(pentadecane ) (decane) (pentene)

(pentene) (ethylene) (propene)

The Production of Materials

1.1 construct word and balanced formulae equations of chemical reactions as they are encountered

- Crude Oil provides us with raw materials for making plastics technically called polymers
- Starting substance for making polymers is ethylene, obtained from crude oil by petrol refining or deliberate
decomposition of some

1.2 identify the industrial source of ethylene from the cracking of some of the fractions from the refining of
petroleum
Summary
- Crude oil must be refined before use
- First step in oil refining is fractional
distillation
- In this process, the components of crude oil
are separated by their boiling points
- The crude oil is vaporised by heating, then fed
into the bottom of the fractionating column
- The temperature falls as the vapour rises up
through the column
- The least volatile components (highest boiling
points) condense near the bottom while the
most volatile only condense when they reach
the top of the column
- Liquids are drawn off the column at various
heights

- Cracking: chemical process of breaking large hydrocarbon molecules into small ones
E.g. Breaking dodecane C
12
H
6
into octane C
8
H
18
and butane C
4
H
8

- There are two types of cracking: catalytic cracking and thermal cracking
Ethylene from catalytic cracking
- Generally more petrol is required than is obtained from fractional distillation
- Oil refineries need to balance their outputs (petrol, diesel, fuel oil) to match demands of the marketplace
- Therefore oil refineries increase the proportion of gasoline by converting some of the lower demand
fractions into gasoline
- This process is catalytic cracking
- Note: the products of a fractionating column in fractional distillation is called fractions
- fractionating column for separating crude oil and the fractions it produces
- Catalytic cracking: process in which high molecular weight (high boiling point) fractions from crude oil are
broken into lower molecular weight (lower boiling point) substances in order to increase the output of high-
demand products
- The column in which this occurs is called a cat cracker
- Alkanes with 15-25 carbon atoms per molecule are broken into two smaller molecules: one alkane and one
alkene
E.g.
C
15
H
32
-----> C
10
H
22
+ C
5
H
10

- The alkene is then spilt into smaller alkenes until either ethylene or propene (or both) is formed:
E.g.
C
5
H
10
----> C
2
H
4
+ C
3
H
6


- Products of catalytic cracking are alkanes of shorter chain lengths (used for petrol) and small alkenes
- The catalysts used for cracking alkanes are inorganic compounds called zeolites
- Zeolites: crystalline aluminosilicates (compounds of aluminium, silicon and oxygen with some metal ion
attached)
- This is used to reduce the amount of heat needed to crack molecules; usu carried out at 500
0
C in absence of
air and above atmospheric
- The ethylene and propene (the by-products of catalytic cracking) are starting materials for making plastics
(polymers)
- This production is insufficient to meet current needs for these chemicals
Ethylene from steam or thermal cracking
- Often some fractions of crude oil are decomposed completely to produce ethylene and propene called
steam cracking or thermal cracking
- Steam cracking/thermal cracking: a non-catalytic process in which a mixture of alkanes with steam is passed
through very hot metal tubes (700-1000
0
C) and just above atmospheric pressure to decompose the alkanes
completely into small alkenes such as ethylene, propene, and butane as well as hydrogen
- Steam is present as an inert diluent: allows for the process to operate at just above atmospheric pressure
(which enables easy flow of gases through the hot tubes), while keeping the concentrations of the reacting
gases low enough to ensure that the desired reactions occur

1.3 identify that ethylene, because of the high reactivity of its double bond, is readily transformed into many
useful products
Reactions of Alkanes
- For alkanes there are only two important reactions:
1. Alkanes burn in air to form carbon dioxide and water; in this combustion reaction that makes alkanes
useful to us as fuels (EXAMPLES)
2. Alkanes react with chlorine and bromine when the mixtures are exposed to ultraviolent light (dont react
in the absence of u.v light)
- These reactions are substitution reactions: an atom in a molecule is replaced by another atom or group of
atoms

Reactions of Alkenes
- Alkenes burn in air to form carbon dioxide and water (same way as alkanes) (EXAMPLES)
- However, presence of the double bond in alkenes makes them much more reactive than alkanes
- There are many substances which react with alkenes by opening out the double bond to form two single
bonds: there are called addition reactions
- ALKYL GROUPS??

- The reactive double bond in ethylene means that it can easily be converted into a range of very useful
products such as ethanol and starting materials for plastics (polymers) (DIAGRAM PAGE 11)
1. Reaction of ethylene with water to form ethanol
- Ethylene is converted to ethanol by heating it with water (steam) at 300
0
C at high pressure and using
phosphoric acid as a catalyst: (insert)
- This addition of a water molecule across a double bond is called a hydration reaction
- It is a special type of addition reaction

- Ethanol is widely used as a reactant and as a solvent in the making of pharmaceutical products and perfumes
to varnishes and plastics
- In the home it is used as an antiseptic and a solvent in such items as food colourings and flavourings and
many medications

- Ethanol belongs to a group of compounds called alkanols (continue, havent finished pg 12)

2. Catalysed reactions of ethylene with oxygen
- Ethylene glycol, made from ethylene is used for the manufacture of polymers and as an automotive
antifreeze
- The first step, react ethylene with oxygen in the presence of a silver catalyst to form ethylene oxide: (ADD
DIAGRAMS PG 12)
- Some ethylene oxide is used as a fumigant, while larger amounts are converted to ethylene glycol by treating
it with dilute acid solution: (insert)

- Other catalysed reactions are used to convert ethylene to starting materials for making a variety of plastics
Styrene has the structure: (INSERT)
E.g. Ethylene is heated to 150
0
C with chlorine and oxygen in the presence of a copper chloride catalyst to
form vinyl chloride ( starting material for making very common plastic)
- The most important reaction of ethylene is its conversion to polyethylene (or polyethene) in a reaction
called polymerisation

1.4 identify that ethylene serves as a monomer from which polymers are made
- Polymerisation: is a chemical reaction in which many identical small molecules combine together to form
one large molecule
- The small molecules are called monomers while the large product molecule is called a polymer
The monomer ethylene polymerises to form the polymer polyethylene: (PICTURE PG 13)
- These polymers are basically long alkane molecules where each molecule contains from a few hundred to a
few thousand monomer units
- The structure is abbreviated to:


- Where n is the number of monomer units in the molecule

1.5 identify polyethylene as an addition polymer and explain the meaning of this term
- Polyethylene is called an addition polymer
- Addition polymer: the polymer formes by molecules adding together without the loss of any atoms
- Basically each double bond opens out to form single bonds with the neighbouring molecules

1.6 outline the steps in the production of polyethylene as an example of a commercially and industrially important
polymer
- There are two processes used to make polyethylene

1.7 identify the following as commercially significant monomers: vinyl chloride, styrene by both their systematic
and common names
- Several other common polymers are addition polymers made from monomers in which one of the H atoms
of ethylene has been replaced by a different atom or group such as Cl or CH
3
.
- We can represent such monomers as CH
2
= CH X
- The polymer as: (INSERT pg 15)
- We can abbreviate it to: (INSERT)

vinyl chloride
- poly (vinyl chloride) or PVC, is made from the monomer, vinyl chloride CH
2
= CH Cl
- Systematic name for monomer: chloroethene ; Systematic name for polyer: poly(1-chloroethene)
- Apart from polyethylene, this is the cheapest and most widely used polymer
- Its structure: (insert PAGE 15)
- Abbreviation ( insert)
Styrene
- Another addition polymer is polystyrene, made from the monomer styrene
- Sometimes written as: (INSERT)
- Systematic name: phenylethene
- A segment of polystyrene: (insert pg 16)

Naming Polymers
- Polymers are named by putting poly in front of the name of the monomer
- Brackets are used:
when the monomer name is more than one word
E.g. monomer: vinyl chloride ; polymer: poly(vinyl chloride)
when the monomer name begins with a number
E.g. poly(1-chloroethene), which is the systematic name for PVC


ADD ADDITION POLYMERS HERE??
1.8 describe the uses of the polymers made from the above monomers in terms of their properties
Relating Properties and uses to structure
- In selecting a polymer for a particular use, important properties to consider are:
Melting or softening point
Stability to heat and light
Chemical stability
Mechanical strength
Flexibility or rigidity
- Another factor is cost: generally selected are the cheapest polymer that will do the job
- The properties of polymers depend on their structure. Important structural features for addition polymers
are:
Average molecular weight (or chain length)
Crystallinity (extent of chain branching)
Chain stiffening
Cross-linking

Average molecular weight
- Average molecular weight reflects the number of monomer units that combine to make on polymer
molecular
- Not all the molecules in a batch of polymer have the same molecular weight: there will be a range of
different chain lengths)
- For a given type of polymer, the longer the polymer chain ( higher the molecular weight) and the smaller the
spread of the molecular weights (as in: are they long or packed) , then the higher the melting point and the
harder the substance is
- SO WHEN TALKING ABOUT MOLECULAR WEIGHT, ITS TALKING ABOUT THE LENGTH?
Chain branching
- We can get chain branching (branch together into a chain) in polyethylene
- If polyethylene forms in long unbranched chains, these chains are able to intertwine and align closely
- This leads to an orderly arrangement and the substance becomes crystalline
- The high degree of crystallinity leads to high density, high melting point and a relatively hard and tough
material
- High density polyethylene crackles when it is crumpled (FOIL?)

- However, if there is a lot of chain branching then molecules are not able to get so close to one another
- So the material is non-crystalline or amorphous ( ADD FIGURE 1.3??)
- This leads to low density, low melting point, greater flexibility and softness
- Low density polyethylene is much softer and clingy
E.g. Gladwrap
Chain Stiffening
- Chain stiffening of an addition polymer involves putting a bigger side-group into the linear chain to reduce its
flexibility
- Changing from H of polyethylene to CH
3
of polypropylene stiffens the chain only slightly
- When the side-group is changed to a chlorine atom ( line in PVC) or to a benzene ring in polystyrene, both
much bigger than CH
3
group, the ability of the chain to flop around is greatly restricted
- The material becomes stiffer and much more rigid
Cross-linking
- The rigidity or hardness of a polymer can be increased by what is called cross-linking
- Cross-linking is a process in which two or more linear chains are joined together to form a more extended
two dimensional network (ADD DIAGRAM)
- More common in condensation polymers than addition polymers, however one example is vulcanizing of
rubber
- -S-S- bridges between pairs of linear chains makes it harder and more elastic

- Average Molecular weight, chain branching, chain stiffening and cross-linking can all be controlled during the
manufacture of various polymers. It is possible to tailor make molecules to make materials with specific
physical properties

Suited for:
- Kitchen utensils and containers
- tougher carry bags
- more rigid toys
- variety of building products
- wheely bins
- Pipes for transporting natural gas
Suited for:
(Soft)
- Electrical insulation
- Garden hoses
- Insulation on household electrical
wiring
(Rigid)
- Household items
- Drainage and sewage pipes
- Household guttering
- Window frames
Suited for:
- Tool handles
- Car battery cases

Solubility of addition polymers
- The mentioned polymers so far contains no OH groups or O atoms, so polymers cannot form hydrogen
bonds with water and thus are quite insoluble in water
- Polymers are generally hydrophobic (water repelling) meaning they are not easily wetted by water
Stability
- Most of the bonds in these polymers are strong C-C and C-H bonds and so these molecules are fairly stable
- Polytetrafluroethene has C-F bonds which are much stronger than C-H bonds thus it is the most stable
polymer discussed
- PVC has C-Cl bonds which are weaker than C-H bonds and are vulnerable to ultraviolent light (which can
break C-Cl bonds)
- Special additives are needed to protect from sunlight however PVC is extremely stable underground or in the
dark
- Strongest to weakest bond: C-F , C-H , C-Cl
- When heated in high temperatures: PVC decomposes to from hydrogen chloride which is extremely
corrosive
- Acrylics decompose to from hydrogen cyanide which is an extremely poisonous gas

Uses of Polyethylene, PVC, and Polystyrene
Low density polyethylene, LDPE
Properties:
- Extensive chain-branching
- lack of stiffening side groups
- lack cross-linking
- relatively soft
- very flexible
- fairly low melting point
- Not particularly strong

High density polyethylene, HDPE
Properties:
- Virtually no chain branching: molecules
are packed closely together
- Harder and stronger
- Higher melting point than LDPE
- Absence of chain stiffening and
cross-linking limits the hardness and
brittleness

Poly (vinyl chloride), PVC
Properties:
- Chain stiffening of Cl side groups
- Polar C-Cl bonds
- Results in quite strong intermolecular forces
- Hard inflexible polymer
- Degrades fairly quickly in daylight
(Inhibitor needed to absorb u.v light)
- Rigidity can be adjusted by adding
non-volatile plasticisers (softens it)


- Both PVC and polyethylene are cheaper than other plastics so they tend to be used unless the product
requires properties they dont have

Polystyrene
Properties:
- Most stiffened of common plastics
- Hard and Rigid
Suited for:
- wrapping materials
- disposable shopping bags
- flexible toys
- milk bottles
- squeeze bottles
- Furniture and ornaments
- CD Cases
- Drink glasses
- Foam drinking cups
- Foam packing materials
- Only C-C and C-H bonds: very stable to
heat and u.v. light
- Minimal chain branching: very crystalline
- Soft due to gas bubbles trapped inside
the polymerized material (actual polystyrene
is quite hard)

Summary
Polymer Name and Structure of Monomer Common Uses
Polyethylene
Common name: ethylene
Systematic name (ethene)
CH2 = CH2
LDPE: milk bottles, soft toys, wrapping
film (cling wrap)

HDPE: kitchen utensils and containers,
more rigid toys,
rubbish bins, tougher carry bags
poly(vinyl chloride) PVC Common: vinyl chloride
Systematic: (chloroethene)
CH2 = CH - Cl
electrical insulation, garden hoses,
drainage and sewerage
pipes, household guttering and
downpipes
polystyrene Common:styrene
Systematic: (phenylethene)

car battery cases, tool handles, modern
furniture, CD cases,
disposable drink cups (both foam and
clear), foam packing
material


OTHER ADDITION POLYMERS
2.1 discuss the need for alternative sources of the compounds presently obtained from the petrochemical
industry
- raw material for polymers: ethylene and propene from crude oil
- The world is going to use up all its available oil reserves within the next few decades
- How long oil supplies will last depends on our rate of consumption
- There is pressure to reduce energy use and develop alternative fuels due to greenhouse problem, and the
diminishing supply of oil increasing cost
- Major crude oil uses: fuel for cars, planes and trains
- Petrochemical industry (mainly plastics) consumes only about 3-5% of total oil used in the world today
- Alternative sources of raw materials for plastics: ethanol obtained from agricultural crops as a possible
source of ethylene for making polymers
- Others argue: as oil supplies diminish, costs will increase and oil will become too effective to use a fuel:
overall energy use will fall and alternative fuels will become cost effective (cheap to buy)
- The petrochemical industry will be less affected by price rises (as cost of raw materials less than cost of
finished products)
- Regardless of argument, it would be prudent for plastics industry to develop alternative sources of ethylene
and propene
- Ethanol, produced by fermentation of star and sugars from variety of agricultural crops, is prime candidate
for an alternative source of ethylene
- However, an even more tantalising (exciting) starting material for many polymers is cellulose as it is a major
component of plant material whereas starch and glucose are minor

2.2 explain what is meant by a condensation polymer
- Condensation polymers are polymers that form by the elimination of a small molecule (often water) when
pairs of monomer molecules join together
2.3 describe the reaction involved when a condensation polymer is formed
- Cellulose, formed from the monomer glucose, is a naturally occurring condensation polymer
- To illustrate condensation polymerisation:
1. Write glucose C
6
H
12
O
6
as HO C
6
H
10
O
4
OH
- Polymerisation occurs by elimination of water molecules from between pairs of glucose molecules:






- Alternatively we can write this condensation polymer reaction as:


- n molecules of glucose combine to form one molecule of cellulose (which contains n glucose units) by
eliminating (n-1) molecules of water
- So basically: if I 2 molecules of glucose make up one molecule of cellulose, 1 molecule of water was used
(Write two molecules and put box around the molecule of water made)



2.4 describe the structure of cellulose and identify it as an example of a condensation polymer found as a major
component of biomass
- Molecular formula: HO C
6
H
10
O
4
OH
- Structural formula:









- Structure 1 is quite cluttered , so chemists commonly abbreviate it to 2, leaving out C atoms: it is understood
that there is a C atom at every apex of the structure
- It has 5 carbon atoms and an oxygen atom that forms a puckered ring with OH groups on each of the 5 C
atoms
- Puckered ring: Bent in figure and not flat. Carbon forms tetrahedral shaped molecules and when they
connect, they form a ring that looks like molecules are poking upwards , downwards and diagonally
- The sides of the ring on which each OH group is positioned is important; swap an OH and an H on one C
atom and you get a different compound like galactose or mannose

- When glucose molecules combine to form cellulose, the OH on the right- hand C atom of one molecule
combines with the left hand OH, thus forming: (like where two molecules gets rid of one molecule of water)





(For clarity several H and OH groups have not been shown)
- Important notes:
For bonding to occur, alternating glucose units must be inverted (upside down)
This bonding produces a very linear molecule. The geometry of rings and C O C bond angles
cause this linearity

- Cellulose is the major component of plant material or of biomass
- Biomass is material produced by living organisms; mainly it is plant material but also includes animal
excreta and material made by algae

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

3.1 describe the dehydration of ethanol to ethylene and identify the need for a catalyst in this process and the
catalyst used + 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

- Ethanol is an alternative source of ethylene for the plastics industry
- Ethanol is an alkanol (section 1.5): an alkane with one H atom replaced by an OH
- Geometrical arrange of bonds in molecule: tetrahedral around each carbon
atom and bent around the oxygen atom
- For printing convenience we generally draw it with bonds at right angles
- (DRAW HOW U SEE THE TETRAHEDRAL SHAPE PG 30)

- Ethylene is made from ethanol by dehydration
- Dehydration is a chemical reaction in which water is from a compound
- Ethanol is dehydrated by heating it with concentrated sulfuric or phosphoric acid which acts as a catalyst



- Reverse reaction: the addition of water to ethylene is called hydration (end product is ethanol)
- Hydration also needs heat and a catalyst generally dilute aqueous sulfuric acid




- Dehydration and hydration are quite general reactions: they apply to any alkanol or alkene (WHAT ABOUT
ALKANE?)
- E.g. 1 pentanol dehydrated to 1-pentene and 3-hexane hydrated to 3-hexanol

3.3 describe and account for the many uses of ethanol as a solvent for polar and non-polar substances

- Ethanol is widely used as a solvent in the home and industry
- In the home, it is a common solvent in:
Cosmetics (perfumes, deodorants, after-shaves)
Food colourings and flavourings (vanilla essence, cochineal)
Medicinal preparations (antiseptics)
Some cleaning agents

- Ethanol is a good solvent for both polar and non-polar substances
- Polar substances: chloroform CHCl
3
and common ether CH3 CH2 O CH2 CH3
- Ethanol is a good solvents for polar substances because one H atom is replaced by an OH
end making it very polar
- In addition Ethanol can form hydrogen bonds with many other substances thus increasing its ability to
dissolve to dissolve substances like glucose, sucrose, carboxylic acids, amino acids and some proteins
- Ethanol is miscible with water in all portions ( from 100% water through to 100% ethanol due to hydrogen
bonding

- Because of its alkyl part, the CH3 CH2 , which is non-polar, ethanol often dissolves non-polar
substances (remember like dissolves like)
- Dispersion forces form between this hydrocarbon tail and the non-polar solute
- Non- polar: non-polar iodine, short-chain hydrocarbons such as pentane and heptane




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

Ethanol has a fuel
- Ethanol is a liquid which readily burns:
- It is an easily transportable liquid, often used as hikers and campers (to create fires and burn) and even
proposed as possible alternative liquid fuel for automobiles
- Used as a petrol extender (esp. during WWII): petrol containing 10-20% ethanol can be used in ordinary
petrol without any engine modification
- Modification is needed to use 100% ethanol

Advantages of using ethanol as fuel are:
- Renewable source and thus reduce use of non-renewable fossil fuel ( provided less fossil fuels are used to
make ethanol than to save it)
- Reduce greenhouse gas emissions (less CO
2
released from use of ethanol in cars compared to CO
2
released in
fossil fuels use to make the ethanol)
Disadvantages are:
- Large areas of agriculture land would be needed to grow suitable crops with consequent environmental
problems such as soil erosion, deforestation, fertilizer runoff and salinity
- Major environmental problems from disposal of large amounts of smelly waste fermentation liquors after
removal of ethanol

Ethanol as a
renewable resource
- Ethanol is used as
fuel for motor cars
to add or replace
petrol on the
grounds that it is a
renewable source
- Basically it is made
from: carbon
dioxide, water and
sunlight to produce
glucose, and when it
is burnt, it returns to
carbon dioxide and
water which can be
re-converted to
ethanol

- In Australia, many people add it to petrol to reduce consumption of crude oil, particularly local reserves of
oil are likely to run out
- Ethanol is neutral with respect to the greenhouse effect: the carbon dioxide that it liberates when it burns is
just that which was used in its synthesis
- Blue cycle: Greenhouse neutral
- Red: energy inputs are quite significant- the manufacture of fertilizers has large fossil fuel input and
distillation process (95% ethanol from 15% fermentation) requires much energy
- Currently ethanol has potential as a liquid fuel when oil runs out provided coal is available for making
fertilizers and supplying energy for distillation

THE CURRENT SITUATION IN AUSTRALIA?!?! (NEED TO ADD?)

3.5 describe conditions under which fermentation of sugars is promoted
- Sixty years ago the major source of ethanol was fermentation of starches and sugars from plant material
- Large supplies of quite cheap ethylene became available as a by-product of refining to increase yield of
petrol
- This ethylene was available close to places of greatest demand for ethanol , the industrial cities
- Hence it became more economical to produce ethanol from ethylene
- Fermentation is a process in which glucose is broken down to ethanol and carbon dioxide by the action of
enzymes present in yeast
- For fermentation:
1. Suitable grain or fruit is mashed up with water
2. Yeast is added
3. Air is excluded, and
4. The mixture is kept at about 37
o
C

- Enzymes in the mixture first convert any starch or sucrose in the mixture into glucose and/or fructose, then
other enzymes concert glucose