PRODUCTION OF MATERIALS

Syllabus Section 1.1: Polymer Chemistry & Uses

Contents
1 Cracking of Petroleum Fractions

2 Properties of Alkanes and Alkenes

2.1 Physical Properties . . . . . . . . . . . . . . . . . .
2.2 Chemical Properties . . . . . . . . . . . . . . . . .
2.2.1 Alkanes (Substitution Reaction) . . . . . .
2.2.2 Alkenes (Addition Reactions) . . . . . . . .
2.3 Confirming that an addition reaction has occurred
3 Important Products
3.1 Ethanol . . . . .
3.2 Ethylene Oxide .
3.3 Ethylene Glycol .

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Derived From Ethylene

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4 Polymerisation of Ethylene
4.1 Methods To Produce Polyethylene . . . . .
4.1.1 Older Gas Phase Process Conditions
4.2 Ziegler-Natta Process (Newer) . . . . . . . .
4.3 Pictorial Representation of the Polyethylene
4.4 Steps Involved In Producing Polyethylene .
4.4.1 Initiation . . . . . . . . . . . . . . .
4.4.2 Propagation . . . . . . . . . . . . . .
4.4.3 Termination . . . . . . . . . . . . . .
4.5 Other Important Addition Polymers . . . .
4.5.1 Poly(vinyl Chloride) (PVC) . . . . .
4.6 Polystyrene . . . . . . . . . . . . . . . . . .

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5 Uses of polymers based on chemical structure

5.1 Crystallinity (Chain Branching) . . . . . . . . .
5.1.1 High-Density Polyethylene (HDPE) . .
5.1.2 Low-Density Polyethylene (LDPE) . . .
5.2 Chain-Stiffening . . . . . . . . . . . . . . . . . .
5.3 stability . . . . . . . . . . . . . . . . . . . . . .

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Section 1

Cracking of Petroleum Fractions

You may recall from the Preliminary Course of your work in the module, Energy. This HSC module
serves to be a continuation of your understanding of hydrocarbons and their uses in everyday life and in
industry. Let us revise some prerequisite knowledge you should already have in this area of chemistry.
1. Identify the raw material extracted to which we obtain petroleum fractions from and the industrial
process used to obtain these fractions. (2 marks)

2. Recall three petroleum fractions obtained from this process and name a use for each fraction.
(3 marks)

3. Draw the chemical structure of the compound, 2,4-methylhexane

4. Write a balanced chemical equation for the combustion of octane fuel

For this subsection, we focus on particular fractions obtained from the refining of crude oil which are
cracked into smaller chain fractions that are in higher demand.
5. Identify the fractions which undergo this cracking process. Hence, identify the name associated to
these fractions. (2 marks)

This cracking process is called catalytic cracking.

Catalytic cracking is a process where higher molecular weight fractions of crude oil are broken
into lower molecular weight substances in order to increase the output of high-demand products.
These higher-demand products are typically motor fuels (gasolene) used in cars, Liquified Petroleum Gases
(LPG) for cooking, heating etc. and more importantly, as an ingredient in the production of plastics.
Catalytic cracking operates in a column called a cat cracker. The process requires the use of a catalyst called zeolites which are crystalline aluminosilicates. Catalytic cracking can be further understood
through a series of chemical equations.
First Step
The higher molecular weight fraction is cracked into a smaller alkane and alkene. i.e.

Long chain fraction alkane + alkene

6. Write a chemical equation representing the first step in cracking pentadecane

Second Step
The alkene is then further cracked into smaller fractions. A smaller alkane and alkene is still produced
as with the first step. Typically, the alkene produced is ethylene (IUPAC: ethene) and an alkane.
7. From Question 6, write a 2nd chemical equation representing the cracking of the alkane.

However, these reactions will only occur if these conditions are met:
Temperature
Pressure
Catalyst / Initiator

Another cracking process is called thermal cracking. This process does not require the use of a catalyst
and requires on high temperature steam to decompose long chain fractions. Under specific conditions,
thermal cracking of long chain hydrocarbons will always produce ethylene, a small alkane and hydrogen
gas.
8. Write a chemical equation that represents the thermal cracking of tridecane (C13 H28 )

This can also work with the steam cracking of ethane.

9. Write a chemical equation that represents the thermal cracking of ethane

The conditions in order for these cracking reactions to occur and go forth can be summarised in a table.
Temperature
Pressure

Section 2

Properties of Alkanes and Alkenes

2.1

Physical Properties

By now, you should be aware of the physical properties of hydrocarbons and the reason why those
properties arise. We begin this section with some revision of your knowledge from the Preliminary
Course.
10. Define the term homologous series (2 marks)

11. Analyse the polarity of hydrocarbon compound and hence relate this to the physical properties they
exhibit. Data for physical properties (e.g boiling point, solubility etc.) is not required. Draw a
diagram to assist with your answer. (5 marks)

In terms of physical properties, hydrocarbons in the alkane, alkene and alkyne series share very similar
physical properties. However, their chemical properties differ greatly. We shall focus on the stark
difference in chemical properties between alkanes and alkenes.

2.2
2.2.1

Chemical Properties
Alkanes (Substitution Reaction)

Alkanes are relatively unreactive towards other reagents. The two most important chemical reactions
they are involved in are combustion reactions and substitution reactions. Let us illustrate substitution
reactions with an example.
12. Using structural formulae, write a chemical equation for the reaction between ethane and chlorine
gas.

Due to the unreactive nature of alkanes, substitution reactions will only go forth if U.V light is present.
The U.V light helps to break the bonds of the reactants to produce highly reactive free radicals

2.2.2

Alkenes (Addition Reactions)

Alkenes on the other hand are much more reactive than alkanes. This due to the weak nature of the double
bond in the alkene. As a result, the other reagent readily reacts with the alkene through an addition
reaction. We illustrate this with an example.
13. Using structural formulae, illustrate, via a chemical equation, the addition reaction between 1-butene
and hydrogen gas, via a catalyst.

We say that the reagent has been added over the double bond.

2.3

Confirming that an addition reaction has occurred

You will perform a first-hand investigation in your school laboratory to confirm an addition reaction
between an alkene and another reagent. The alkene commonly used is called cyclohexene and exists in
the liquid state.
14. Draw the structural formula for cyclohexene and cyclohexane. (2 marks)

15. Why would cyclohexene be better to use as opposed to ethylene? (1 mark)

16. Outline a procedure to determine if an addition reaction has occurred. A diagram will assist with
your answer. (4 marks)

17. Using structural formulae, write a chemical equation for the reaction between cyclohexene and
bromine water. You may assume bromine water is Br2 (aq). (2 marks)

18. Cyclohexane does not readily react in such a manner. However, under U.V light, a reaction will
go forth. Using structural formulae, write an equation for the reaction between cyclohexane and
bromine water under U.V light. (2 marks)

19. Outline some of the health issues that may arise from this first-hand investigation and ways with
which these issues can be minimised. (3 marks)

Section 3

Important Products Derived From

Ethylene
The high reactivity of ethylene leads to many addition reactions that can occur. Furthermore, changes to
reaction conditions and the use of catalysts will lead to the formation of different products. We discuss
some important products in this section.

3.1

Ethanol

The production of ethanol is very useful as a fuel-extender in motor vehicles that ensures cleaner burning
of fuel (more on this in Syllabus Section 1.3). Ethanol is also used as a solvent in perfumes, antiseptics
and food colouring.
20. Using structural formulae, write a chemical equation that represents the production of ethanol from
ethylene.

3.2

Ethylene Oxide

The production of ethylene oxide is a preliminary ingredient to the production of ethylene glycol. However,
it is readily used as pesticide. A silver catalyst is used.
21. Using structural formulae, write a chemical equation that represents the production of ethylene
oxide.

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3.3

Ethylene Glycol

This is the main product to be produced from ethylene oxide. Reacting it with water using dilute acid as
a catalyst produces the ethylene glycol.
22. Using structural formulae, write a chemical equation that represents the production of ethylene
glycol.

Ethylene glycol is used to produced PET plastics and used as an automotive antifreeze.

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Section 4

Polymerisation of Ethylene
We mentioned, in Section 1, that fractions such as gasolene and kerosene played the role as petrochemical
feedstock to produce smaller fractions that were in higher demand. We also learnt that cracking was the
method to produce these smaller fractions. Why is this so important?
You may recall from section 1 of the two most important reasons for the high demand of smaller molecular
weight fractions.

23. What are the two reasons for the high-demand of small molecular weight petroleum fractions?

The high-demand for small-chain hydrocarbons is met through the concept of polymerisation. Let us
define some new terms before moving on.
24. Define polymerisation and, hence, define polymer.

25. Define monomer

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4.1

Methods To Produce Polyethylene

There are two methods with which are used to industrially produce polyethylene. The process is similar,
in both methods, except one is older than the other and the reaction conditions are much more efficient
in the newer process.

4.1.1

Older Gas Phase Process Conditions

Temperature
Pressure
Initiator/Catalyst
Type of Polyethylene Produced

26. What is the difference between an initiator and a catalyst?

27. Draw the chemical structure of the initiator used in the older gas phase and the abbreviated form
we shall be using instead.

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4.2

Ziegler-Natta Process (Newer)

Temperature
Pressure
Initiator/Catalyst
Type of Polyethylene Produced

4.3

Pictorial Representation of the Polyethylene Produced

4.4

Steps Involved In Producing Polyethylene

We will now explain and illustrate the process of addition polymerisation of ethylene monomers to produce
polyethylene. For convenience, we will illustrate the process with the organic peroxide initiator. We
simplify the chemical structure to

We summarise the addition polymerisation process in three steps:

Initiation, Propagation, Termination

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4.4.1

Initiation

4.4.2

Propagation

4.4.3

Termination

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4.5

Other Important Addition Polymers

The same stages of initiation, propagation and termination apply to different kinds of monomers. These
will have different side groups and branches that allow for different types of plastics to be produced.

4.5.1

Poly(vinyl Chloride) (PVC)

28. Draw the structure of the monomer, vinyl chloride. Hence, give the IUPAC systematic name for
this monomer.

29. With reference to the stages of initiation, propagation and termination, illustrate, with diagrams,
the addition polymerisation process of 3 vinyl chloride monomer units.

30. Describe two uses of poly(vinyl chloride) and relate these two the properties and chemical structure
of polyethylene.

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4.6

Polystyrene

31. Draw the structure of the monomer, styrene. Hence, give the IUPAC systematic name for this
monomer.

32. With reference to the stages of initiation, propagation and termination, illustrate, with diagrams,
the addition polymerisation process of 3 styrene monomer units.

33. Describe two uses of polystyrene and relate these two the properties and chemical structure of
polyethylene.

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Section 5

Uses of polymers based on chemical

structure and properties
The most important properties to consider when manufacturing and using polymers as plastics in everyday
products is the physical properties they exhibit. These properties are:
Melting Point
Stability to Heat & Light as well as chemical stability
Mechanical Strength
Flexibility and rigidity
In the context of polymers, what gives rise to these properties are the following structural features that
most polymers will exhibit:
Average molecular weight (chain length)
Crystallinity (due to chain branching)
Chain-stiffening
Stability
Here, we will also shed light on some of the uses of two different types of polyethylene as well as polystyrene
and PVC.

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5.1

Crystallinity (Chain Branching)

We discussed the two methods with which we can produce polyethylene. These industrial methods are:
Older Gas Phase
Ziegler-Natta Process
You also illustrated, with pictorial representations, of the two different structures of polyethylene that
arise from these two industrial methods.
34. In the space below, sketch the chemical structures for the polyethylene produced from the ZieglerNatta Process and the Older Gas Phase. Hence, identify the name of each type of polyethylene.

35. Identify the main difference between these two structures

For a unit volume of polyethylene produced. you should notice that each type of polyethylene display different arrangements. One is more tightly packed while the other is more more spaced out. For this reason,
we identify that both types of polyethylene exhibit different densities and we highlight the importance in
the names:
High-Density Polyethylene (HDPE)
Low-Density Polyethylene (LDPE)
Their densities are due to the extent of their chain-branching. Chain-branching is essentially the presence
of side-chain alkyl groups off the parent chain of the polyethylene molecules.

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5.1.1

High-Density Polyethylene (HDPE)

The absence of chain-branching gives rise to their tight alignment and orderly arrangement, giving rise
to its high-density. The lack of side-chains is due to the use of the Ziegler-Natta Process. Why does this
mean for its physical properties?
36. Circle the appropriate physical properties attributed to HDPE:
High or Low Melting Point?
Hard or Soft Material?
Rigid or Flexible?
The second property of HDPE being hard is due to its dense alignment which we say the HDPE is very
crystalline. This leads to its everyday use in common consumer products:
37. Identify three uses of HDPE

5.1.2

Low-Density Polyethylene (LDPE)

As mentioned prior, LDPE is produced through means of the Older Gas Phase via the organic peroxide. We have illustrated through diagrams the extensive chain-branching of LDPE. This means the
polyethylene chains are further away from each other meaning a less dense molecular arrangement.
This also means its physical properties greatly contrast those of HDPE
38. Identify three uses of LDPE

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5.2

Chain-Stiffening

This involves associating a larger side-group to the polymer chain. A CH3 alkyl group added produces
polypropylene gives rise to chain stiffening. The styrene (phenylethene) group also gives rise to chainstiffening
39. In the space below, draw diagrams for the structure of a propylene and styrene monomer.
Chain-stiffening is useful in making plastics much more rigid as the side-groups prevent chain flexibility.
Polystyrene is the main candidate for chain-stiffening.
40. Identify three uses of polystyrene

5.3

Stability

The C C and C H bonds are very strong in polymer molecules and hydrocarbons in general. However,
we note the structure of the monomer, vinyl chloride. The C Cl bond weakens when exposed to UVLight. This causes the PVC pipe to decompose.
Hence, it is important that PVC pipes are kept under the ground with minimal exposure to the sunlight.
Additives are added to absorb the UV light and minimise degradation.
41. What are some of the uses of PVC?

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