium nuclei.

1.5.4 Process information from secondary sources to describe recent discoveries of elements

Ununpentium Element 115 (Uup):

Element 115 was discovered by Russian scientists in 2004, following experiments carried out
during 2003 by scientists at Dubna in Russia as a collaboration with Lawrence Livermore National
Laboratory, USA. It is synthesised by bombarding calcium ions at a thin film of americium.

Ununseptium Element 117 (Uus):

Element 117 was discovered in Dubna, Russia, by a joint Russian-American collaboration (Joint
Institute for Nuclear Research). It is produced by the bombardment of a radioactive berkelium
target with Ca-48 ions in a cyclotron.

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 Module 1 Production of Materials

1.5.5 Identify instruments and processes that can be used to detect radiation

Cloud chamber:

Radiation detection can take the form of devices which trace the path of radiation, such as the
cloud chamber which contains supersaturated water or alcohol vapour that can be ionised by
radiation. Ions formed from this process act as centres of condensation, drawing nearby molecules
to form droplets which indicate the path of radiation. Magnetic fields can also be used in
conjunction as positive alpha particles are deflected in different directions from those of negative
beta particles while gamma rays are unaffected, allowing the type of radiation present to be
determined.

Geiger-Muller counter:

Nuclear radiation is able to ionise materials the Geiger-Muller counter is used to measure the
strength of ionising radiations. Beta radiation is readily detected, although the device can be
designed to detect other types of radiation. The radiation enters the tube via a thin mica window,
and ionises the argon gas present, causing the formation of ( ) and an electron. Due to their
negative charge, the electrons are attracted to the positively charged central wire (anode). An
amplified electric pulse is created at the anode and is detected by the digital counter. The positive
ions are attracted to the negative casing, and accept the electrons to complete the circuit.

The thin window serves two purposes to allow radiation with low penetrating power to be
detected, and to prevent the Argon gas from escaping.

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 Module 1 Production of Materials

1.5.6 Identify one use of a named radioisotope in industry and in medicine

Industry: Cobalt-60 (Co-60) is used to irradiate food to prolong its shelf life.
Medicine: Technetium-99m (Tc-99m) is used in the diagnosis of disease.

1.5.7 Describe the way in which the above named industrial and medical radioisotopes are
used and explain their use in terms of their properties

Cobalt-60 (Industry):

Cobalt-60 is produced by the bombardment of cobalt with neutrons:

Thickness gauge:

Co-60 is used as a thickness gauge in measuring the thickness of industrially produced

paper. The paper is passed in between a radiation detector and the Co-60, using the amount
of beta radiation that passes through as an indicator for how thick the material is. This
information is then fed back to the rollers, which automatically adjust to achieve the desired
paper thickness.
Beta radiation emitter: Moderate penetrating and ionising ability, hence changing the
thickness significantly decreases the amount of radiation that passes through without
causing damage to the paper.
Long half-life of 5.3 years: Does not require regular replacement, an important practical
consideration in industry.

Industrial radiography:

Co-60 is also used in industrial radiography to detect invisible cracks in pipes and structures.
Beams of radiation are directed at the object, while radiographic film detects the amount of
radiation that passes through to indicate where such flaws are. By studying the film, structural
problems can be detected.

Gamma radiation emitter: Co-60 is also a potent gamma emitter, radiation which can
easily penetrate structures for detection.
Chemically inert: When kept within a sealed container, it can be used in a chemically
inert form. This enables the equipment to have a long lifetime and require less
maintenance.

Sterilisation of food:

Co-60 can also be used to irradiate food materials to minimise spoilage and extend shelf-life.
Food on a conveyor belt is gamma irradiated by passing it through a chamber containing a
safely shielded Co-60 source, however this is not common in Australia.

Gamma rays can easily penetrate hermetically sealed packaging and its contents, killing
harmful microbes without making the food radioactive. However, there are concerns that
gamma radiation can destroy vitamin content in food and may lead to the formation of
harmful compounds in the food. In addition, workers must be protected from irradiation.

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 Module 1 Production of Materials

Technetium-99m (Medicine):

Tc-99m is produced by the following procedure:

1. Bombardment of molybdenum-98 with a neutron:
2. Emission of a beta particle:

Medical diagnosis:

Tc-99m is commonly used in nuclear medicine as a radioactive tracer. In this application, the
isotope is chemically attached to a molecule that has been chosen for its tendency to collect
in specific organs of the body and is injected into the patient. The Tc-99m then decays to Tc-
99 through the emission of gamma rays, and an image is collected with a gamma ray camera
for analysis. This technique is very useful in identifying cancers that spread to different
locations distant from primary tumours.
Short half-life of 6 hours: Its rapid decay means that it quickly eliminated from the body,
causing minimal damage. However, this means that the source of the radioisotope must
be stored and managed in close proximity to the hospital, or produced at the hospital,
both of which are costly.
Gamma radiation: The ionising ability of gamma rays is low, meaning that patient
damage is minimal, while the high penetrating power means that external sensors can
detect the radiation.
Chemically versatile: Can be combined with a variety of other chemicals to form
complexes which are taken up by specific body parts (eg. tin compound which binds to
red blood cells, detecting internal bleeding).

1.5.8 Use available evidence to analyse benefits and problems associated with the use of
radioactive isotopes in identified industries and medicine

Benefits:
Provided a range of non-invasive diagnostic techniques within the field of medicine.
Radiotherapy provides effective treatment of many cancerous tumours.
Monitoring equipment is more sensitive and precise than earlier equipment, carrying tasks
more efficiently (eg. gamma sterilisation of medical supplies, which is effective compared to
other sterilisation methods).

Problems:
Radiation from radioisotopes is harmful to humans and all other life forms. It can cause
undesirable reactions in living tissue and upset the delicate balance among the complex
chemical reactions occurring in living cells.
Continued exposure to radiation can lead to diseases such as tissue damage, cancer and
genetic damage which leads to deformities in offspring. Workers who work with radioactive
elements must be continually protected and avoid any form of irradiation.
Nuclear reactors (the source of neutrons) produce nuclear waste which must be disposed of
safely. The storage of radioactive material also presents a problem, as it must be kept in
shielded containers to prevent radiation leaks (eg. ANSTO uses a waste storage material called
synroc, which immobilises the waste in a glassy ceramic to prevent leaching by groundwater).

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