MATERIALS

In this topic students consider chemical and physical properties of a range of materials, and develop an
understanding of the chemistry behind these properties.
SUBTOPIC 6.1: POLYMERS
Polymers are important in nature and synthetic polymers represent one of the benefits of scientific advances.
Key Ideas Intended Student Learning
The production of synthetic polymers presents the Discuss the advantages and disadvantages of
opportunity to manufacture materials with a diverse synthetic polymers.
range of properties.
Polymers or macromolecules are very large molecules Identify the repeating unit of a polymer, given the
composed of small repeating structural units. structural formula of a section of a chain.
Polymers are produced from small molecules Identify a polymer as being the product of an
(monomers) by one of two main polymerisation addition polymerisation or a condensation
reactions: addition or condensation. polymerisation, given its structural formula.
Addition polymerisation occurs when monomer Draw the structural formula of an addition
molecules link without loss of atoms. The monomer polymer that could be produced from monomers
usually has at least one carbon–carbon double bond per containing one carbon–carbon double bond,
molecule. given the structural formula(e) of the
monomer(s), or vice versa.
Polyesters and polyamides are large molecules in Identify the ester link in a polyester and the
which monomer units are linked by ester and amide amide link in a polyamide.
groups respectively.
Condensation polymerisation occurs when one or more Draw the structural formula of the polyester or
compounds (such as water) are produced as the polyamide polymers that could be produced from
monomer molecules link. monomers, given the structural formula(e) of the
monomer(s), or vice versa.
Organic polymers can have different properties, such Describe the effect on rigidity of increasing the
as rigidity, depending upon the monomers and the number of primary and secondary bonds between
degree of cross-linking between chains. polymer chains.
Heat affects thermoplastic and thermoset polymers Describe the effects of heating on thermoplastic
differently. and thermoset polymers, and the consequent
difference in ease of recycling.
Fillers are used to modify the properties of polymers. Describe the advantages and disadvantages of
fillers in polymers.

Introduction
The term polymer literally means many parts. The term is used to describe large molecules or ions made by
joining many smaller units together with covalent bonds. Commonly there is one unit repeated up to
thousands of times to make one giant molecules or ion.

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The repeating units are often indicated in a structure by enclosed brackets and the formula of the polymer as
the formula of the repeating unit with a subscript ‘n’ to indicate the number of repeating units.

CH3

Si O

CH3
n

EXERCISE. : Draw brackets around the repeating unit on each of the following polymer segments and then
write the formula of the polymer next to it.
1.

2.

3.

4.

5.

Polymer molecules are:

 usually long chains, either linear or branched.
 They can be cross linked by covalent, hydrogen or dipole-dipole bonds. (eg DNA)
 Usually carbon based, but can be silicon or phosphorus based. (see Exercise above).
Common polymers include
 Polythene  Polyester
 Polystyrene  Rubber
 Nylon  Acrylics
The properties of polymers are diverse and can be designed for a particular end use. The properties that can
be manipulated include
 Flexibility  Colour
 Hardness  strength
 Melting point  density

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This is usually done by:

changing features like chain length, the extent of branching and cross linking and the polarity of side groups:
Adding substances like UV absorbers, plasticisers and dyes.
Polymers are used in
 plastic film eg Gladwrap  adhesives
 plastic sheets  paints
 fibres  lubricants
They are made into
 toys  computer components
 household utensils  furniture
The usefulness of polymers has lead to them replacing many traditional materials like metals, glass, cotton,
wool and timber. They have become so pervasive that we are becoming dependant on them and, since the
raw material that many of them are made from is oil, it is important that we find alternative energy sources to
preserve this raw material (oil).
Polymerisation reactions
Polymer molecules are formed from small molecules called monomers in reactions called polymerisation
reactions. There are two common types of polymerisation reactions – addition and substitution.
Addition polymers
These are formed when monomers with C=C groups are reacted (added together) under special conditions of
temperature and pressure with the aid of initiators. The double bond breaks and one pair of electrons from
bond is used to make a C–C link between monomers units. If the monomers units have only one double
bond, then the polymer has no double bonds.
The following diagram is a general representation of addition polymerisation.

From the structure of the polymer the monomer can be determined.

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Examples of addition polymers (+complete the empty boxes)

Monomer Polymer

Polyethene

Polytetrafluoroethene (‘teflon’)

orlon

polystyrene

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Condensation polymers
Condensation polymers are formed from monomers with two functional groups per molecule that can
undergo condensation reactions. Examples include polyesters and polyamides.
Polyester formation
Polyesters form from diol and dicarboxylic acid monomers eg

This example is polyethene terephthalate (PET). What are its monomers? What is its repeating unit?

EXERCISE: The following monomers can react to form a condensation polymer. Draw the structure of the
polymers, the repeating unit and labelling the connecting group.

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Polyesters from hydroxycarboxylic acids

EXERCISE: The following are diagrams of two polyesters. For each

 Circle the polyester links
 Circle the repeating unit.
 Draw the structures of the monomers they are made from.
Polyester 1:

Polyester 2:

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Polyamides
Polyamides have amide links holding the polymer chain together.

Polyamides form from diamine and dicarboxylic acid monomers in a condensation reaction.

Here is an example of the formation of nylon, a polyamide. Name the diamine and bracket the repeating unit
and link group.

EXERCISE : Draw the structure of the polymer formed from these to monomers and bracket the repeating
unit and circle the link group.

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Polyamides from aminocarboxylic acid monomers

EXERCISE: The following are diagrams of polyamides. On each diagram circle the amide links, bracket
the repeating unit and draw structures for the monomers that they could be made from.

Bonding between polymer chains

They type and strength of the bonding between polymer chains is determined by the polarity of side chain
groups and affects the properties of the resulting polymer.
Type of bonding Notes Effect on Polymer
Dispersion forces Between with nonpolar side groups Soft, flexible and nonelastic.
and main chain Low melting, softening point.
Strength increases with chain length (Thermoplastic)
Can be softened and reshaped repeatedly,
making them suitable for recycling.
eg polyethene, polypropene

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Type of bonding Notes Effect on Polymer

Hydrogen bonding Have polar O–H, N–H and/or C=O stronger, more rigid and elastic
groups present eg cellulose and polyamides
Covalent bonding Called crosslinks increased rigidity, elasticity, hardness and
With extensive crosslinking called a durability
resin eg epoxy resin, araldite, silicone rubbers
Amount off cross linking can be Thermoset Polymers
controlled.
The presence of double bonds in the
monomer enables cross linking to
occur

Rubber
Natural rubber is a soft solid. Its present usefulness occurred only after the discovery of the vulcanising
process. During this process, sulphur is added to the polymer chain to link between the chains. Varying the
amount of crosslinking changes the hardness and rigidity of the rubber. Note – extreme crosslinking has
produced the hard solid ebonite.

Thermoplastic and thermoset polymers

Thermoplastics are polymers that soften when heated and then return to their original condition when cooled.
There are only dispersion forces or hydrogen bonds between the polymer chains of these materials. They are
suited to recycling.
Thermosets are polymers that do not soften and change when heated. They have highly cross-linked
networks structures and must be shaped during the polymerisation process, because they set irreversibly. If
it is heated it will eventually start to decompose, commonly charring in the process. They are not suited to
recycling.

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Additives
Commonly used additives used to alter the properties of polymers include
Plasticisers small molecules that soften and improve the flexibility and strength of polymers
Flame retardants lower the ignition potential and rate of combustion
UV stabilisers slow down the degradation of polymer materials by UV radiation.
Antioxidants slow down the effect of oxygen on the polymer chains.
Heat stabilisers prevent the breakdown of polymers at higher temperatures.
Environmental Impact of polymers
Polymers are made from crude oil, which is non-renewable and therefore manufacturing based on this is not
sustainable.
Polymers are, in general, not biodegradable.
Disposal of wastes by incineration can release toxic additives into the environment.

ASSIGNMENT 6.1 : POLYMERS

1. A number of commonly used polymers begin with the prefix ‘poly’.
(a) Name three such polymers.
(b) By considering the structure of such polymers, justify the use of the prefix ‘poly’.
(c) Give the uses for the three polymers named in a).
(d) Is there a downside to the benefits of polymers? Explain.
2. The scientists Ziegler and Natta were awarded a Nobel Prize for chemistry in 1963 for their work on
polymerisation. Part of this work involved the polymerisation of propene into poly(propene)
What type of polymerisation forms polypropene?
(a) Draw a section of polypropene to show two repeat units.
(e) State two difficulties in the disposal of polypropene.
3. For the following part formulae for some polymers, give the structural formulae and names of the
individual monomer(s) that was/were used in the original polymerisation.
H H H H H
(a)
C C C C C

H H H H H
H H H H H
(b)
C C C C C

H H H

O O H H O
(c)
C (CH2)4 C N (CH2)6 N C

4. The polymer perspex has the structural formula shown:

COOCH3 COOCH3

CH2 C CH2 C CH2

CH3 CH3

(a) Draw a structural formula for the monomer of perspex.

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(f) Name the functional groups present.

(g) Write an equation to show how these monomers combine to form the polymer perspex.
(h) What name is given to this type of reaction?
(i) When the monomer of Perspex is heated under reflux with NaOH(aq), an organic acid and
alcohol form. Give the equation for this reaction.
(j) The NaOH(aq) present then reacts with the acid to produce a salt of this acid. Give the
equation for this reaction.
5. The woodworking glue, PVA, consists of a polymer which can be represented by the structural
formula (-CHOHCH2-)n.
(a) If PVA was prepared by a simple addition polymerisation, draw the structural formula for the
probable monomer molecule from which it would be prepared, and name the monomer.
(k) Suggest what PVA stands for, ie. name the polymer.
In practice, the monomer suggested in part (a) cannot be isolated. Instead the polymer PVA is
prepared indirectly from another polymer, which is prepared from vinyl acetate, CH 3COOCH=CH2.
(l) Vinyl acetate may be prepared by a simple addition reaction of the form A + B  C, where A
and B represent two readily available organic molecules (ethyne and acetic acid), and C
represents vinyl acetate. Draw the structural formulas of A and B and write a balanced
equation for the reaction.
(m) Draw the structure of an addition polymer of vinyl acetate and suggest a simple reagent which
might be used to convert this polymer to PVA.
6. Write a paragraph on each of the following topics. Be sure to include the chemistry, not just a
descriptive answer. Use specific examples where appropriate.
(a) ‘Proteins and polyamides are chemically similar’. Discuss this statement.
(n) ‘polymers are an indispensable part of life’. Discuss some types of polymers found naturally
and synthetically produced. Refer to types of polymerisation reactions which are used to
manufacture different polymers.
7. (a) Briefly explain the molecular difference between thermoplastics and thermoset polymers. Draw
suitable diagrams.
(b) Describe the effect of heat on thermoplastic and thermoset polymers. Which are the more
suitable for recycling and why?
(o) Sulfur is used to vulcanise rubber. Describe how this changes soft rubber into a useable
material.
(p) Inert fillers are added to detergents to form a crisp powder. What is the role of a filler in
polymers (eg. Carbon black).
(q) What are the environmental problems associated with the use of filler in polymers?
8. The following diagram represents part of the structure of a nylon polymer:
O O O

(CH2)6 N C (CH2)4 C N (CH2)6 N C (CH2)4

H H H

(a) Write the structure for the repeating unit for this polymer.
(r) Write the formulae of the monomers from which the polymer has been formed.
(s) Name the type of polymerisation process used to prepare this polymer.

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(b) Name the class of naturally occurring polymers which contain amide groups. State the name
normally used for the amide group in natural polymers.
9. Given the molecules ethylene glycol (CH2OHCH2OH) and terephthalic acid (HOOCC6H4COOH).
(b) Write a reaction equation for the formation of a polyester.
(t) Clearly identify the repeating unit.
(u) Classify the polymer as an addition or condensation polymer. (Give a reason)
(v) Give two reasons why some people may wish to see the use of plastics discontinued.
10. (a) Burning of plastics containing only carbon and hydrogen (eg. Polyethylene etc), gives CO 2(g)
and H2O(g). PVC (polyvinyl chloride) when burnt produces CO2(g), H2O(g) and an acid gas. What
acid gas is this likely to be?
(w) In many refuse tips limestone dust settles over the rubbish. When PVC is burnt with limestone
dust the acid produced is far less than expected. Why is this?

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11. Rubber that comes from the latex tree is quite soft, but becomes brittle in cold weather, sticky in hot.
Vulcanised rubber has far superior properties for use in rubber tyres.
(a) Describe the process of vulcanisation and the changes that occur to rubber molecules that are
vulcanised.
(x) Draw a diagram to show the arrangement of atoms in:
(i) natural rubber, like isoprene, which has the repeating unit:

(ii) vulcanised rubber.

(y) A lot of synthetic rubber is a copolymer of styrene and butadiene.
Given the following monomers,

draw the repeating unit of polystyrene butadiene (SBR).

(z) Discuss one disadvantage of vulcanised rubber.

Subtopic 6.2: Silicates

Silicates and aluminosilicates are the most common materials in the Earth’s crust. They form the basis of
rocks and most minerals and are the major components of soils. The silicates of which they are composed
determine the soils’ chemical properties. Healthy soils are essential for adequate food production.
Key Ideas Intended Student Learning
Silicon dioxide, silicates, and aluminosilicates are Write the formula of the anion in a silicate or
important components of rocks and soils. aluminosilicate, given its formula.
The structure of silicates is based on SiO4 tetrahedra. Identify the SiO4 structural unit in diagrams of
silicate anions.
In silicates oxygen atoms can be shared between two Draw the repeating unit and write the formula of
SiO4 tetrahedra. an extended silicate anion, given its structural
formula.
In silicates the oxidation state of silicon is +4 whereas State the charge on a silicate anion, given the
that of oxygen is –2. Si:O ratio.
The charge balance in silicate minerals is achieved by Write the formula of a silicate mineral, given the
the presence of cations, most commonly Ca 2+, Mg2+, structural formula of the silicate anion and the
K+, Na+, Fe2+, and Fe3+. metal ions present.
In minerals known as ‘aluminosilicates’, aluminium State the charge of an aluminosilicate ion, given
atoms replace some of the silicon atoms. its formula.
Cations held on the surface of soil silicates are in Explain how cations held on the surface of soil
equilibrium with the cations in soil water which are silicates are made available to plants.
available as sources of plant nutrients.
Soil silicates are able to adsorb H+ in the soil water and Describe the effect of acid rain in releasing
release cations. cations from soil silicates.
The surface of fine silicate particles in clays is Explain the use of aluminium ions in flocculating
negatively charged and can be flocculated into larger
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Key Ideas Intended Student Learning

particles by the addition of salts containing highly clay particles suspended in water.
charged cations such as aluminium ions.
Silicates such as zeolites are able to soften water by Explain the use of silicates in water softeners.
exchange of cations.

Silicates
Silicon is the second most abundant element in the earth’s crust. It never occurs as the free element in nature,
but is almost always combined with oxygen in the form of SiO 4 tetrahedral units.

These units can be linked into chains, rings, sheets or three dimensional covalent networks. These silicon-
oxygen structures, in the form of silicate minerals, make about 95% of crustal rocks.
The silicates often have metal cations incorporated into the structure. If these metals are transition metals,
they often impart a colour to the mineral.
The total positive charges of the metal cations in the structure must exactly balance the negative charges on
the silicate anions. Some also have some other anions like hydroxides, chlorides and fluorides. Water is also
often part of the structure.
Many silicate minerals contain aluminium in place of some of the silicon atoms. These are called
alumininosilicates.
Formulae of silicate and aluminosilicate anions
The formula of an anion can be deduced from the formula of a silicate in two ways:
 Using the charge balance
Show that in lawsonite, CaAl2Si2O7(OH)2.H2O, the Si2O7 unit has a charge of 6- using charge balance,
Show that in sodalite, Na8(AlSiO4)6Cl2, the AlSiO4 unit has a charge of –1 using charge balance.
Deduce the formula and charge on the silicate or aluminosilicate ion in the following minerals:
Talc Mg3Si4O10(OH)2
Natrolite Na2AlSi3O10.2H2O
 Using oxidation numbers
Show that in beryl, Be3Al2Si6O18, the Si6O18 is 12- using oxidation numbers
Show that in albite, NaAlSi3O8, the AlSi3O8 is -1 using oxidation numbers.
Deduce the charge on the following silicate or aluminosilicate ions:
Al2Si7O18
Al2Si3O10
Si4O11
Al2Si4O12
Silicate ion structure
Silicate structures are made of various combinations of SiO 4 units. The can exist as single units, chains,
sheets or three dimensional networks. Linking of SiO4 tetrahedra in this way produces polymer silicate ions

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in which the repeating units is used as the formula of the polymer ion. Note there are no Si-Si links, the
silicons are always joined via Si-O-Si links.
Some common silicate structures are shown below
Type of anion Structure of anion

4−
Individual SiO4 ions

6−
Individual Si2 O7

12−
Cyclic ions Si6 O18

2−
Single chains SiO3

6−
Double chains Si4 O11
eg Asbestos

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Type of anion Structure of anion

4−
Sheets Si 4 O10
eg talc

These structures determine the properties of the resulting mineral. eg the chains give fibrous or prismatic
crystals, the sheets give flaky minerals, the others are mainly hard 3-D crystals.
Soil silicates
Clays are one of the most important constituents of soils. They are made up of hydrated aluminosilicate
minerals with sheet structures stacked together to form layers.

In some clays, like kaolinite, the layers are held together by hydrogen bonding which prevents water entering
the structure.

Montmorillonite clay is a three-sheet structure. There is no hydrogen bonding possible between the oxygens
on the bottom surface of one layer and oxygens on the top surface of the layer below and so water molecules
and cations can enter the interlayer spaces.
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There is considerable substitution of magnesium for aluminium in the octahedral sheets and aluminium for
silicon in the octahedral sheets. Thus the surfaces have high negative charge. Cations such as K +, Na+, Ca2+,
NH4+, and H+ are adsorbed onto theses surfaces to balance the charge.

These clays have a number of important properties because of these structures:

 When water is added to these clays the cations become hydrated and some become detached from the
surface. As they move out into the space between the layers, they force the layers apart and the clay
swells. If the clay layers become completely separated, then dispersal of the clay as a colloidal
suspension results. This lowers the quality of soils and causes turbidity.
Dispersal of clays can be reversed by treating the colloidal suspension with solutions of highly charged
cations such as Fe3+ and Al3+. These attach to the negatively charged layers and pull the layers together
again. This process is called flocculation.
+
 When a solution containing cations like a fertiliser containing NH 4 or acid rain containing H+ ions is
added to clay, they can replace some of the adsorbed metal ions on the surface in a process called cation
exchange. An equilibrium between the ions in solution and those on the surface is established. If the pH
of the water is too low, then too many cations are released. Some of these cations, such as Al 3+, may be
toxic to plants.
 Zeolites are hydrated aluminosilicates with an open and stable honeycomb structure. The open spaces
contain water molecules and exchangeable cations. When hard water, containing Ca 2+ and Mg2+ ions,
passes through a bed containing zeolite beads, the ions replace sodium in the structure. This has the
effect of softening the water. Periodically the zeolite is ‘regenerated’ by flushing with concentrated
sodium chloride which reverses the ion exchange.

ASSIGNMENT 6.2 : Silicates

4
1. A geology text reads “the silicon tetrahedron, SiO 4 , is the most important ‘building block’ in the
architecture of the earth’s crust.
4
(aa) Draw the structure of SiO 4 and name the structure type.

(bb) Silica, SiO2, makes use of this structure. Explain
(cc) Olivine has the formula MgFeSiO4. Discuss the types of bonding present in olivine.


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6
12. Draw a diagram to show the structure of Si2O 7 , made by linking two silicate tetrahedral together.
Show charges.
13. The mineral beryl, Be3Al2Si6O18, contains a silicate structure.

(a) What is the charge on the Si6O18 ion?
(dd) Write a formula for another silicate mineral containing this silicate ion, but with different metal
cations.
(ee) Show the charges on all ions present in (b).
(ff) Is beryl an aluminosilicate? Give your reason!
14. Silicate ions are found in the Earth’s crust. If aluminium has replaced one or more silicons in the
silicate they become aluminosilicates.
(a) Selecting from this list of metal ions found in soil, Na, K, Ca, Mg, Fe(II) and Fe(III) and these

silicates Si2 O7
6− 12−
, Si 6 O18 , and (SiO2-3 )n write possible formulae for silicates containing
these ions:
Si 2 O 6−
7 Si 6 O12−
18 (SiO2-3 )n
(b) If one Al replaces a Si in the above anions write the formula with its charge.
(gg) Has the overall negative charge in (b) increased or decreased? How is the charge balanced?
15. What is the overall charge on these aluminosilicate ions? AlSiO7, AlSi5O18, Al2Si4O18.
16. Kaolinite, Al2(OH)4Si2O5, is one of the clay minerals. What structural feature of kaolinite could
account for its plasticity when mixed with water?
17. The ability of a clay mineral to exchange ions is measured by its cationic exchange capacity. Cationic
exchange capacities vary widely. What factors determine the cationic exchange capacity of a soil?
18. Many minerals in the earth’s crust are silicates, for which the basic building block is the silicate ion,
SiO 4
4 . These silicate units can join up in several ways. In clay minerals they occur as tetrahedral
2
sheets, which are negatively charged and can be represented by the formula (Si2O5 ) n . During
weathering of silicates Al3+ ions are substituted for some of the silicon atoms, leading to a variety of
 minerals. As well as these tetrahedral sheets containing some Al3+ ions, clays contain octahedral
aluminate sheets. The aluminate units consist of Al3+ ions bonded tooxide or hydroxide ions.
4
(a) (i) Draw an electron dot-cross diagram for the SiO 4 ion.
Silicon and carbon are both in Group IV. Explain why SiO2 is a solid but CO2 is a gas.
(hh) The diagram below shows the arrangement of the sheets in two different types of clay:


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A common example of a 1:1 type clay is kaolinite, whereas vermiculite has a 2:1 type layer
structure
Explain why in vermiculite water can force the layers apart, whereas in kaolinite this does not
happen.
(ii) (i) How is the negative charge on the silicate sheets balanced?
What effect do the substituted Al3+ ions have on the silicate sheets?
(i) Explain how clays can act as ion-exchange materials.
(ii) Why does wet clay have a characteristic sticky feel?
(jj) Suggest an explanation for the fact that in ion-exchange K+ ions are held more strongly on the
resin than Na+ ions.
19. In a laboratory experiment, a solution of ammonium nitrate(V) is allowed to seep slowly through a
sample of clay soil.
(a) Describe what happens to the ammonium ions and the nitrate(V) ions.
(kk) Ammonium nitrate(V) is commonly added to soils as a nitrogen fertilizer. Use your answer to a)
to explain why heavy rain can leach out nitrate(V) ions from clay soils more quickly than
ammonium ions.
20. (a) In nature H+(aq) from rain and from plants can displace Ca2+ and other ions from soils. What are
the effects resulting from this change?
(ll) As the pH of a soil increases the release of Al3+(aq) from the aluminosilicate ions begins. Why is
this a problem?
(mm) How can acidity in soils be reduced?
21. A solution of aluminium sulfate is added to a milky suspension made from a clay soil being shaken
with water. What would you observe and explain why.
22. Naturally occurring zeolite, an aluminosilicate mineral, has a much higher cationic exchange
capability than do clays. They are used to soften water.
(a) Explain how ion exchange columns are used to soften water.
(nn) Is this reaction reversible? What use is made of this?
(oo) Water softened by ion exchange should not be used for drinking. Suggest a reason for this?

SUBTOPIC 6.3: CLEANING AGENTS

Cleaning agents are familiar household chemicals that help in the maintenance of a healthy lifestyle. They
function in a variety of ways that include dissolving, suspension, and oxidation.
Key Ideas Intended Student Learning
Soaps form an insoluble material when used in hard Write an equation for the formation of
water. magnesium or calcium precipitate from soap,
given the structural formula of the soap anion.
The effectiveness of soaps is significantly reduced Describe how the reaction of soap with hard
when they are used in hard water, whereas the water differs from that of synthetic detergents.
effectiveness of synthetic detergents is not greatly
changed when they are used in hard water.
The structure of phosphates is based on PO4 tetrahedra. Draw the structural formula of the PO43 ion.
In tripolyphosphates oxygen atoms can be shared Draw the structural formulae of linear and cyclic
between PO4 tetrahedra. tripolyphosphate ions.

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Key Ideas Intended Student Learning

Tripolyphosphates are added to many detergent
formulations.
Tripolyphosphates improve the effectiveness of
detergent formulations.
Phosphates can cause eutrophication in bodies of
water.
Chlorine bleaches are most stable at a pH above 7.
Enzymes are added to some detergent formulations.
Oxygen bleaches involve the use of hydrogen peroxide
or oxygen as an oxidising agent.
Perborates are added to some detergent formulations
because they release hydrogen peroxide and hence
oxygen in solution.
Hydrogen peroxide decomposes to release oxygen.
State that tripolyphosphate ions keep calcium and
magnesium ions in solution, keep clay particles
in suspension, and keep the pH mildly alkaline.
Explain the importance of the actions of
tripolyphosphate ions.
Describe the advantages and disadvantages of the
use of phosphate fertilisers and polyphosphates in
detergent formulations.
Explain the effect of lowering pH on the
decomposition of hypochlorites to chlorine.
Describe the use of enzymes in detergents, and
explain why they are sensitive to changes in pH
and temperature.
State the change in oxidation number of oxygen
when hydrogen peroxide and oxygen act as
oxidising agents.
Describe how perborates release oxidising agents
when dissolved in water.
Explain why the effectiveness of perborates is
affected by changes in temperature.

Soaps and detergents

Dirt is a mixture of water soluble and insoluble substances. The water soluble parts can be washed off. The
insoluble substances are often fats which need soaps and detergents to remove them.
Soaps and detergents are surface-active cleaning agents, or surfactants, that are used to remove grease.
They are long hydrocarbon chain sodium carboxylates (soaps) or sulfonates (detergents) with structures like
those below.
The structural features that that distinguish a soap anion from a detergent anion are as follows
The ionic head of a soap anion is a carboxylate ion while the ionic head of a detergent anion is a sulfonate
ion;
The hydrocarbon chain of a soap anion is a straight chain, while the hydrocarbon chain of a detergent anion
is a straight chain that includes a benzene ring and one branch.

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How do they work?

The nonpolar hydrocarbon chains of soap and detergent are soluble in the nonpolar grease whereas the ionic
ends are not soluble. Thus the hydrocarbon chain dissolves into the grease with the ionic heads sitting on the
surface of the grease still in contact with water. When agitated, the grease globules, with soap/detergent ions
embedded in them, are dislodged from the surface to which they are attached. In water surface tension draws
these globules into spheres called micelles. The micelles repel each other because they have negatively
charged surfaces, and therefore do not join together. Spread through the water, they are easily washed away.
The are called surfactants or wetting agents that lower the surface tension of a liquid, allowing easier
spreading, and lower the interfacial tension between two liquids.

Formation
Soaps are produced by the alkaline hydrolysis of fats and oils. This is commonly called saponification. The
products of the hydrolysis are glycerol (propan-1,2,3-triol) and a carboxylate salt of sodium (soap) R-
COONa which is soluble in water.

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 MATERIALS

The main problem with the use of soaps as cleaning agents arises from the reaction of the soap anions with
dissolved calcium and magnesium ions to form a precipitate called ‘scum’ which can leave an unsightly
deposit on clothes, hair etc.
Ca2+
( aq) +
2RCOO−( aq)  (RCOO)Ca(s)
These ions are present in large amounts in ‘hard’ water, and they remove soap anions from solution meaning
more soap has to be used to get the same cleaning effect.
Detergents do not form scum and so retain the cleaning ability.
Tripolyphosphates in detergent formulations
Modern detergents may contain as little as 15% of anionic surfactant. The rest of the mixture contains
compounds that aid the surfactant like the water soluble sodium tripolyphosphate.
3−
Polyphosphate ions have various structures. They are based on the phosphate ion, PO 4 , which has a
tetrahedral shape. The other structures are based on the sharing of oxygens at the corners of the tetrahedra to
give cyclic or linear forms as shown below.

The tripolyphosphate ions serve three main functions:

They produce a slightly alkaline solution which keeps the soap anions in ionic form and helps dissolve
grease.
5−
P3 O10 + H O
5−
HP3 O10 -
2 + OH
They remove free Ca2+ and Mg2+ ions from hard water by forming water-soluble complex ions.
Ca2+
( aq) + P3 O5−
10  CaP3 O3−
10

They act as deflocculates that keep clay particles from settling back on the clothes being washed. Whereas
Ca2+ and Mg2+ ions reduce the repulsion between the clay particles and allow them to coagulate and settle

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 MATERIALS

onto the clothes. The tripolyphosphates, being negatively charged, prevent the negatively charged clay
particles from joining together.
Unfortunately the phosphates can find their way into natural waterways where they act as fertilizers for
algae. This causes algal blooms and can lead to eutrophication. The thick layer of algae prevents sunlight
reaching plants lower down, thus preventing photosynthesis and the replenishment of oxygen in the water.
When the algae die, dissolved oxygen is consumed as the organism decay. This creates anaerobic conditions
in the water and further decay produces anaerobic products such a hydrogen sulfide, ammonia and methane.
Aquatic animals that require oxygen for respiration die. In addition, some algae, notably blue-green algae
produce toxins that are released into the water. The water becomes unsuitable for consumption.
Enzymes
Modern detergent mixtures also contain enzymes which aid the break down of stains etc. by catalysing
hydrolysis reactions. They are especially effective a lower temperatures, but, being proteins, they are
sensitive to pH and temperature. To work in most washing machines they do need to work in temperatures
up to 60C and pH in the range of 8 to 10.5.
Bleaches
Bleaches are used to remove coloured stains by oxidising the coloured substances to colourless ones. Many
coloured compounds contain the C=C bond which can be oxidised.
There are two types of bleaches:
Chlorine bleaches, in which the active constituent is hypochlorous acid, HClO.
Oxygen bleaches, in which the active ingredient is hydrogen peroxide, H 2O2.
Both HClO and H2O2 are oxidising agents.
HClO is a stronger oxidiser than either the chlorine molecule, Cl 2, or the hypochlorite ion, ClO- and so
conditions that favour the formation of hypochlorous acid will increase the bleaching action. Commercial
bleaches for domestic use are either solutions of sodium hypochlorite or powdered calcium hypochlorite
which act as the source of hypochlorous acid.
OCl−(aq ) + H2O(l) HOCl(aq) +
OH−( aq)

Domestic bleaching solutions are made slightly acidic to remove OH- ions and move the equilibrium to the
right and thereby increasing the concentration of HClO. If the pH is lowered too much, the HClO
decomposes to give chlorine.
HOCl + H3O+ +Cl- Cl2 + 2H2O
Thus the bleach is more stable at higher pH’s.
The bleaching activity of hydrogen peroxide and oxygen is based on the chemical oxidation of stains by
these substances that themselves are reduced. The equations below show the reduction of the oxygen during
the reaction as the oxidation numbers decrease.
Type of oxidation Equation
−1 −2
Hydrogen peroxide as an oxidiser H2 O 2 + 2H+ + 2e  2H2 O
Oxygen can be used as an oxidiser. The −1 −2 0
source of the oxygen is the decomposition H2 O 2  2H2 O + O 2
of hydrogen peroxide.
0 −2
Oxygen under acid conditions O 2 + 4H+ + 4e  2H2 O
0 −2
Oxygen under alkaline conditions O 2 + 2H2O + 4e  4 O H-

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 MATERIALS

The most common and convenient source of hydrogen peroxide in laundry powders is sodium perborate
tetrahydrate, NaBO3.4H2O. When dissolved in water it decomposes, releasing hydrogen peroxide, which can
in turn decompose to form oxygen.
NaBO3.4H2O  NaBO2 + H2O2 + 3H2O
This is most effective if the material left to soak and decomposes faster at higher temperatures.

ASSIGNMENT 6.3 : Cleaning Materials

1. (a) What is a polar solvent? Give an example.
(b) What is a non-polar solvent? Give an example.
(pp) Describe the use of polar solvents to dissolve polar dirt and stains, and non-polar solvents to
dissolve non-polar materials.
23. This diagram represents a detergent molecule.
H H H H H H H H H H H H O

H C C C C C C C C C C C C S O- Na+

H H H H H H H H H H H H O

Which is the hydrophobic tail? Give a reason for your answer.

(b) Which is the hydrophilic tail? Give a reason.
(qq) Describe how soaps and detergents remove grease and dirt. Use diagram(s) and the terms
micelle and emulsion to assist with your answer.
24. Some of the ingredients in washing powders are listed. State the function of each and, where possible,
give an example.
Synthetic detergents and soap, builder, enzymes, blueing ingredient, brightening agent, perfume,
oxygen bleach.
25. Why do the instruments for removing protein stains with enzyme washing powders say that you should
soak the clothes at 40C? Will increasing the temperature increase the rate for an enzyme reaction?
26. Saponification is derived from the fact that the alkaline hydrolysis of fats produces soaps.
(a) Name the functional group present in all fats.
(c) State the experimental conditions necessary to obtain a high conversion of fat to soap.
(d) Write a full chemical formula for a soap.
(e) Glycerol is an important by-product in soap making. Give its formula and one use.
27. Sodium tripolyphosphate is a builder used in detergent mixtures.
(a) Explain how it assists in the cleaning process.
(f) The tripolyphosphate ion is a trimer. Write down the structure of this ion if it were a pentamer
(ie. a pentapolyphosphate)
(g) Sodium carbonate is also used as a builder.
(i) Explain with the help of an equation how it removes calcium ions from solution.
(ii) Explain with an equation why it is necessary to remove calcium ions when using soap.
(iii) Why is it not necessary to remove calcium ions when using a ‘soapless’ detergent?
28. Tripolyphosphates are added to many detergent washing powders. Explain the purpose(s) of sodium
tripolyphosphates in detergents.
29. Draw the structural formulae of linear and cyclic tripolyphosphate ions.
30. A washing powder states, ‘This powder complies with the agreed industry standards on phosphorus
which imposes a maximum content of 7.8g per wash. The level of phosphorus in our high performance
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 MATERIALS

powder is about 5.5g per wash.’

Why is it important that the use of phosphates in washing powders and in fertilisers should be
restricted?
31. Sodium perborate is a white crystalline powder made from sodium borate and hydrogen peroxide. It
has a formula NaBO2.H2O2.3H2O or NaBO3.4H2O. In water it releases hydrogen peroxide, which is a
powerful oxidant. The oxidation removes a lot of stains but not fast colours. It is most effective at high
(60C) temperatures.
(a) What is the oxidation state of oxygen in H2O2, and in oxygen?
(h) Write an equation to show H2O2 acting as an oxidant.
(i) When decomposing H2O2 has oxygen atoms that are both oxidised and reduced. Write an
equation for the decomposition of H2O2 and assign oxidation numbers to the atoms that change
their oxidation states.
32. Domestic bleaches are either oxygen based (eg. The perborates) or chlorine based (eg. The
hypochlorites).

(a) Complete and balance the equation: Cl2(g) + H2O

ClO−( aq) +
−
(j) Explain how the concentration of
ClO( aq) can be increased?
−
(k) Explain the effect of lowering the pH on the decomposition of
ClO( aq)

33. The formula for sodium perborate tetrahydrate can be given as NaBO 3.4H2O(s).
(a) Show by an equation why this compound is an excellent oxygen bleach.
(rr) Both enzymes and perborates are active ingredients in washing powders yet enzymes will not
react above 40C while perborates need a hotter environment (60C) to bleach. What is the
solution to this problem?
34. (a) Soaps have some advantages over synthetic detergents. List two.
(l) Detergents have some advantages over soaps. List three.

ASSIGNMENT 6.1 ANSWERS : POLYMERS

1. (a) Polystyrene, polythene, polyvinyl chloride (PVC), polyester, polycarbonate.
(b) Poly’ means many. Each of these is made from many units (monomer) covalently bonded to
make one very large molecule (polymer).
(ss) Packaging, pipes, bottle type containers, hoses, pipes, fibre for clothing.
(tt) Yes, they use finite resources to make, non biodegradable, and recycling can be expensive.
35. (a) Addition polymerisation
(b) Draw a section of polypropene to show two repeat units.
H H H H H H

C C C C C C

H CH3 H CH3 H CH3

(b) Very stable and expensive to recycle.

36.

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 MATERIALS

H H H H H H H
(a) ethene
C C C C C C C

H H
H H H H H
H H H H H H H
(b) styrene
C C C C C C C

H
H H H

O O H H O H H
(c) Hexane-1,6-
C (CH2)4 C N (CH2)6 N C H N (CH2)6 N H diamine
O O
Hexanedioic
HO C (CH2)4 C OH acid
37. (a)
H3CO

H C
O
C C

H CH3

(b) Alkene, ester

(uu)
H CH3 H CH3 COOCH3 COOCH3
C C C C
H COOCH3
+ H COOCH3
 CH2 C CH2 C CH2

CH3 CH3

(vv) Addition polymerisation

(ww)
H CH3 H CH3
H2 O OH- CH3OH
C C + C C +
H COOCH3 H COOH

(xx)
H CH3 H CH3
C C + NaOH C C + H2O
H COOH H COO- Na+

38. (a)
H H

C C ethenol
H OH

Polyvinylalcohol
(yy)
A + B  C
H H

H C C H + CH3COOH  C C

H OOCH3

ethyne acetic acid

26
 MATERIALS
H H H H

C C C C

H OOCH3 H OOCH3

(b) Sodium hydroxide could be used to convert the polymer to PVA

39. (a) Both are polymers. Protein is a natural polyamides (eg nylon) are commercially made. Both
contain – CO – NH – links, called peptide link in proteins. Hence proteins are often called
polypeptides. Proteins form from amino acids (diagrams may assist)
(b) Natural polymers are essential for life eg skin, flesh, hair. Casein plastic skin has been made
from milk for buttons and knitting needles. Silk is another natural polymer as is natural rubber.
Synthetic polymers with a wide range of very useful properties are made by two main reaction
types, addition polymerisation and condensation polymerisation. A typical addition reaction is
the formation of polythene from ethene.
40. (a) Thermoplastics (shaped by warming) have straight or branched chain molecules with no cross
linking. They remain plastic as there is little or no cross linking.

Thermoset plastics (rigid and hard will burn or char before melting) have large cross-linked
molecules to form a 3D network.

(b) Weak forces between polymer chains easily broken by heating. Thermoplastic can be moulded
into a new shape. Thermosetting polymer keeps shape on heating.
(b) Sulfur forms sulfide cross-links between the rubber polymer chains converting them from
thermoplastic to thermosetting.

Polymer chain is now hard and wears well

(c) Fillers modify the properties of polymers eg Carbon black makes rubber tougher and tear
abrasion resistant.
(d) Stronger and not able to be recycled. Give off pollutants if burnt.
41. (a)

O O O

(CH2)6 N C (CH2)4 C N (CH2)6 N C (CH2)4

H H H

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 MATERIALS

H2N(CH2)6NH2, HOOC(CH2)4COOH
(b) Condensation
(c) Proteins, Peptides
42. (a) + CH2OHCH2OH + HOOCC6H4COOH +  ..OO[CH2CH2OOCC6H4COO]nCH2CH2.. + nH2O
Condensation because it produces water
(b) Hard to dispose of, use up resources, difficult to recycle etc
43. (a) Hydrogen chloride, HCl
(b) It reacts with limestone: CaCO3 + 2HCl  CaCl2 + CO2 + H2O
44. (a) Heating rubber with sulfur. The polymer molecules become cross-linked with sulfide chains.
(b) (i) &(ii)

(c) Disposal. If burnt releases C(s), CO, SO2. It is tough.

ASSIGNMENTS 6.2 ANSWERS : SILICATES

1. (a) tetrahedron
O-

Si
-O O-
O-
(b) Each silicon is covalently bonded to 4 oxygens in a tetrahedra arrangement. Each oxygen then
links onto another silicon.
(d) There are covalent bonds within the SiO4 tetrahedron and ionic bonds to the Mg and Fe.
45.

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 MATERIALS

O- O-

Si Si
-O O O-
O- O-
46. (a) -12
(b) Mg3Ca3Si6O18
(b) Mg2+, Ca2+, Si6O1812-
(c) No, Al has not replaced a Si within the Si6O1812- unit.
47. (a)
6− 12−
Si 2 O7 Si6 O18 (SiO2-3 )n
Ca2FeSi2O7, , K2Mg2Fe2Si6O18 Can(SiO3)n
(b)
7− 13−
AlSiO7 AlSi 5 O18 ( AlSiO5-6 )n
(c) The negative charge has increased. This is balanced by extra cations.
48. AlSiO7 – (-7), AlSi5O18 – (-13), Al2Si4O18.- (-14)
49. Layer structure, with – OH present, means water can penetrate layers and is held by hydrogen
bonding  wet clay is soft.
50. Increased by bigger surface area, tetrahedral/octahedral/tetrahedral structure, eg. layered, the
cations present, low pH.
51. (a) (i)
.o
: O : O-
.x :
:
O . x Si . x
.o O .o Si
: .x :
-O O-
: O :

.o
O-

(ii) CO2(g) has weak intermolecular forces, SiO2 has continuous covalent bonding. Si is
larger than C, hence it can fit 4 oxygen’s around it.
(b) In vermiculite metal cations line the interlayer space and they are easily hydrated, with ion –
dipole bonds, to water. This absorption of water leads to the interlayer space expanding.
(c) (i) With cations
(ii) Increase the negative charge.
(i) Cations held on inner and outer layers of clay minerals can be replaced by different
ions from the soil solution. This is cationic exchange. An equilibrium is established. For
example add fertiliser (NH4)2SO4 to soil.
Clay – Ca2+(s) + 2NH4+(aq) clay – (NH4+)2(s) + Ca2+(aq)
(ii) Water is hydrogen bonded around the clay crystals gives wet clay its sticky (slippery)
feel
(d) K atoms are larger than Na atoms therefore K+ larger than Na+ therefore is more attracted to
spread of –ve charge on surface of clay.
52. (a) NH4+(aq) undergo cationic exchange onto clay surface. NO3-(aq) not attracted or held.
(b) NO3-(aq) not held onto clay surface
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 MATERIALS

53. (a) pH lowered, H+ not a nutrient, displaces nutrient eg Mg2+, Ca2+ from soils (leaching).
(c) Al3+ is toxic to plants
(b) Add bases, eg lime, CaO, limestone, CaCO3
54. The milkiness clears. Flocculation occurs. The Al 3+(aq) attracts the small negatively charged clay
particles (responsible for milky suspension) and as they collect (coagulate) they become too large
(floc) to be held in suspension.
55. (a) Ca2+(aq) and Mg2+(aq) exchanged with Na+(clay)
(d) 2Na+(clay) + Ca2+(aq) 2Na+(aq) + Ca2+(clay)
(b) Yes, recharge the softener with brine (concentrated sodium chloride solution)
(c) Ca2+ needed for bone development, high sodium levels are not healthy.

ASSIGNMENT 6.3 ANSWERS : CLEANING MATERIALS

1. (a) A liquid that contains polar molecules that dissolves other polar molecules eg water, meths
(b) A liquid that contains nonpolar molecules that dissolves other non-polar molecules.eg petrol
(d) ‘Like dissolves like’. Ionic compounds, polar compounds use water. Grease etc use non-polar
solvents. Soap is universal. Why?
56. (a) Hydrophobic, water hating – hydrocarbon chain (like dissolves like)
(b) Hydrophilic, water attracting – SO3- end
(b) Surfactants dissolve grease and, oils and attached dirt in the hydrocarbon end (hydrophobic),
agitation shakes them loose of the surface, and are then suspended in water as micelles
(spherical balls of surfactant) with the –ve end (hydrophilic) around the surface of the micelle
and the oil, grease, dirt and hydrophobic end inside. These micelles form an emulsion in water
ie. small insoluble groups spread out, but not coalescing. The dirt is not deposited because the
outer ring of –ve’s are mutually repulsive. The dirt is rinsed away with the micelles.

57. Detergent/soap – increase wetting power, loosen bond between fabric and dirt, keep dirt in suspension
Builder – softens, suspends dirt, sodium silicate, sodium carbonate, tripolyphosphate.
Enzymes – break down protein stains eg blood, gravy.
Blueing agent – whitens (by giving a blue touch to white clothes), blue dyes.
Brightening agent – makes whites and coloured clothes brighter, fluorescent agents.
Perfume – lemon, lavender etc give a fresh smell.
Oxygen bleach – sodium perborate monohydrate clean by oxidising bonds.
58. No, enzymes are denatured (destroyed) by higher temperatures.
59. (a) Ester functional group
(b) Heat, NaOH(aq) in excess, remove soap as it forms (salting out)
(c) Palmolive soap CH3(CH2)14COO-Na+ from palm oil, CH3(CH2)7CH=CH(CH2)7COO-Na+ olive
oil
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 MATERIALS

(d) Glycerol is use to make moisturisers and other cosmetics

H2C OH

HC OH

H2C OH

60. (a) Gives an alkaline pH to the solution. (alkalis react with grease, oils to form soap). Softens
water by reacting with Ca2+(aq) and Mg2+(aq) ions (which are responsible for hardness in water).
The Ca2+ and Mg2+ cannot then react with soap. This is called sequestering (means to exclude).
Outer –ve charges help to prevent flocculation of dirt. Also act as buffers to maintain an
alkaline pH.
(b)
O O O O O

P P P P P
-O
O O O O O-
O- O- O- O- O-

(b) (i) It forms an insoluble precipitate with Ca2+(aq)

ie Ca2+(aq) + CO32-(aq)  CaCO3(s)
(ii) Ca2+(aq) “destroys” soap by reacting with it, forming an insoluble compound called
scum.
Ca2+(aq) + 2C17H35COO-Na+(aq)  2Na+(aq) + Ca(C17H35COO)2(s)
(i) The Ca2+(aq) does not react with the detergent unlike soap, so no insoluble scum forms.
61. Tripolyphosphates soften hard water (they react with Ca2+, Mg2+ preventing these ions forming a scum
with soap); alkaline (helps reactions with grease/oils); prevent flocculation of dirt.
62.
O
O O O
P
P O
P P O- O
-O
O O O- O- -O
O- O- O- P P
O O O

63. Major environmental concern. It gets into water and provides nutrients for accelerated algae growth
(‘bloom’). This takes available oxygen from water so killing fish/plants.
64. (a) -1, 0
−1 −2

(b) H 2 O 2 +2H+ +2e− → 2H 2 O

−1 −2 0

(c) 2H 2 O 2 → 2H 2 O +O 2

65. (a) Cl2(g) + H2O

ClO−( aq) + 2H+ + Cl-
(b) Increasing the pH removes H+ and so the equilibrium moves to the right.
(c) Equilibrium concentration of ClO- reduced with lower pH ie [H+] increases and therefore
[ClO-] decreases

66. (a) NaBO3.4H2O 60 o C

⃗ NaBO2(aq) + H2O2 + 3H2O
H2O2  H2O + ½ O2(g)
(b) Soak with warm water less than 40oC before beginning hot wash cycle.
67. (a) Made from renewable materials (fats/oils/NaOH). Very effective cleaning agents (better than
detergents). Require less additives than do detergents.
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 MATERIALS

(b) Effective in hard water, do not form scum. Cheap to produce (while petroleum oil is cheap!).
Can be made biodegradable (as are soaps). Soluble at low temperatures and therefore cold
wash use.

32