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12 Option A: Materials

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Essential ideas Light micrograph of high
carbon steel. It contains 0.65%
A.1 Materials science involves understanding the properties of a material, carbon by mass alloyed with
and then applying those properties to desired structures. iron. It is very strong but
brittle and is used for cutting
tools, high-strength wires and
A.2 Metals can be extracted from their ores and alloyed for desired
springs.
characteristics. ICP-MS/OES spectroscopy ionizes metals and uses
mass and emission spectra for analysis.

A.3 Catalysts work by providing an alternate reaction pathway for the


reaction. Catalysts always increase the rate of the reaction and are
left unchanged at the end of the reaction.

A.4 Liquid crystals are uids that have physical properties which are
dependent on molecular orientation relative to some xed axis in the
material.

A.5 Polymers are made up of repeating monomer units which can


be manipulated in various ways to give structures with desired
properties.

A.6 Chemical techniques position atoms in molecules using chemical


reactions whilst physical techniques allow atoms/molecules to be
manipulated and positioned to specic requirements.

A.7 Although materials science generates many useful new products,


there are challenges associated with recycling and high levels of
toxicity of some of these materials.

A.8 Superconductivity is zero electrical resistance and expulsion of


magnetic elds. X-ray crystallography can be used to analyse
structures.

A.9 Condensation polymers are formed by the loss of small molecules as


functional groups from monomers join.

A.10 Toxicity and carcinogenic properties of heavy metals are the result of
their ability to form coordinated compounds, have various oxidation
states, and act as catalysts in the human body.

One of the key roles of the chemist is to transform natural resources which are readily
available into more useful materials. Civilizations are sometimes characterized by the
technology they have developed to accomplish this. The Bronze Age, for example,
marks the time when the ancients were able to produce copper from smelted ores.
The extraction of iron from its ores in the blast furnace is probably one of the most
significant developments in the Industrial Revolution of the 18th century. These
technological advances, however, often came without a full understanding of the
underlying scientific principles. Today chemists are able to use their understanding of
the bonding and structure of materials to develop new substances with properties to
serve modern needs. This chapter discusses the materials we have used to make our life
more comfortable, and our understanding more complete. We outline the extraction
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12 Option A: Materials

and analysis of metals, the properties of


different addition plastics and their impact
on their environment, the use of catalysts
in improving the effectiveness of our
chemistry to bring about important changes
more effectively and more selectively,
and liquid crystals, superconductors, and
nanoparticles, which are modern materials
with interesting properties.

Computer graphic
of a molecular tube.
Nanotechnology, which
has grown rapidly since
the 1990s, involves the
construction of such devices.
It has been described as the
A.1 Materials science introduction
science of the very small
with big potential and could
revolutionize computing,
Understandings:
Materials are classified based on their uses, properties, or bonding and structure.
medicine, and manufacturing.
The properties of a material based on the degree of covalent, ionic, or metallic character in a
Each of the coloured spheres
compound can be deduced from its position on a bonding triangle.
represents a single atom:
Composites are mixtures in which materials are composed of two distinct phases, a reinforcing
carbon (blue), oxygen (red)
phase that is embedded in a matrix phase.
and hydrogen (yellow).
Guidance
Consider properties of metals, polymers, and ceramics in terms of metallic, covalent, and ionic
bonding.
See section 29 of the data booklet for a triangular bonding diagram.

Applications:
Use of bond triangle diagrams for binary compounds from electronegativity data.
Evaluation of various ways of classifying materials.
Relating physical characteristics (melting point, permeability, conductivity, elasticity, brittleness) of a

material to its bonding and structures (packing arrangements, electron mobility, ability of atoms to
slide relative to one another).
Guidance
Permeability to moisture should be considered with respect to bonding and simple packing
arrangements.

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Materials are classied based on their uses, properties,
or bonding and structure
Whereas most living things survive by adapting to their environment, human beings
have been particularly effective at doing the opposite. We have adapted the material
in our environment to meet our needs. Initially this was a trial and error process. We
made buildings out of strong materials such as wood, stone, and iron, made windows
and drinking implements from transparent glass, and attractive jewellery from shiny
minerals or precious metals.
A more systematic scientific approach has led us to identify and measure the
properties of different material more precisely and classify them into groups
accordingly. Metals are strong and malleable, glasses are transparent and brittle, and
ceramics are generally excellent insulators (superconductors are notable exceptions).
In recent times our chemical understanding has allowed us to make great advances in
the synthesis and uses of materials as we understand the link between their properties
and their structure and composition. If the focus is on understanding the properties of
a material, a classification based on its bonding and structure is helpful, whereas if we
are interested in its properties and possible uses a classification based on the material
type, metal, ceramic, composite, or polymer, is more appropriate.

% %
The properties of a material based covalent ionic
8 92
on the degree of covalent, ionic, or 3.0 electronegativity
difference
metallic character can be deduced 2.5 X = (Xa + Xb) ionic
from its position on a bonding triangle 25 75
2.0
The structure and bonding of the different substances
eneg

was discussed in Chapter 4. Although we generally 1.5 50 50


polar
classify solids as metallic, ionic, molecular, or giant
covalent
covalent this is a simplification as many materials show 1.0 75 25
intermediate properties. The bonding in a material is
determined by the magnitude and difference of the 0.5
metallic covalent
electronegativities () of the constituent elements.
This is illustrated by the triangle of bonding shown in 0.0 100 0
Figure 12.1. 0.79 1.0 1.5 2.0 2.5 3.0 3.5 4.0

To understand the triangle, consider the position of the average electronegativity X = (Xa + Xb)
2
elements caesium and fluorine and the binary compound
they react to form.
Figure 12.1 Metals have low
Substance average Position in triangle electronegativities and small
electronegativity differences,
Top of the triangle as 100% ionic
which places them in the
4.0 + 0.8 compound. Made up from the most
CsF = 2.4 4.0 0.8 = 3.2 lower left corner. Ionic
2 electropositive metal and most
compounds are found at the
electronegative non-metal. top centre. Covalent structures
Bottom left as 100% metallic. are found in the lower right
Cs 0.8 0.8 0.8 = 0 Cs has the lowest absolute corner. They are made from
non-metals that have high
electronegativity.
electronegativities.
Bottom right corner as 100%
F2 4.0 4.0 4.0 = 0.0
molecular covalent.

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12 Option A: Materials

The percentage ionic character of a compound can be approximated using the


formula:
D
% ionic characacter = 100%
3.2
According to this equation, sodium chloride is 72% ionic and hydrogen chloride is 32%
ionic. We describe the bonding in NaCl as ionic and HCl as polar covalent.

Worked example
Locate the position of the following substances on the triangle of bonding:
(a) diamond
(b) silicon dioxide
(c) bronze (an alloy of copper and tin).
Solution

Substance average

(a) diamond 2.6 0


1.9 + 3.4
(b) silicon dioxide = 2.65 3.4 1.9 = 1.5
2
1.9 + 2.0
(c) Cu/Zn = 1.95 2.0 1.9 = 0.1
2

% %
covalent ionic
8 92
3.0 electronegativity
difference
2.5 X = (Xa + Xb) ionic
25 75
silicon
2.0
dioxide
eneg

1.5 50 50
polar
covalent
1.0 75 25

0.5
metallic covalent
bronze diamond
0.0 100 0
0.79 1.0 1.5 2.0 2.5 3.0 3.5 4.0
average electronegativity X = (Xa + Xb)
2

There are four distinct classes of materials


Materials fall into four distinct classes: metals, polymers, ceramics, and composites.
We have discussed the properties of metals in Chapter 4 and polymers in Chapter 10.
Details of thermoplastic plastics, thermoset plastics, and elastomers are given later in
this chapter.

Ceramics are made by baking metal oxides and other minerals


to high temperature
The term ceramic comes from the Greek word for pottery. This class of materials is
so broad that it is often easier to define ceramics as all solid materials, except metals
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and their alloys, that are made by the high-temperature processing of inorganic raw
materials. Their properties are generally the opposite of those found in the metals.
Glasses and semiconductors can also be included in this class.
Ceramics can either form giant ionic or giant covalent structures, which explains why
they are so hard. The presence of ions also explains their brittle properties. A shear
force moves one layer of ions relative to another so that ions of the same charge are
forced next to each other (Figure 12.2).

(a) (b)
shear force Figure 12.2 Ionic materials
+ + + + and ceramics are brittle. (a)
A strong force is applied to a
layer of ions. (b) Ions of the
same charge are now closer
+ + together and so the top layer
repels the bottom layer and
the structure falls apart.
Ceramics can be porous materials as there are gaps in their structure that allow water
molecules to pass.
Glasses have many properties in common with ceramics as they are made from giant
covalent structures such as silicon dioxide fused with some metal oxide with an ionic
structure. The key difference is that glasses are transparent and waterproof. They are
made by cooling the molten mixture of silicon dioxide and metal oxide quickly so the
solid formed retains some of the disorder of the liquid. They are hard and brittle like
the ceramics.

Composites are mixtures composed of two distinct phases, a


reinforcing phase that is embedded in a matrix phase
A composite material is a mixture of two materials. Generally a composite material
is made up from fibres of a strong hard material embedded in a matrix of another
material (Figure 12.3). The properties of the composite depend on the properties of its
constituents.

fibre

Figure 12.3 A composite


matrix material has fibres of one
material embedded in a matrix
made from a different material.

If the composite is designed and fabricated correctly, it combines the strength of the
fibre with the toughness of the matrix to achieve a combination of desirable properties
not available in any single conventional material. Some composites also offer the
advantage of being tailor-made so that properties, such as strength and stiffness, can
easily be changed by changing the amount or orientation of the fibre.
The compositions of some common composites are shown on page 586.
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12 Option A: Materials

Composite Fibre Matrix

fibreglass glass plastic

carbon fibres carbon plastic

concrete steel cement

wood cellulose lignin

cermet ceramic metal

We can classify materials according to their composition, their bonding and


structure, or their properties. No single classification is perfect. How do we
evaluate the different classification systems we use in the different areas of
Light micrograph of fibreglass. Fibreglass is a knowledge? How does our need to categorize the world help and hinder the
lightweight, extremely strong, and robust material. pursuit of knowledge?
The plastic matrix may be a thermosetting plastic
or thermoplastic.

Some physical properties of materials


All solid materials have a number of physical properties. Here are some which affect
how different materials are used.

Property Comments

Melting point The temperature at which a solid begins to liquefy. Pure crystalline
materials melt at constant temperature. Glasses have no defined
melting point as they are generally mixtures. Thermosetting plastics
do not melt when they are heated but burn. The carbon atoms
combine with oxygen when the strong covalent bonds which hold
the structure together are broken. Themoplastics have molecular
covalent structures and so have intermediate melting points as
only intermolecular forces are broken when the plastic melts. The
melting points of metals generally increase across a period as more
delocalized electrons are used in bonding and decrease down a
group as an increase in ionic radius leads to reduced attraction
A technologist removing between the ions in the lattice and the bonding electrons. The
a sample of cermet from melting points of the transition metals are generally high as the d
a furnace. Cermet is a electrons are involved in bonding.
composite material made from
the ceramic boron carbide
Permeability The facility with which a material allows the passage of liquid or gas.
and the metal aluminium. Some ceramics and composites are porous as there are gaps in their
The cermet is lighter than structure. For example, pores can form in the matrix structure of
aluminium but stronger than cement which allows water to pass through the material.
steel.
Electrical A measure of the ability to conduct a current at a given potential
conductivity difference. Metals and graphite are good conductors in the solid
state as they have delocalized electrons which are free to move
throughout their structures. Ionic compounds can conduct electricity
in the liquids state or in aqueous solution where their ions are free to
move. Composites made from metal or graphite can conduct.

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Property Comments

Elasticity The ability of a material to return to its origin shape once the
stretching force has been removed. The physical reasons for elastic
behaviour can be quite different for different materials. In metals,
the atomic lattice changes size and shape when stretched. When the
stretching force is removed, the lattice goes back to the original as
the atoms are pulled back by the bonding electrons. Elastomers are
elastic polymers, generally with double bonds in their structure. Their
chains uncoil when a force is applied but return to a more stable
coiled arrangement when the force is removed. More details are
given later in the chapter (page 622).

Brittleness A brittle material breaks into parts when it is stretched. Ionic


and covalent bonds lead to brittle structures. Some ceramics and
thermosetting are brittle. This property is the opposite of toughness.
Metals and thermoplastics are tough.

Ductility / A ductile material can be stretched into long strands. Metals are
malleability ductile as their atoms can slide across each other without breaking
their metallic bonds. The delocalized electrons adopt a new
arrangement which ensures that the metallic bonding is maintained.
A malleable material can be squeezed into any shape. Metals are
malleable again because the delocalized electrons can accommodate
any changes in structure without breaking the metallic bonding.

Damaged concrete. Scanning


electron microscope of cracks
that have formed around a
trapped air bubble in a sample
of concrete that has been
damaged through chemical
reactions.

The properties of the different materials are summarized on page 588. These are only
general rules and there are many exceptions.

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Property Metal Ceramic Glass Polymer Composite

588
Melting Transition metals have the High: ionic and covalent High: covalent bonds are Thermoplastics have High: depends on the
point highest melting points bonds are strong. strong. low melting points as constituents.
as more electrons are intermolecular forces are
involved in bonding. Group weak. Thermosetting
1 metals have the lowest plastics dont melt but
melting points. Pure metals burn when heated to high
have fixed melting points; temperature.
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alloys melt over a range of
temperatures.

Permeability Low Can be porous as there are Low No Can be porous as there are
gaps in the structure. gaps in the structure.
Electrical High: there are delocalized Low Low, but some conductivity Low, but some polymers Generally low but can
conductivity electrons. at very high temperature as with extended delocalized conduct if structure
ions are free to move. electrons have been includes metal or graphite
synthesized which conduct which have delocalized
electricity. electrons.
Elasticity Generally low: some metals Low Low Low, but elastomers show Low, but carbon fibres
show elastic properties; elastic properties. show elastic properties.
steel springs for example. Elastomers uncoil when a
The distance between stretching force is applied
Option A: Materials

the atoms increase when but coil when force is


the metal is stretched but removed.
the atoms return to their
original position due to the
metallic bonding when the
load is removed.
Brittleness Low High: contain strong High: contain strong Some thermosetting Generally low, but depends
covalent or ionic bonds. covalent or ionic bonds. plastics, which have a giant on composition.
When force is sufficiently When force is sufficiently covalent structure, can be
strong to break these, the strong to break these, the strong but brittle.
structure falls apart. structure falls apart. Thermoplastics and
elastomers are not brittle.
Ductility High: metal ions can be Low High Low Low
pulled apart without
breaking the metallic bonds
as the delocalized electrons
can accommodate changes
to the lattice structure.

19/09/2014 09:53
NATURE OF SCIENCE
The use of materials has characterized the development of different civilizations in history. In
the stone age, humans used materials which could be modified for use by simple physical
processing but the iron age involved chemistry in which the element was extracted from
available minerals. Scientific knowledge during this period was limited and these were
essentially technological developments which relied on empirical knowledge gained through
trial and error. More modern times have been characterized by the use of materials such as
aluminium and plastic. This has relied on the application of available technology; the extraction
of reactive metals such as aluminium relied on the use of electricity, but more importantly
on our understanding of the link between the properties of a material and its structure. The
evolution of science has made our environment more accommodating through technological
developments and more understandable in terms of the models and theories we have
developed. Both these motivations continue to drive materials science forward. It is a cross-
disciplinary area of science which attracts scientists of different skills with different objectives. We
are now more aware of the impact on our environment of our use of natural resources. This has
made us more aware of our ethical responsibilities as scientists and brought new challenges.

Exercises
1 Identify which of the following statements refers to the composition of a composite material.
A It is a mixture in which one material acts as the matrix or glue.
B It contains at least three different materials, one of which is glue.
C It must contain a metallic element.
D It is a compound of two elements.
2 Use electronegativity values from section 8 of the data booklet to classify the bonding in the following
materials: Cl2O, PbCl2, Al2O3, HBr, and NaBr.
3 Copper oxide can be added to give glass a blue or green colour. Deduce the position of copper oxide
in the bonding triangle and describe the nature of its structure and bonding.
4 Explain why metals are ductile and ceramics are brittle.
5 Concrete is a composite of steel and cement. Outline its structure and suggest how the material could
conduct electricity.

Metals and inductively coupled


A.2 plasma (ICP) spectroscopy
Understandings:
Reduction by coke (carbon), a more reactive metal, or electrolysis are means of obtaining some
metals from their ores.
The relationship between charge and the number of moles of electrons is given by Faradays

constant, F.
Alloys are homogeneous mixtures of metals with other metals or non-metals.

Diamagnetic and paramagnetic compounds differ in electron spin pairing and their behaviour in

magnetic fields.
Trace amounts of metals can be identified and quantified by ionizing them with argon gas plasma

in inductively coupled plasma (ICP) spectroscopy using mass spectroscopy ICP-MS and optical
emission spectroscopy ICP-OES.
Guidance
Faradays constant is given in the IB data booklet in section 2.
Details of operating parts of ICP-MS and ICP-OES instruments will not be assessed.

Applications:
Deduction of redox equations for the reduction of metals.
Relating the method of extraction to the position of a metal on the activity series.
Explanation of the production of aluminium by the electrolysis of alumina in molten cryolite.

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12 Option A: Materials

Explanation of how alloying alters properties of metals.


Solving stoichiometric problems using Faradays constant based on mass deposits in electrolysis.
Discussion of paramagnetism and diamagnetism in relation to electron structure of metals.

Explanation of the plasma state and its production in ICP-MS amd ICP-OES.

Identify metals and abundances from simple data and calibration curves provided from ICP-MS

and ICP-OES.
Explanation of the separation and quantification of metallic ions by MS and OES.

Uses of ICP-MS and ICP-OES.

Guidance
Only analysis of metals should be covered.
The importance of calibration should be covered.

The method of extraction is related to its position in the


activity series
The ability to extract metals was an important technological step in the development
of our civilization. Some unreactive metals, such as gold and silver, occur in nature
as the free element. More reactive metals are found in rocks or ores as compounds,
combined with other elements present in the environment. These ores are usually
oxides, sulfides, or carbonates of the metal mixed with impurities. The extraction of
metals from these ores involves the reduction of the metal compounds (Chapter 9,
page 416) and the removal of impurities.
The method of extraction is related to the position of the metal in the reactivity series.

Metal Method of extraction


potassium
sodium
electrolysis of molten compounds
magnesium
aluminium
carbon
decreasing reactivity

zinc
chromium reduction of oxides with carbon/carbon
iron monoxide

tin
hydrogen
copper
silver occur native in the ground or produced
mercury by heating the ore

gold

A more complete activity series is given in section 25 of the IB data booklet.

Reduction of compounds using more reactive metals


The more reactive elements, at the top of the series, will reduce the oxides of the less
reactive elements at the bottom of the series. The practical use of this route depends on
the relative cost of the two metals involved.
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Magnesium could in theory reduce iron(III) oxide but is generally not used as the
magnesium is too expensive to be wasted in this way:
3Mg(s) + Fe2O3(s) 3MgO(s) + 2Fe(s)
However, aluminium is used to extract the more expensive chromium from its ores:
2Al(s) + Cr2O3(s) Al2O3(s) + 2Cr(s)

Metals in the middle of the series are extracted from their


oxides or sulfides with carbon
Coke, an impure form of carbon, formed by heating coal, is used as a relatively cheap
reducing agent for metals in the middle of the activity series.
PbO(s) + C(s) Pb(s) + CO(g)
In the case of lead and zinc the sulfide is the most available ore. The sulfide is first
roasted to produce the oxide, which is then reduced by carbon. Carbon monoxide is
often the product of the reaction.
2ZnS(s) + 3O2(g) 2ZnO(s) + 2SO2(g)
ZnO(s) + C(s) CO(g) + Zn(s)

Metal oxides can be reduced with carbon monoxide


Iron oxide is reduced with carbon monoxide in a blast furnace (Figure 12.4).
iron ore,
coke, limestone

hot gas used to


heat incoming air

250 C

700 C

furnace
gets
hotter
8001000 C

heat-resistant
brick Heamatite is a form of iron oxide (Fe2O3), mined as one of the
main ores of iron.
1500 C

hot air blast hot air blast

molten slag
molten slag
run off

molten iron
molten iron
run off Figure 12.4 A blast furnace.

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12 Option A: Materials

Iron ore, coke, and limestone (CaCO3) are added at the top of the blast furnace and a
blast of hot air is blown in from near the bottom.
The coke burns in the preheated air to form carbon dioxide:
C(s) + O2(g) CO2(g) H = 298 kJ mol1
The carbon monoxide acts as the reducing agent and reduces the iron(III) oxide:
Fe2O3(s) + 3CO(g) 2Fe(l) + 3CO2(g)

Less reactive metals can be produced by heating their ores


The less reactive metals at the bottom of the activity series can be extracted without
carbon as the oxides are unstable at higher temperature. Mercury is produced when its
sulfide ore, cinnabar, is heated in oxygen.
HgS(s) + O2(g) Hg(l) + SO2(g)

Cinnabar, an ore of mercury.

More reactive metals are extracted from their molten


compounds by electrolysis
As discussed in Chapter 9, reducing agents are suppliers of electrons. The most direct
way to supply electrons is via an electric circuit. The more reactive metals at the top
of the series, which cannot be reduced by carbon, are extracted using electrolysis. The
electrolysis of aqueous compounds of these metals cannot be used, as the less reactive
element hydrogen, present in the water, would be produced in preference to the metal
at the cathode.

The equations for the extraction can be deduced from


changes in oxidation numbers
Worked example
Copper is extracted from its sulfide ore by a combination of two reactions:
1 copper(I) sulfide is heated in air to produce copper(I) oxide and sulfur dioxide
2 the air supply is removed and copper(I) oxide is heated with excess copper(I)
sulfide to produce sulfur dioxide and the metal.
Identify the element that is reduced in both redox reactions and deduce the equations.

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Solution

1 Copper(I) sulfide has the formula (Cu+)2 S2 = Cu2S


We can write an unbalanced equation that has the oxidation numbers below
each element:
Cu2S + O2 Cu2O + SO2 unbalanced
+1 2 0 +1 2 +4 2 oxidation numbers (ON)

sulfur is oxidized: (2 +4): (ON) = (+4) (2) = +6


oxygen is reduced: (0 2) : (ON) = (2) (0) = 2
To balance these changes: three Os must be reduced for each S. The copper is
unchanged.
Cu2S + 3/2O2 Cu2O + SO2 balanced
+1 2 3/2(0) +1 2 +4 2(2)

multiplying by 2:
2Cu2S + 3O2 2Cu2O + 3SO2 balanced
2 The unbalanced equation with oxidation numbers below each element:
Cu2O + Cu2S Cu + SO2 unbalanced
+1 2 +1 0 +4 2 oxidation numbers (ON)

sulfur is oxidized (2 +4): (ON) = (+4) (2) = +6


copper is reduced (+1 0): (ON) = (0) (+1) = 1
To balance these changes: six Cu must be reduced for each S oxidized. The
oxygen is unchanged.
2Cu2O + Cu2S 6Cu + SO2 balanced

Aluminium is extracted from its ore


(bauxite) by electrolysis
Aluminium is the most abundant metal in the Earths crust and is
found in the minerals bauxite and mica as well as in clay. It was,
however, not discovered until 1825 by H.C. Oersted in Denmark.
It is a reactive metal which means that its compounds are
extremely difficult to break down by chemical reactions.
Nowadays, aluminium is a relatively cheap metal. The extraction
of aluminium from the mineral bauxite involves three stages.
Purification: the mineral is treated with aqueous sodium
hydroxide. Bauxite is an impure form of hydrated aluminium
oxide: Al2O3.xH2O. The amphoteric nature of the oxide allows it to be separated from Bauxite is the primary ore from
other metal oxides. Unlike most metal oxides, aluminium oxide dissolves in aqueous which aluminium is obtained.
sodium hydroxide. The soluble aluminium oxide is separated by filtration from the
insoluble metal oxides (iron(III) oxide) and sand.
Al2O3(s) + 2OH(aq) + 3H2O(l) 2Al(OH)4(aq)
The reaction can be reversed by passing carbon dioxide through the solution. Carbon
dioxide forms the weak acid, carbonic acid, which neutralizes solution.

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12 Option A: Materials

Napoleon III, the Emperor


Solvation: the purified aluminium oxide is dissolved in molten cryolite a mineral
of France from 1848 form of Na3AlF6. This reduces the melting point of aluminium oxide and so reduces
to 1870, owned an the energy requirements of the process. Pure aluminium oxide would not be a
aluminium dinner service suitable electrolyte because it has a very high melting point and it is a poor electrical
which was said to be more
conductor even when molten. Its bonding is intermediate between ionic and polar
precious than gold. The
high value reflects the covalent, as discussed earlier in the chapter.
difficulty of extracting the Electrolysis: the molten mixture is electrolysed (Figure 12.5). Graphite anodes are
metal at the time. dipped into the molten electrolyte. The graphite-lined steel cell acts as the cathode.

An amphoteric oxide 1 graphite anode


is an oxide that can act
either as an acid or a molten mixture
base. of aluminium oxide
and cryolite
Figure 12.5 The electrolysis of molten aluminium
molten aluminium oxide. collects on the floor
of the cell
The top of the Washington 2
Monument is a 2.8 kg tank lined with graphite cathode
pyramid of aluminium.
Installed in 1884, it was The negatively charged O2 ions are attracted to the anode, where they lose electrons
as valuable as silver at the and are oxidized to oxygen gas:
time.
2O2(l) O2(g) + 4e
In an electrolysis cell,
At the high temperature of the process, the oxygen reacts with the graphite anode to
the positive electrode
is called the anode and form carbon dioxide:
the negative electrode is
C(s) + O2(g) CO2(g)
called the cathode.
As the graphite is burned away, the anode needs to be regularly replaced.
The electrolytic extraction
of aluminium was The positive aluminium ions, Al3+, are attracted to the cathode, where they gain
developed almost electrons and are reduced to molten aluminium:
simultaneously by Charles
Martin Hall and Paul Al3+(l) + 3e Al(l)
Hroult, who worked
The aluminium produced by this method is 99% pure with small amounts of silicon
independently on different
sides of the Atlantic. and iron impurities. As the electrolyte contains fluoride ions, fluorine gas is also
They both discovered the produced in the process. This needs to be removed from the waste gases before they
process in the same year, pass into the atmosphere as it would lead to environmental damage.
1886. Both were born in
the same year (1863) and The need for high temperatures means that the process needs to be continuous to be
died in the same year economical. The cost of electricity is the most important factor to consider when
(1914).

Worker controlling the


pouring of molten aluminium
from a crucible into an ingot
casting vessel. This casting
is taking place at one of
the largest producers of
aluminium in Russia.

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deciding the location of an aluminium plant and they are often sited near hydroelectric
power stations. The high energy demand emphasizes the importance of recycling. The
energy requirements of recycling aluminium are less than 5% of that needed to extract
the metal directly.

The amount of metal produced depends on the number


of electrons supplied
The electric current (I) passing an point in an electric circuit is a measuring of the
amount of charge (Q) passing each point in a given time, t.
charge (Q) charge (Q) = current (I)
current (I) =
time ( t ) time (t)
This allows the amount of charge delivered to an electrolysis cell to be calculated from
the current and the time:
charge (Q) = current (I) time (t)
If the time is measured in seconds and the current in amperes, the charge is given in
coulombs.
To calculate the number of electrons, N(e), passing any point any second we need to
divide the total charge by the charge of one electron (e = 1.602189 1019 C). This
value is given in section 5 of the IB data booklet.
charge (Q)
N(e) =
1.602189 10 19 C
The amount of electrons, measured in moles, n(e), can be obtained by dividing this
number by Avogadros constant (L).
charge (Q)
n(e) =
1.602189 10 19 C 6.02 10 23 mol 1
This expression can be simplified by combining the constants to give a new constant:
Faradays constant (F) = 1.602 189 1019 C 6.02 1023 mol1 = 96 500 C mol1
Faradays constant is the charge of 1 mol of electrons. Faradays constant is
The amount of product formed by an electric current is chemically equivalent to the the charge of 1 mol of
electrons.
amount of electrons supplied; a statement of Faradays law of electrolysis. These
Faradays constant (F) =
relationships allow the amount of metal produced during electrolysis to be calculated 96 500 C mol1
from the current and time using the stoichiometric strategies developed in Chapter 1.
Faradays law of
Worked example electrolysis states that
Calculate the mass of aluminium that can be produced from an electrolytic cell in the amount of product
formed by an electric
one year (365 days) operating with an average current of 1.20 105 A.
current is chemically
Solution equivalent to the
amount of electrons
Equation at cathode: supplied.
Al3+(l) + 3e Al(l)
1 mol 3 mol 1 mol
n(Al) 1
=
n(e) 3
1
n(Al) = n(e)
3

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12 Option A: Materials

It is more economical to The number of moles of electrons can be calculated from the current:
recycle aluminium than
steel. The extraction of Q It
n(e) = =
aluminium requires more F F
energy than the extraction
of iron. 1.20 105 A 365 24 60 60 s
=
96500 C mol 1
This gives
1 1.20 105 365 24 60 60
n(Al) = mol
3 96500
m(Al) = n(Al) M(Al)
1.20 105 365 24 60 60
m(Al) = 26.96 g mol1 mol
3 96500
= 352 680 323 g
= 352 680.32 kg
= 3.53 105 kg

Exercises
6 (a) State the ore from which aluminium is extracted.
(b) Explain why aluminium is not extracted from its oxide by carbon reduction in a blast furnace.
(c) Describe and explain how aluminium atoms are formed during the extraction process.
(d) Explain why aluminium cannot be obtained by electrolysis of an aqueous solution of an
aluminium compound.
The aluminium drink can is (e) Explain the low conductivity of aluminium oxide.
the worlds most recycled (f) Explain with chemical equations why the carbon anodes need to be replaced at regular intervals.
container more than 63% 7 0.100 F of electric charge is passed through a saturated solution of copper(II) chloride. Calculate the
of all cans are recycled mass of copper produced and the volume of chlorine gas produced, assuming the reaction is carried
worldwide. You could watch out under standard conditions of temperature and pressure.
three hours of television on 8 A molten sample of titanium chloride was electrolysed using a current of 0.0965 A for 1000 s. 0.011
the energy saved by recycling 975 g of the metal was produced. Deduce the formula of the titanium chloride.
one aluminium can.
9 Methane is sometimes added to the preheated air in a blast furnace, instead of coke. Deduce the
equation for the complete reaction between methane and haematite (Fe2O3(s)), in the presence of air.
10 The extraction of titanium involves the conversion of titanium(IV) oxide to titanium(IV) chloride.
Carbon is oxidized to carbon monoxide in the process.
(a) Deduce the chemical equation for the reaction.
(b) Titanium(IV) chloride is reduced to the metal by magnesium. Deduce the equation for this
reaction.

Alloys are homogeneous mixtures of metals with other


metals or non-metals
The iron produced by the blast furnace contains about 4% carbon. This high level
of impurity makes the metal brittle and reduces its melting point. As this iron has
limited uses, the majority is converted into an alloy: steel. An alloy is a homogeneous
mixture containing at least one metal formed when liquid metals are added together
and allowed to form a solid of uniform composition. Alloys are useful because they
have a range of properties that are different from the pure metal. The presence of
otherelements in the metallic structure changes the regular arrangement of the
metalatoms in the solid, making it more difficult for atoms to slip over each other,
andso change the shape of the bulk material (Figure 12.6, page 597). Alloys are
generally stronger than the pure metal. Alloying can also make metals more resistant
to corrosion.

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An alloy is a
force force force homogeneous mixture
containing at least one
metal formed when
liquid metals are added
together and allowed to
pure metal alloy form a solid of uniform
The shape of a pure metal can be changed as The presence of atoms composition.
the atoms can easily slip over each other. of different sizes
disrupts the regular
structure and prevents Figure 12.6 An alloy is a
the atoms from stronger, harder, and less
slipping across each malleable metal than the pure
other. metal.

There is no single material called steel. Instead, steel is the general


name for a mixture of iron and carbon and other metals. Small
differences in the composition of the steel can produce a range
of different properties. This makes steel a versatile material with
properties that can be adjusted to suit its use.
Changing the composition of an alloy is not the only way to adjust
its properties. Different forms of heat treatment can change the
structure of the alloy. The atoms in a piece of metal are not all
arranged in a regular way. This is shown by the different orientation
of the squares in Figure 12.7. Areas of regular structure are called
crystal grains. The properties of an alloy depend on the size and
orientations of the grain boundaries.
Light micrograph of high carbon
steel. It contains 0.65% carbon
by mass alloyed with iron. It is
very strong but brittle and is
used for cutting tools, high-
strength wires, and springs.

Figure 12.7 The atoms in a metal are not all


perfectly arranged in a regular way. Areas of regular
structure are called crystal grains. The grain structure of brass, an
alloy of copper and zinc..
NATURE OF SCIENCE
The history of the extraction of the metals can be used to measure the evolution of civilization.
Most of the elements are metals and the history of their extraction illustrates many features
about the development of science and technology. Fire was the crucial agency which brought
about the extraction of metals and the mixing of alloys. Fire was originally considered to be
an element, but later came to be recognized as a form of energy. It breaks down ores like
malachite to the soft metal copper and facilitates the reduction of the ore haematite to the
hard metal iron. As there was limited scientific understanding as to the basis of these changes,
many experimental procedures were based on ritual or mysticism. The need to repeat
experimental procedure was recognized but as the underlying theory was not understood it
was couched in ritual language; to heat steel to the correct temperature to make a Japanese
sword it has to glow to the colour of the morning sun. The metal gold has always held a
special place in different cultures and became a focus for alchemy; gold is precious because it
is incorruptible and hence eternal. Gold resists decay and thus prolongs life. The alchemist saw
a sympathy between the metals of the earth and health of the human body. We now see these
false analogies as nave, but should appreciate that many scientific theories are also analogies
which have turned out to be false. The scientific theories of today solve the problems of today
but they are only provisional.
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12 Option A: Materials

Paramagnetic and diamagnetic materials display


different behaviour in magnetic elds because of their
different electron spin pairings
Materials are classified as diamagnetic, paramagnetic, or ferromagnetic based on their
behaviour when placed in an external magnetic field (Figure 12.8).
Diamagnetic materials are repelled by an external magnetic field as the orbital
motion of their electrons produces a very weak opposing magnetic field.
Paramagnetic materials are attracted by an external magnetic field as they have
unpaired electrons which behave like small magnetics which align with the external
field. The level of magnetization is proportional and in the same direction as the
applied field. All atoms have orbiting electrons and so show diamagnetic behaviour
but paramagnetic behaviour dominates in cases of single atoms or ions with unpaired
electrons.
Substances with paired electrons are diamagnetic, as electrons with opposite spins
behave like minute bar magnets with opposing orientation and so cancel each other
Figure 12.8 The electrons in out.
an atom have two types of
motion which both lead to
Many individual atoms and ions have unpaired electrons and display paramagnetic
magnetic effects, equivalent to effects. Chemical bonding often involves the pairing of electrons and so most materials
that of the bar magnet shown. with ionic and covalent structures are diamagnetic. Free radicals and some transition
(a) Orbital motion leads to metal ion complexes have unpaired electrons and so display paramagnetic effects. The
diamagnetic behaviour. (b)
interaction of electrons is more complex in metallic structures and some metals are
Electrons lead to paramagnetic
behaviour. paramagnetic.
Ferromagnetism occurs when materials retain their
magnetism after they have been removed from an
(a) (b)
external field. It occurs in materials containing iron,
N cobalt, and nickel where there is long-range ordering of
e e the unpaired electrons, which remains in regions called
nucleus domains after the external magnetic field is removed.
N

S
Ferromagnetism is the largest effect, producing
S

magnetizations sometimes orders of magnitude greater


than the applied field.

Paramagnetic materials Worked example


are attracted by an
Distinguish between the magnetic properties of H2O and [Fe(H2O)6]3+.
external magnetic field
as they have unpaired Solution
electrons. Diamagnetic
materials are weakly All the electrons are paired in the water molecule and so it is diamagnetic.
repelled by an external
magnetic field. They The Fe3+ in the complex ion has the electron configuration [Ar]3d5 and so has 5
have no unpaired unpaired electrons. It is paramagnetic.
electrons.

Exercises
11 Alloys of aluminium with nickel are used to make engine parts. Explain why this alloy is used rather
than pure aluminium.
A free radical is a species
with an unpaired 12 Classify the period 3 atoms as paramagnetic or diamagnetic and explain your answer. Identify the
electron. element which is likely to show the strongest paramagnetic properties.
13 Arrange the following atoms in order of increasing paramagnetism and explain your choice: K, Sc, V,
Mn, Ga, As.

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Inductively coupled plasma (ICP)
spectroscopy determines the identity and
concentration of metals
Inductively coupled plasma optical emission
spectroscopy (ICP-OES)
Inductively coupled plasma (ICP) spectroscopy is one of the most
powerful and popular analytical tools for the determination of
metals and other elements in a variety of different samples. The
technique is based upon an analysis of the elements emission
spectra. We saw in Chapter 2 (page 71) that an emission
spectrum is produced when the radiation from an excited
sample is analysed. A line spectra is produced, with each line
corresponding to an electron transition between different energy
levels as electrons fall from a higher to lower energy levels. As
each element has a unique set of energy levels it produces its own
distinctive emission spectrum which can be used to identify the
element (Figure 12.9).
The intensity of the lines depends on the concentration of the
element in the sample. In ICP the sample is injected into a high-
temperature argon plasma and the photons corresponding
to the different frequencies are separated using a diffraction
grating and counted using a photomultiplier which generates an
electric signal.

(a) Flame emission spectra of


Group 1 and Group 2 metals,
sample in high as recorded by Robert Bunsen
energy level (18111899) and Gustav
emission spectrum
Kirchhoff (18241887). They
were the first to observe that
heated elements emitted
a light of characteristic
wavelength.
(b)

argon plasma at very Figure 12.9 (a) An emission


photons photons of different data output
high temperature spectrum is produced from
emitted frequencies separated count rate of
coupled inductively to by diffraction grating photons at an excited atom when an
radio frequency and measured by different n/ electron drops from a higher
source photomultiplier to a lower energy. The different
lines correspond to different
transitions. (b) In ICP the
sample injected sample is excited by injecting
it into an argon plasma.
The emitted photons are
Plasma is a high energy state composed of isolated atoms, analysed using a diffraction
ions, and electrons. grating and photomultiplier.
The high temperature of the
The plasma state occurs at very high temperatures when some or all of the gaseous argon plasma is generated by
atoms have been ionized. The interactions in the plasma are dominated by charge coupling the argon to a high-
interactions between positive ions and electrons. The atoms and ions in the plasma are energy radio frequency coil.
excited and emit photons at characteristic frequencies.
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12 Option A: Materials

The high temperature of the argon


plasma is generated by inductively
coupling the gas to a high-energy
radio frequency source.
The energy to form the argon plasma used in ICP
is generated by a high-frequency radio frequency
source, which is inductively coupled to the argon
in a similar manner to the coils in an electric
transformer. An electric discharge produces a
seed of ions and electrons in the argon which
are then accelerated by the oscillating magnetic
field of the radio waves, which results in further
ionization as the excited electrons knock off
An argon gas electric discharge electrons from other atoms. The processes continue until a high-temperature (10 000
plasma.
K) plasma is formed. The induction coil controls the position of the plasma and keeps
it away from the walls of the container, which would melt at such high temperatures.
The plasma is a high-
energy state composed
of isolated atoms, ions, Atoms from the sample are excited by colliding with the
and electrons.
plasma particles and their emitted photons analysed.
The plasma state is Sufficient energy is available to convert the atoms of the injected sample to ions and
uncommon on earth, but promote the electrons to excited states, which then fall to the lower energy levels with
is the most common state the emission of photons at characteristic energies. The wavelength of the photons
for the visible matter in the can be used to identify the element and the total number of photons is directly
universe.
proportional to the concentration of the element in the sample.

The concentration of an element can be determined from


a calibration curve.
The number of photons emitted by sample atoms at a characteristic wavelength
is proportional to the concentration of the element in a sample. Unknown
concentrations can be determined by comparing its photo emission rate with those
of some standard solutions over a range of concentrations on a calibration curve
(Figure 12.10). A calibration curve is necessary as there are possible variations in
the intensity of the signals due to the operating conditions of the plasma such as the
flow rate of the argon and temperature of the plasma. The intensity of each line is
compared to the intensities of the same line from samples with known concentrations
ppm = one part in of the elements. The concentrations are then computed by interpolation along the
a million 106; ppb calibration lines. As each element produces a number of characteristic lines, different
= one part in a
billion 109: they are units
calibration curves can be produced for different wavelengths. Standard calibration
of concentration. curves for most elements are linear. The solutions used in the calibration are generally
made by successive dilution of a standard solution. An acid solvent is often used in
the analysis of metal samples. The concentration of the unknown solution should fall
inside the calibrated region. Generally, the wavelengths of high intensity are selected
for the analysis.
As the sample is vaporized and broken into atoms in the plasma, ICP determines
the concentration of atoms irrespective of how they are combined together. It is an
extremely sensitive method, allowing concentrations as low as 0.1 ppb (one part in
1010) to be measured.
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Worked example
The amount of lead in alloys used in electrical and electronic equipment needs to be
carefully monitored as it can pose risks to human health.
A range of solutions were made up with different lead concentrations. The resulting
calibration curve is shown, with the intensity measured in 1000 counts per second.

Pb: 220 nm
450
400
Figure 12.10 A calibration
350 curve for lead.
intensity/kc s1

300
250
200
150
100
50
0
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
[Pb]/mg dm3

(a) Explain the number in the title of the graph.


(b) Suggest how the solutions used in the calibration curve were prepared, assuming
the balance has a precision of () 0.0001 g and the concentrations need to be
determined to three significant figures.
(c) Two alloy samples were tested using the same conditions.
Alloy sample Intensity / kc s1
I 120
II 20

Determine the concentration of lead in the two samples and comment on the
reliability of the results.
Solution
NATURE OF SCIENCE
(a) 220 nm is the wavelength of the photons emitted.
The development of ICP
(b) The smallest amount of Pb that can be accurately measured 0.0100 g spectroscopy illustrates
the fuzzy boundary
To make the most concentrated solution (1.50 mg dm3) needs 0.0150 g in 10 dm3 of between pure and applied
solution, which is 0.00150 g in 1 dm3 of solution. science. It is based on
atomic processes and
Concentrated acid (solvent) is added to dissolve the Pb metal. (A mixture of makes use of a state of
concentrated nitric acid and hydrochloric acid is actually used.) matter not generally
found on the Earth, but it
The other solutions were prepared by successive dilution of this most concentrated is a very sensitive method
solution. of analysis which can
show the presence of
(c) Alloy sample Intensity / kc s1 [Pb] /mg dm3 material which would
I 120 0.469 be undetected by other
methods, and has
II 20 0.078 helped the production
of improved materials.
The concentration of II is less reliable as it is outside the range of the concentrations
Improved instrumentation
used in the calibration. has allowed us to collect
data beyond human sense
perception.

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12 Option A: Materials

Inductively coupled plasma (ICP) mass spectroscopy (ICP-MS)


Inductively coupled plasma (ICP) mass spectroscopy is capable of detecting metals
and non-metals at concentrations of one part in 1012. The sample is ionized with
inductively coupled plasma and analysed using a mass spectrometer to separate and
count the abundance of the ions. The technique is more effective with metals than
non-metals. Metals have lower ionization energies and so form positive ions more
readily. The ability to obtain isotopic information has made the method particularly
effective in geochemistry.

Exercises
14 (a) Describe the plasma state used in ICP spectroscopy.
(b) Identify one element that cannot be identified by ICP spectroscopy.
(c) Which method is more sensitive to measuring lower concentrations: ICP-OES or ICP-MS?
(d) Identify the ICP method which is more effective in determining non-metal concentrations. Explain
your answer.
15 Levels of heavy metal ions in soil need to be carefully monitored as they can cause serious damage to
the environment and human health.
A range of solutions were made up with different mercury concentrations. The resulting calibration
curves are shown.

1200
I
1000
intensity/kc s1

800
II
600
III
400

200

0
0 0.5 1.0 1.5 2.0 2.5 3.0
[Hg]/g dm3

(a) Explain how three calibration curves could be produced for the same metal.
(b) One sample of soil was analysed in accordance with the methods for red line (II). It produced
3.00 107 counts in one minute. Deduce the mercury concentration of the sample.
(c) Deduce the intensity of photons produced by the sample when it is analysed in accordance with
the blue line (I).
(d) Which line will produce the most precise concentration determination?
16 The metallurgical properties of aluminium and its alloys are highly dependent on chemical
composition. The presence of manganese increases the hardness of the alloy.
The manganese content in an alloy was determined by ICP-AES with alloys of known composition.
The intensity signal = 120 kc s1. What is the manganese content in the alloy?

= 590 nm
350
300
250
intensity/kc s1

200
150
100
50
0
0 0.2 0.4 0.6 0.8 1.0 1.2
Mn content (% by mass)

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A.3 Catalysts

Understandings: Catalysts increase the


rate of some reactions
Reactants adsorb onto heterogeneous catalysts at active sites and the products desorb.
but they do not
Homogeneous catalysts chemically combine with the reactants to form a temporary activated
change the position of
complex or a reaction intermediate.
Transition metal catalytic properties depend on the adsorption/absorption properties of the metal
equilibrium. They are
not chemically changed
and the variable oxidation states.
Zeolites act as selective catalysts because of their cage structure.
at the end of the
Catalytic particles are nearly always nanoparticles that have large surface areas per unit mass.
reaction.

The word catalyst derives


Applications: from the Chinese word for
Explanation of factors involved in choosing a catalyst for a process. marriage broker.
Description of how metals work as heterogeneous catalysts.
Description of the benefits of nanocatalysts in industry. In the Haber process,
Guidance chemists can produce
Consider catalytic properties such as selectivity for only the desired product, efficiency, ability to work ammonia at an
in mild/severe conditions, environmental impact, and impurities. economical rate at
The use of carbon nanocatalysts should be covered. temperatures of 525 C
and a pressure of 20 atm
(2 106 Pa). To make one
Catalysts play an essential role in the chemical industry. Without them many chemical
gram of ammonia at the
processes would go too slowly to be economical. Catalysts work by providing same temperature and
reactions with alternative reaction mechanisms that have lower activation energies. pressure but without a
catalyst would require a
A catalyst cant make more of a product than would eventually be produced without it. reactor 10 times the size of
It can however act selectively when two or more competing reactions are possible with the Solar System.
the same starting materials, producing more of the desired product by catalysing only
that reaction.

(a) reactants

Homogeneous and heterogeneous


catalysis
Chemists divide catalysts into two types: homogeneous
and heterogeneous. Homogeneous catalysts are in products
the same state of matter as the reactants, whereas in
heterogeneous catalysis, the catalyst and the reactants are in
different states. For example, the catalyst may be a solid and
the reactants gases or liquids (Figure 12.11). catalyst
heterogeneous catalysis
The area on the catalyst where the reaction takes place
is called the active site. In heterogeneous catalysis the (b)
reactant molecules can only collide with the active sites
on the surface. For the reactions to go significantly faster

Figure 12.11 Diagram representing


(a) homogeneous catalysis and
(b)heterogeneous catalysis. catalyst solvent
reactants products
homogeneous catalysis
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12 Option A: Materials

there must be a significant drop in activation energy to compensate for this. There are
more active sites available in homogeneous catalysed reactions and a small drop in
activation energy can lead to a dramatic increase in rate.
Heterogeneous catalysis is generally preferred in industrial processes as the catalyst can
be easily removed by filtration from the reaction mixture. The use of iron in the Haber
process and vanadium(v) oxide in the Contact process is discussed in Chapter 7 (pages 327
and 328).
The use of homogeneous catalysis, which often requires expensive separation
techniques, is generally reserved for the production of complex organic molecules. As
they have greater activity, they work under milder conditions with greater selectivity.
Enzyme-catalysed reactions in cells, which take place in aqueous solution, are
examples of homogeneous catalysis.

Examples of catalysts: transition metals


A substance is adsorbed Industrial process Catalyst
when it is weakly Haber process: finely divided iron
attached to a surface. N2(g) + 3H2(g) s 2NH3(g)
It is absorbed when
it enters pores in the Contact process: vanadium(v) oxide, platinum
material. 2SO2(g) + O2(g) s 2SO3(g)
hydrogenation of unsaturated oils to make nickel
margarine
reaction of CO and H2 to make methanol: copper
CO(g) + 2H2(g) CH3OH(g)
catalytic cracking, e.g. Al2O3/SiO2, zeolites
C10H22(g) C4H8(g) + C6H14(g)
polymerization of ethene to poly(ethene) ZieglerNatta catalyst, AIR3 + TiCl4

Many catalysts are either transition metals or their compounds. Transition metals
show two properties that make them particularly effective as catalysts.
They have variable oxidation states. They are particularly effective catalysts in redox
reactions.
They adsorb small molecules onto their surface. Transition metals are often good
heterogeneous catalysts as they provide a surface for the reactant molecules to come
together with the correct orientation. The products desorb from the surface once the
reaction is complete.

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Catalyst having variable oxidation state Catalyst allowing adsorption onto surface

Vanadium(V) oxide as a catalyst:


V2O5(s) 1 SO2(g) V2O4(s) 1 SO3(g)
V2O4(s) 1 _12 O2(g) V2O5(s)

Overall reaction
SO2(g) 1 _12 O2(g) SO3(g) The reactants are both gases.

Vanadium shows variable oxidation states.


It is reduced from the 15 state to the 14 state
and then oxidized back to the 15 state. The reactants are both adsorbed
on the Ni surface.

Bonds are broken and formed on


the surface.

The product moves away from


the surface.

Nickel, shown in blue, adsorbs both C2H4 and H2 and provides a surface
for reaction. It brings the reactants together with the correct orientation
for a successful addition reaction. C2H6 is the product.

Activated complexes and intermediates An activated complex is


an unstable combination
An activated complex is an unstable combination of reactant molecules that can go
of reactant molecules
on to form products or fall apart to form reactants as it corresponds to a state with that can go on to form
partial bonds of maximum energy in the reaction profile. A heterogeneous catalyst products or fall apart to
decreases the activation energy by stabilizing the activated complex (Figure 12.12). form reactants.

(a) (b) Figure 12.12 Heterogeneous


catalysis stabilizes the activated
complex. (a) The activated
activated complex complex has more energy
lowering of Ea
in presence than either the reactants or
stabilized activated products. It is an unstable state
of catalyst
complex with partial bonds as they are
energy

reactants partially broken and partially


catalysed formed. (b) Heterogeneous
products catalysis allows the formation
reaction
of a stabilized activated
complex.
extent of reaction
A reaction intermediate
The V2O4 formed with vanadium in the +4 oxidation state in the homogenous reaction is a species that
above is a reaction intermediate (Figure 12.13). This is a species that occurs at a is produced and
local minimum on the reaction profile that allows the reaction to follow a mechanism consumed during a
reaction but does not
where all steps have lower activation energies then the uncatalysed reaction. occur in the overall
equation.

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12 Option A: Materials

(a) (b)
Figure 12.13 Homogeneous
catalysis can involve the
activated complex activated activated
formation of reaction
complex 1 complex 2
intermediates. (a) A reaction Ea Ea1 Ea2

energy

energy
of one step which involves
no intermediate step. (b) A reactants reactants intermediate
reaction of two steps in which products
products
an intermediate is formed. An
intermediate is more stable
than an activated complex extent of reaction extent of reaction
as it corresponds to a local
minimum on the reaction
energy profile.

Zeolites act as selective catalysts


because of their cage structures
Zeolites are a family of naturally occurring minerals of
aluminium silicates.
The open caged structure of zeolites gives them excellent
catalytic properties.
They offer a huge surface for reactants to be adsorbed. Almost
every atom in the solid is at a surface and is therefore available
as an active site.
The shape and size of the channels makes them shape-selective
catalysts. Only reactants with the appropriate geometry can
interact effectively with the active sites, and only smaller
molecules can escape so the products can be controlled.

Computer graphic Nanoparticles


representation of the structure are effective
of zeolite-Y, a mineral used in
the catalytic cracking process in heterogeneous
which large alkane molecules catalysts as they have
break down into smaller
alkanes and alkenes. In this a large surface area
image, silicon and aluminium per unit mass
atoms are shown in yellow and
oxygen atoms in red. Nanoparticles with very small
particle size are particularly
The word zeolite derives effective heterogeneous
from the Greek words zein
meaning to boil and lithos
catalysts as they have a large
meaning stone. The first number of active sites on the
zeolite to be discovered surface relative to their mass. The
released water when it was surface structure and electronic
heated.
properties of the particles can
The open structure of also be modified to improve their
zeolites is illustrated by
the fact that a teaspoon of A coloured scanning electron
zeolite has a surface area micrograph (SEM) of gold
of two tennis courts. nanoparticles.

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catalytic performance. The benefits of nanoparticles are
illustrated by the catalytic action of gold. Gold is relatively
chemically inert, but in 1 nm clusters, which contain
about 20 atoms, it becomes a very effective catalyst for a
range of reactions which include the oxidation of carbon
monoxide to form carbon dioxide in catalytic converters.
The performance of a catalyst can be affected by local
differences in composition, size, shape, and surface
structure.
The hollow structures of carbon nanotubes discussed on
page 629 also makes them very good candidates for shape-
selective heterogeneous catalysis. They have large surface
areas per unit mass, excellent electron conductivity, and
are generally chemical stable. The catalytic properties can
be varied by lining the tubes with different elements.

NATURE OF SCIENCE
Think about how models are used in science. Catalysts
were used to increase reaction rates before the
development of an understanding of how they work.
This led to models that are constantly being tested and
improved.

Supercomputer model
of the structure of a gold
Catalytic activity can be modied with the use of nanoparticle (gold-coloured
lattice) as it adsorbs carbon
promoters and inhibitors or inactivated by poisons monoxide, CO (top). There are
Catalytic activity can be deliberately modified with the use of promoters and several hundred gold atoms in
the lattice.
inhibitors. The addition of promoters in small concentrations increases catalytic
activity whereas inhibitors reduce the activity as they react with and remove the
reaction intermediates.
Some catalysts have a limited working life as they can be poisoned or inactivated.
Catalytic poisons block the active sites because they are adsorbed on the surface
more strongly than reactant molecules. The iron catalysts in the Haber process work
for between 5 and 10 years. Sulfur from traces of hydrogen sulfide in the natural gas
used as the source of hydrogen presents the greatest problems. Similarly, the use of
platinum as an effective catalyst for the Contact process is affected by even the smallest
amounts of arsenic.
Other catalytic poisons include mercury(II) salts, carbon monoxide, and hydrogen
cyanide.

Catalyst choice depends on selectivity for only the


desired product and environmental impact
The choice of catalyst will depend on a number of factors.
Selectivity: does the catalyst give a high yield of the desired product?
Efficiency: how much faster is the reaction with the catalyst?
Life expectancy: for how long does it work before it is poisoned?
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12 Option A: Materials

Environmental impact.
Some materials used
as effective catalysts Ability to work under a range of conditions of temperature and pressure. A
are toxic and harmful heterogeneous catalyst may melt and or become less effective if its operating
to the environment. temperatures are too high or its surface becomes coated with unwanted products.
Is environmental
degradation justified in the Although some catalysts, such as the transition metals platinum and palladium, are
pursuit of knowledge? very expensive, their use is economical. They reduce the energy costs of the process,
increase yields, and can be reused as they are not chemically changed.
Palladium, platinum,
and rhodium are used
as catalysts in catalytic NATURE OF SCIENCE
converters in cars. The Catalysts are widely used in industry and it has been estimated that they contribute about
value of these metals one-sixth of the value of all manufactured goods in the industrialized world. Our understanding
makes them an attractive of the mechanisms of catalytic action has greatly improved recently because of the use of
target for thieves. improved analytical spectroscopic and X-ray diffraction techniques. However, catalysis is a
complex subject and there are still many areas where our understanding is incomplete. The
growth in computing power has made modelling catalytic action much more powerful. These
models can then be tested against the experimental results and modified accordingly.

Platinum catalyst molecular modelling. Supercomputer model of the geometric


and electronic structure of a platinumcarbon monoxide complex. A platinum
cluster (seven yellow spheres) has adsorbed a carbon monoxide (CO) molecule
(red and green spheres, bottom). The energetics of the bonding shown here
is being studied because carbon monoxide can act to poison catalysts by
adsorption on the surface of the metals used.

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Exercises
17 Explain why transition elements and their compounds are effective heterogeneous and homogeneous
catalysts.
18 (a) Although many catalysts are very expensive, their use does allow the chemical industry to operate
economically. Outline the advantages of using catalysts in industrial processes.
(b) Sulfur in crude oil must be removed before the crude oil is refined as the sulfur can poison the
catalysts. Explain how the sulfur impurities poison the catalyst.
19 (a) Distinguish between a reaction intermediate and an activated complex. Which species can, in
theory, be isolated?
(b) Explain why heterogeneous catalysts are generally used in industrial processes.
(c) Suggest two reasons why gold nanotubes are effective catalysts.
(d) Suggest a reason why it is difficult to regulate for the toxicity of nanoparticles.

A.4 Liquid crystals

Understandings:
Liquid crystals are fluids that have physical properties (electrical, optical, and elasticity) that are
dependent on molecular orientation to some fixed axis in the material.
Thermotropic liquid crystal materials are pure substances that show liquid crystal behaviour over a

temperature range.
Lyotropic liquid crystals are solutions that show the liquid crystal state over a (certain) range of

concentrations.
Nematic liquid crystal phase is characterized by rod-shaped molecules which are randomly

distributed but on average align in the same direction.


Guidance
Soap and water is an example of lyotropic liquid crystals and the biphenyl nitriles are examples of
thermotropic liquid crystals.
Smectics and other liquid crystal types need not be discussed.

Liquid crystal behaviour should be limited to the biphenyl nitrates.

Applications:
Discussion of the properties needed for a substance to be used in liquid crystal displays (LCD).
Explanation of liquid crystal behaviour on a molecular level.
Guidance
Properties needed for liquid crystals include: chemically stable, a phase which is stable over a suitable
temperature range, polar so they can change orientation when an electric field is applied, and rapid
switching speed.

The solid and liquid states are discussed in Chapter 1 (page 11). When a solid crystal
melts, the ordered arrangement of the particles breaks down, to be replaced by the
disordered state of the liquid. Some crystals, however, melt to give a state which
retains some of the order of the solid state. This intermediate state of matter with
properties between the solid state and the liquid state is called the liquid crystal state.
Liquid crystals have many of the physical properties of solid crystals; however, these
properties can be easily modified. In digital watches, for example, a small electric field
can alter optical properties by changing the orientation of some of the molecules.
Some areas of the display go dark and others remain light, allowing the shape of
different digits to be displayed. Over the past 40 years liquid crystals have gone from
being an academic curiosity to the basis of big business.
Liquid crystals typically all contain long, thin, rigid, polar organic molecules. Imagine
a large number of pencils put into a rectangular box and shaken. When you open
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12 Option A: Materials

the box, the pencils will be facing in


approximately the same direction, but
will have no definite spatial organization.
They are free to move, but generally line
up almost parallel. This gives a simple
model for the nematic type of a liquid
phase liquid state. The molecules are
randomly distributed as in a liquid, but
the intermolecular forces are sufficiently
strong to hold the molecule in one
orientation in some regions or domains.
These domains can be observed by
viewing the liquid under a microscope
with polarized light.

Although liquid crystals flow


like a fluid, there is some Thermotropic liquid crystals show liquid crystal
order in their molecular
arrangement. When viewed
behaviour over a temperature range
under a microscope using The liquid crystal phase is only stable over a small range of temperatures. The
a polarized light, different directional order is lost and the liquid state is formed when the molecules have too
regions, which have the much kinetic energy to be constrained in the same orientation by the intermolecular
molecules in different
orientations, can be identified. forces (Figure 12.14).
Thermotropic liquid crystal materials are pure substances that show liquid crystal
behaviour over a temperature range.
temperature increasing
Figure 12.14 Thermotropic
liquid crystals are formed in a
temperature range between
the solid and liquid state.

Making a liquid crystal


Full details of how to carry
out this experiment with
a worksheet are available
online.

Solid The molecules have a Liquid crystal The molecules Liquid The molecules have
regular arrangement and have an irregular arrangement an irregular arrangement and
orientation. and a regular orientation. orientation.

Lyotropic liquid crystals are solutions


Some substances can form a different type of liquid crystal state in solution. Consider a
solution containing some rod-like molecules as the solute. At low concentrations, the
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molecules generally have a disordered orientation and an irregular arrangement. If the
concentration is increased sufficiently the molecules will adopt an ordered structure
and solid crystals will form. At intermediate concentrations a lyotropic liquid crystal
state may be possible where the molecules have an irregular arrangement with a
regular orientation (Figure 12.15).
concentration decreasing
Figure 12.15 The phase
transitions of lyotropic
liquid crystals depend on
both temperature and
concentration.

The phase transitions


of thermotropic liquid
crystals depend on
temperature, while
those of lyotropic liquid
crystals depend on
both temperature and
concentration.
Solid The molecules have a Liquid crystal The molecules Liquid The molecules have
regular arrangement and have an irregular arrangement an irregular arrangement and
orientation. and a regular orientation. orientation.

The molecules that make up lyotropic liquid crystals generally consist of two
distinct parts: a polar, often ionic, head and a non-polar, often hydrocarbon, tail.
When dissolved in high enough concentrations in aqueous solutions, the molecules
arrange themselves so that the polar heads are in contact with a polar solvent in an
arrangement called a micelle (Figure 12.16).

O
Liquid crystal properties may
play a central role in the
O processing of silk. The water-
hydrophobic hydrocarbon soluble silk molecules are
chain stored in aqueous solution, but
they can be assembled into
rod-like units which form a
lyotropic liquid crystal state.
hydrophobic hydrophilic A micelle is formed when the molecules
non-polar tail polar head group together to form a spherical arrangement.
The hydrophilic heads are exposed to water, Figure 12.16 The formation of
shielding the non-polar tails. a micelle.

Lyotropic liquid crystals are found in many everyday situations. Soaps and detergents,
for example, form lyotropic liquid crystals when they combine with water. Many
biological membranes also display lyotropic liquid crystalline behaviour.
Kevlar can show lyotropic properties in solution as it is a rigid rod-shaped molecule
due to its linked benzene rings. Although it is very resistant to most chemicals, Kevlar
is soluble in concentrated sulfuric acid as the hydrogen bonds between the chains
are broken (Figure 12.17). At high concentrations a lyotropic liquid crystal state is
formed. Some hydrogen bonding is present which forces the molecules into a parallel
arrangement in localized regions like logs floating down a river.

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12 Option A: Materials

O
Figure 12.17 The structure of H C C
Kevlar. There are hydrogen
bonds between the chains O N N O
which can be broken when
it is added to concentrated C C H
sulfuric acid.
O O

H C C

O N N O

C C H

O O

H C C

O N N O

C C H

O
The formation of Kevlar is discussed on page 656.

The elasticity and electrical and optical properties


depend on the orientation of the molecule to some xed
axis in the material
The practical application of liquid crystals makes use of the dependence of their
physical properties, such as their elasticity, and their electrical and optical behaviour
on their molecular orientation to some fixed axis in the material.
To understand the optical properties of liquid crystals, we need to consider the
behaviour of polarized light when it passes through a polarizing filter. We saw in
Chapter 2 (page 70) that light is an electromagnetic wave. It is said to be polarized
when the electric field vector vibrates in one plane only. A polarizing filter will
only transmit light when it is aligned with the electric field. This is illustrated by the
arrangement in Figure 12.18.
(a) unpolarized light (b) unpolarized light

polarizing
polarizing filter 1
filter 1
Figure 12.18 (a) When the
polarizing filters are crossed polarized polarized
so that their planes of light light
polarization are at right angles polarizing
to one another, no light is polarizing filter 2
transmitted. (b) When the filter 2
polarizing filters are parallel,
all of the light passing through no light polarized
the first filter also passes light
through the second.

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The two polarizing filters used together transmit light differently depending on their
relative orientations. The second polarizing filter is sometimes called the analyser.
The ability of liquid crystals to transmit light depends on their relative orientation to
the plane of polarization.

NATURE OF SCIENCE What attributes of the


IB learner profile help
Liquid crystals, like many scientific discoveries, were found by accident. In 1888 the Austrian
scientists turn a lucky
botanist Friedrich Reinitzer was investigating the behaviour of derivatives of cholesterol at
break into a scientific
different temperatures when he observed that cholesteryl benzoate appeared to have two
breakthrough?
melting points. The crystals form a cloudy liquid at 145.5 C which clears at 178.5C. It
takes more than being in the right place, at the right time, to make a serendipitous discovery.
Scientific research may be unpredictable but it is based on highly focussed and creative
thinking. Dans les champs de lobservation le hazard ne favorise que les esprits prpars.
In the field of observation, fortune only favours the prepared mind (Louis Pasteur 1822
1895). Reinitzers experience had taught him the importance of careful observation and his
background knowledge made him appreciate the significance of what he had observed. His
inquisitive mind led him to ask a physics colleague, Otto Lehmann, for an explanation of
the crystals behaviour. Lehemann had the right tools for the task: his own research involved
studying the properties of materials with polarized light. It was Lehmann who first used the
term fliessende Kristalle, or liquid crystals.

CHALLENGE YOURSELF
1 The molecular structure of cholesteryl benzoate is shown here.

(a) Identify a feature of its molecular structure that allows it to form a liquid crystal state.
(b) Classify cholesteryl benzoate as a thermotropic or lyotropic liquid.

Biphenyl nitriles show liquid crystal behaviour


The first liquid crystal molecules with suitable properties to be synthesized were the
biphenyl nitriles (Figure 12.19).

d1 d2
C5H11 C N

d1 d2 Figure 12.19 The biphenyl


nitriles are liquid crystals. They
are polar rigid rod-shaped
The molecule is polar as nitrogen has a molecules.
greater electronegativity than carbon.

These molecules have three key features.

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12 Option A: Materials

Long alkyl chain: this limits the ability of the molecules to pack together and so
lowers the melting point and helps maintain the liquid crystal state. The melting
range can be varied by changing the size and shape of the hydrocarbon chain.
Biphenyl groups: the two planar benzene rings make the molecule rigid and rod
shaped.
Nitrile group: the high electronegativity of nitrogen makes the functional group
polar. This increases the intermolecular interactions between the molecules and
allows the orientation of the molecule to be controlled by an electric field.
The presence of the unreactive alkyl groups and the two stable benzene rings increases
the chemical stability of the molecule.
A number of rod-shaped molecules with thermotropic properties have been
developed. Some examples are shown in Figure 12.20.

C5H11 COO C3H7 H3C CN

Figure 12.20 Rod-shaped


F
molecules that show
thermotropic liquid crystal
behaviour. C5H11 CN C5H11 COO CN

The use of biphenyl nitriles in liquid crystal display


devices
The ability of the rod-shaped biphenyl nitrile molecule to transmit light depends
on its relative orientation to the plane of polarization. As the molecule is polar, this
orientation can be controlled by the application of an electric field. When there is no
applied voltage, light can be transmitted and the display appears light. When a small
The dark areas of the display voltage is applied, the orientation of the molecules changes and light can no longer be
correspond to areas where transmitted through the film and the display appears dark. The areas of the display that
a small voltage changes the
orientation of the liquid crystal
are light and dark can thus be controlled, enabling different shapes to be displayed.
molecules, preventing light As discussed earlier, the nematic state for a thermotropic liquid crystal only exists
from passing through the film.
within a small range of temperatures, which can limit the operating temperatures of
LCDs.
Pentylcyanophenyl is suitable for liquid crystal displays (LCDs) as it has the following
properties.
It is chemically stable.
It has a liquid crystal phase stable over a suitable range of temperatures.
It is polar, making it able to change its orientation when an electric field is applied.
It responds to changes of voltage quickly; i.e. it has a fast switching speed.

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In general, no single compound can fulfil all the properties required for LCD
applications, so complex mixtures are used. They contain 1020 components, each
one used to modify specific display properties, such as threshold voltage, switching
speed, and temperature range.

Twisted nematic LCDs


In a twisted nematic display, the liquid crystal material is located between two glass
plates, all between two polarizing filters at right angles to each other. The surface of
the glass plates is coated with a thin polymer layer with scratches in one direction.
The molecules in contact with the glass line up with the scratches, like matches in the
grooves of a piece of corrugated paper. Intermolecular bonds allow the molecules
between the plates to form a twisted arrangement with the alignment varying
smoothly across the cell (Figure 12.21).
unpolarized light

Glass plate is treated to ensure that


the liquid crystal molecules are
polarizing orientated parallel to the first
filter 1 polarizing filter.

The liquid crystal molecules between


the glass plates twist between the
two orientations. The plane of
polarization of the light follows the
Figure 12.21 Light passes
orientation of the molecules.
through the LCD despite the
Glass plate is treated to ensure that orientation of the polarizing
polarizing the liquid crystal molecules are filters because the plane of
filter 2 orientated parallel to the second polarization of light rotates
polarized polarizing filter. with the orientation of the
light molecules.

In the off state, the light passes through unpolarized light


the second polarizing filter as the plane of
polarization rotates with the molecular
orientation as the light passes through the polarizing
filter 1
cell.
glass plate
However, when a small threshold voltage
is applied across the cell (the on state), the electric
situation changes. The polar liquid crystal field Figure 12.22 The liquid crystal
molecules now align with the field and so molecules align themselves
the twisted structure is lost. The plane- parallel to the electric field
polarized light is no longer rotated, and so glass plate when the threshold voltage is
applied.
no light is transmitted and the cell appears no light
polarizing
dark (Figure 12.22). filter 2

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12 Option A: Materials

CHALLENGE YOURSELF
2 The diagram below is a representation of a liquid crystal display. A liquid crystal has the property of
being able to rotate the plane of polarization of light.

unpolarized
light

polarizer glass plate liquid glass plate analyser mirror


with circular crystal with circular crossed
electrode electrode with
polarizing
filter

(a) State, and explain, what the observer would see if the liquid crystal were not present.
(b) State, and explain, what the observer would see if the liquid crystal were present.
(c) Outline how the application of a potential difference between the circular electrodes allows the
observer to see the circle on the second glass plate.

Exercises
20 (a) Distinguish between the liquid state and the liquid crystal state.
(b) Distinguish between a lyotropic liquid crystal and a thermotropic liquid crystal.
(c) Outline how a micelle forms in a soap solution.
21 Distinguish between thermotropic liquid crystals and lyotropic liquid crystals and state the name of
one example of each.
22 The molecule below has liquid crystal properties.

C5H11 F

(a) Explain how the hydrocarbon chain adds to the chemical stability of the molecule.
(b) How does the presence of two fluorine atoms improve the liquid crystal properties?
23 The structure of a terphenyl molecule is shown below:

d1 d2
C5H11 C N

(a) State the molecular formula of the molecule.


(b) Suggest why the molecule can show liquid crystal behaviour at higher temperatures than the
biphenyl molecules.

A.5 Polymers

Understandings:
Thermoplastics soften when heated and harden when cooled.
A thermosetting polymer is a prepolymer in a soft solid or viscous state that changes irreversibly
into a hardened thermoset by curing.

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Elastomers are flexible and can be deformed under force but will return to nearly their original
shape once the stress is released.
High-density poly(ethene) (HDPE) has no branching, allowing chains to be packed together.

Low-density poly(ethene) (LDPE) has some branching and is more flexible.

Plasticizers added to a polymer increase the flexibility by weakening the intermolecular forces

between the polymer chains.


Atom economy is a measure of efficiency applied in Green Chemistry.

Isotactic addition polymers have substituents on the same side.

Atactic addition polymers have the substituents randomly placed.

Guidance
The equation for percent atom economy is provided in the IB data booklet in section 1.

Applications:
Description of the use of plasticizers in poly(vinyl chloride) and volatile hydrocarbons in the
formation of expanded polystyrene.
Solving problems and evaluating atom economy in synthesis reactions.

Description of how the properties of polymers depend on their structural features.

Description of ways of modifying the properties of polymers including LDPE and HDPE.

Deduction of structures of polymers formed from polymerizing 2-methylpropene.

Consider only polystyrene foams as examples of polymer property manipulation. An addition polymer
is formed when the
double bonds of many
In the 1930s some British scientists were investigating the reactions of ethene with other monomer molecules
carbon compounds under high pressure. In some of the experiments, a hard waxy solid open up to form a long
was produced, which was found to consist of only carbon and hydrogen atoms in the continuous chain.
ratio 1 : 2. This accidental discovery has had a profound effect on all our lives. They had
made poly(ethene). Plastics such as poly(ethene) are now the basis of many everyday Computer graphic
representation of the packed
materials. The addition polymerization reaction of ethene, in which many ethene chains of the poly(ethene)
molecules join together like a chain of paper clips, is outlined in Chapter 10 (page 488). molecule, a long-chain

( ) ( )
hydrocarbon with a high
H H H H molecular mass. Poly(ethene)
is made by the polymerization
n C C C C of C2H4, by heating under
pressure in the presence of
H H H H n oxygen. It may be essentially
monomer polymer considered to be a very long
chain alkane.
ethene poly(ethene)

The double bond in ethene breaks open and allows many


molecules to link together to form a chain. The value of n
varies with the reaction conditions but it is generally in the
thousands. The strength and melting points of the polymers
increase with chain length, as the intermolecular forces
increase with molecular size.
Polymers with different chemical compositions can be
formed by changing the monomer: the formation of
poly(ethene), poly(chloroethene), poly(propene), and
polystyrene follow the same reaction scheme:

( ) ( )
H H H H

n C C C C

H X H X n
monomer polymer with a long straight
chain of carbon atoms
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12 Option A: Materials

Monomer Polymer Monomer Polymer


ethene polyethene propene polypropene

( ) ( )
H H H H H H H H

C C C C C C C C

H H H H n H CH3 H CH3 n

chloroethene polychloroethene styrene polystyrene


(vinyl chloride) (PVC)

( ) ( )
H H H H H H H H

C C C C C C C C

H Cl H Cl n H C6H5 H C6H5 n

Hermann Staudinger was NATURE OF SCIENCE


the first polymer chemist
Although plastics were one of the key materials of the last century the notion of very large
to be awarded the Nobel
molecules was not widely accepted by the scientific community until 1929. The story of the
Prize in 1953 for his
acceptance of the theory of large molecules is the story of Hermann Staudingers determination
discoveries in the field of
to push forward an idea despite widespread resistance from his academic peers. The academic
macromolecular chemistry.
chemistry community at the beginning of the 20th century thought that the newly invented
plastics and natural materials such as rubber, starch, and cellulose had structures in which bundles
What role do of small molecules were held together by unknown intermolecular forces. Staudingers idea
disagreements play in the that there was a covalent bond between the units had little support. He was told by one of his
pursuit of knowledge? colleagues to drop the idea of large molecules. The eventual acceptance of Staudingers theory
was a key step in our scientific understanding that led to the practical development of polymer
chemistry. Science is a human activity and disputes of this sort are common. They are constructive
if they focus on the science and do not degenerate to personal squabbles.

Worked example
Deduce the structure of the addition polymer formed from methylpropene. You
should include three repeating units in the structure.
Solution

1 Draw three structures with the alkene double bond in the middle:
H CH3 H CH3 H CH3

C C C C C C

H CH3 H CH3 H CH3

2 Open the double bond in each molecule so that single bonds extend in both
Many students have directions:
difficulty drawing the
structure of poly(propene).
H CH3 H CH3 H CH3
It is important to note
that it follows the
C C C C C C
general scheme with
the methyl group as
H CH3 H CH3 H CH3
a side chain. Practise
drawing structures for Changing the chemical composition of the monomer and the chain length is not the
polymers with side groups only strategy used to change the properties of a polymer. The description of a polymer
(formed from monomers as one straight chain is an oversimplification as branching can occur along the main
such as propene and
chloroethene).
chain. The relative orientation of all the groups along the chain can also affect the
properties of the polymer.
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The density of poly(ethene) depends on the branching
in the structure
The poly(ethene) used to make plastic bags has very different properties from the
poly(ethene) used to make plastic buckets and toys. The carbon and hydrogen atoms
are in the same ratio 1 : 2 but the molecules have different molecular structures. If Areas of regular
arrangement between
poly(ethene) is polymerized at very high pressures, the reaction proceeds by a free
polymer molecules lead
radical mechanism and branched carbon chains are produced (Figure 12.23). This to a crystalline structure.
branching limits the interaction and alignment between neighbouring chains and the Areas of irregular
intermolecular forces are relatively weak. The resulting low-density polymer has a low arrangement lead to
amorphous forms.
melting point and quite flexible carbon chains.

Figure 12.23 Low-density


poly(ethene) (LDPE). Branching
limits the ability of the
chains to pack closely. In this
amorphous (non-crystalline)
form, the intermolecular
branched interactions between the
polymer chains are weak.
chains

The intermolecular forces


between the chains are weak

When ethene is polymerized at a lower


temperature in the presence of a catalyst (a The plastic used to make this
bag was LDPE, low-density
Ziegler catalyst with metalcarbon bonds) poly(ethene).
the reaction occurs by an ionic mechanism
and a more crystalline structure is produced
(Figure 12.24). In this high-density form the
molecules have straight chains. It is more rigid,
as the molecules are more closely packed with
stronger intermolecular forces, and it has a
higher melting point.
A range of poly(ethene)s with varying
properties can be produced by modifying
the extent and location of branching in the
low-density form.

Figure 12.24 High-density


intermolecular poly(ethene) (HDPE). In this
forces between the crystalline form the parallel
straight chains are chains are closely packed with
relatively strong relatively strong intermolecular
bonds.

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12 Option A: Materials

Different orientations of side groups lead to isotactic


and atactic forms
The presence of a methyl group in propene introduces a structural feature into the
polymer chain not found in poly(ethene). Methyl groups can be arranged with different
orientations relative to the carbon backbone. The isotactic form of the polymer, with
methyl groups arranged on one side, is an example of a stereoregular polymer (Figure
12.25). It is crystalline and tough and can be moulded into different shapes. It is used
to make car bumpers and plastic toys and can be drawn into fibres to make clothes and
carpets.

Figure 12.25 Isotactic


poly(propene) has a regular
structure with the methyl H CH3 H CH3 H CH3 H CH3 H CH3
groups pointing in the same
direction, making it crystalline The atactic form, produced when the methyl groups are randomly orientated, is
and tough. softer and more flexible (Figure 12.26). It is useful as a sealant and in other waterproof
coatings.

Figure 12.26 Atactic


poly(propene) has an irregular H CH3 CH3H H CH3 H CH3 CH3H
structure, which prevents the
chains from packing together. The product of the polymerization reaction of propene can be controlled by using
It is soft and flexible.
catalysts allowing chemists to tailor-make polymers with precise properties. A free-
radical catalyst will produce the atactic polymer; a ZieglerNatta catalyst, which leads
Catalysts used to make
stereoregular polymers
to an ionic mechanism, will produce the more ordered isotactic form. The monomer
are called ZieglerNatta binds to the catalyst surface with the correct orientation to produce the more ordered
catalysts. The German polymer. Other polymers with side chains, such as PVC, can also exist in isotactic and
chemist Karl Ziegler and atactic forms.
Italian Guillio Natta shared
the 1963 Nobel Prize for
their work in this field.
The properties of poly(vinyl chloride) are modied by
using plasticizers
The non-systematic name for chloroethene is vinyl chloride and so the polymer
of this monomer is more commonly known as poly(vinyl chloride) or PVC. The
presence of the polar C+Cl bond in PVC gives it very different properties from
both poly(ethene) and poly(propene). The molecule has a permanent dipole, allowing
a strong dipoledipole intermolecular interaction to occur between neighbouring
chains. The presence of the relatively large Cl atom also limits the ability of the chains
to move across each other. The pure polymer is hard and brittle and has few uses.
Its properties are radically improved, however, when plasticizers, such as di-(2-
ethylhexyl)hexanedioate are added (Figures 12.27 and 12.28). The plasticizer molecules
fit in between and separate the polymer chains. This allows the chains to slip across
each other more easily. The most common plasticizers are di-esters such as the
phthalates. The resulting plastic is softer and more flexible and is used, for example, to
make credit cards. PVC with varying degrees of flexibility can be produced by varying
the amount of plasticizer. The possible environmental impact of using plasticizers is
discussed later (see page 633).

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Figure 12.27 The plasticizer
molecules shown here in red
separate the polymer chains.
This allows them to move
freely past each other.

(a) CH2CH3 (b) O


O
C O CH2 CH CH2 CH2 CH2 CH3
OR Figure 12.28 (a) Di-(2-
(CH2)4 ethylhexyl)hexanedioate and
OR the (b) phthalates are common
C O CH2 CH CH2 CH2 CH2 CH3 plasticizers. Note the presence
of the two ester functional
O CH2CH3 O groups in both structures.

Light micrograph of fibres of


PVC. PVC is a tough, white
material, which softens with
the application of a plasticizer.

Expanded polystyrene is widely


used as a thermally insulating
and protective packaging
material.

Expanded polystyrene is made by adding


volatile hydrocarbons
Expanded polystyrene is made by expansion moulding. Polystyrene
beads containing about 5% of a volatile hydrocarbon such as pentane
are placed in a mould and heated. The heat causes the pentane to
evaporate and bubbles of gas to form. The expansion of the gas causes
the polymer to expand into the shape of the mould. The resulting
plastic has a low density, is white, opaque, and an excellent thermal
insulator. These properties should be contrasted with the polystyrene
made without a foaming agent, which is colourless, transparent, and
brittle.

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12 Option A: Materials

Polymers can be classied based on their response to


heat and applied forces
Thermoplastics soften when heated and harden when cooled
The plastics we have discussed are all examples of thermosoftening or
thermoplastic polymers (Figure 12.29). They are made from polymer chains which
interact only weakly via intermolecular forces. When they are heated one chain can
slip across another making the polymer soften. They can be reheated and remoulded
many times.
The intermolecular forces are strongest in crystalline regions, where the molecules
are aligned. These areas increase the hardness of the bulk material. The molecules can
slide across each other in amorphous regions which make the bulk material less brittle.
A fibre has a special crystalline structure in which all the molecules are aligned along
the same direction. Isotactic poly(propene) can be made into such a strong fibre.

(a) (b)
Figure 12.29 Schematic of
thermosoftening plastics.
(a)They are made from
polymer chains which
interact only weakly via
intermolecular forces. (b) If
the chains are allowed to line
up, the intermolecular forces
More generally the crystalline regions are not aligned in the same direction. This can
increase and a strong fibre
with a crystalline structure is be increased if the polymer is stretched. This increases the strength of the polymer in
produced. the direction of the force, but may weaken it in other directions (Figure 12.30).

(a) (b)
Figure 12.30 Stretching
a thermoplastic increases
the alignment between the
crystalline regions of the
polymer. The amorphous
regions have been omitted for
clarity. (a) Different crystalline
regions of a thermoplastic
where the molecules are
aligned. (b) Stretching a
stretching force
thermoplastic increases
the alignment between the
different crystalline regions
and increases the strength in Elastomer polymers show elastic properties when stretched
this direction. Elastomers are flexible and can be deformed under force but will return to nearly
their original shape once the force is removed. Rubber, for example, is a natural
hydrocarbon polymer which can be reversibly extended to over six times its natural
length without losing its natural shape which returns when the stretching force is
removed. Although we have generally represented the polymer chains as relatively
straight, this, as already discussed, is a simplification. Free rotation about the C C
bonds allows some polymer chains to be coiled into many different arrangements.
These coils are straightened when the material is stretched but can return if the force
applied to stretch the material is removed.

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The elastic behaviour of a plastic can be modified with the addition of a small number
of covalent bonds which allow some cross-links to form between the chains (Figure
12.31). This limited cross-linking restricts the overall movement of the molecules but
allows some local movement.

Figure 12.31 Two polymer


chains and
linked by a covalent bond .
The chains can be uncoiled
when the polymer is stretched
but return once the force
is removed. The cross-link
between the chains keeps the
chains knotted together which
increases the elasticity of the
The elastic properties of rubber can be linked to the presence of double bonds in polymer.
the rubber structure ( [CH2 C(CH3)= CH CH2]n), which react with sulfur when
the polymer is heated in the vulcanization process. The sulfur atoms form S S
bridges between neighbouring chains which keeps the molecule knotted together.
The molecules are free to unwind under stress but the cross-links restrict the relative
movement between the chains
Poly(2-chlorobuta-1,3-diene) ( [CH2 CH= CCl CH2]n), which also has an alkene
double bond in the polymer chain, is an elastomer known as Neoprene.

A thermosetting polymer is hardened by heating


There is more extensive cross-linking in the thermosetting polymers. A soft solid
or viscous prepolymer state, made up from molecules of intermediate size, is first
formed which then changes irreversibly into a hardened thermoset by curing. Covalent
bonds are formed between adjacent chains of the polymers. These strong covalent
cross-linkages give the material increased strength and rigidity. The extensive cross-
links prevent the plastic from melting when it is reheated and so they cannot be
softened or remoulded (Figure 12.32).

Figure 12.32 Schematic of


thermosetting plastics The
polymer chains are
linked by a cross-links of
covalent bonds .

One of the first thermosetting plastics was Bakelite, formed from the co-monomers
phenol and methanal (Figure 12.33). Bakelite has a hard rigid structure which does
not melt once it has been heated and set. Modern resins are made in a similar way to
Bakelite but melamine is used instead of phenol (see Exercise 27).

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12 Option A: Materials

OH OH OH OH
CH2 CH2
Figure 12.33 The structure
of Bakelite, a thermosetting
plastic. Methanal (CH2O) OH OH OH OH
provides the CH2 cross-links CH2 H2C CH2 CH2 H2C
(shown in blue) between the
benzene rings of phenol.
OH OH OH OH
H2C CH2 CH2 H2C CH2 CH2

OH OH OH OH
CH2 H2C CH2 CH2 H2C

OH OH OH OH
H2C CH2 CH2 H2C CH2 CH2

OH OH OH OH
CH2 H2C CH2 CH2 H2C

Atom economy is a measure of efciency applied in


Green Chemistry
Green Chemistry is the sustainable design of chemical products and chemical
processes. It aims to minimize the use and generation of chemical substances that are
hazardous to human health and the environment. Traditionally, the efficiency of a
reaction has been measured by calculating the percentage yield (the proportion of the
desired product obtained compared to the theoretical maximum), but this is only a
limited measure as it gives no indication of the quantity of waste produced. A synthetic
route should maximize the atom economy by incorporating as many of the atoms of
the reactants as possible into the desired product.
The atom economy of a reaction can be calculated from the equation provided in
section 1 of the IB data booklet:

molar mass of desired product


% atom economy = 100%
molar mass of all reactants

Efficient processes have high atom economies, and are important for sustainable
development, as they use fewer natural resources and create less waste. Addition
polymerization reactions, for example, have an atom economy of 100% as all the
reacting atoms end up in the polymer and there are no side products. Many real-
% atom economy = world processes in drug synthesis, for example, use deliberate excess of reactants
molar mass of desired product to increase the yield but have low atom economies.
molar mass of all reactants
100% Catalysts have a crucial role in improving atom economy.

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Worked example
Chloroethene is the monomer used in the manufacture of PVC. It can be produced
from 1,2-dichloroethane by the following reaction.
CH2ClCH2Cl CH2 = CHCl + HCl
Calculate the atom economy for the reaction.
Solution

molar mass of reactant = (2 12.01) + (4 1.01) + (2 35.45) = 98.96


molar mass desired product = (2 12.01) + (3 1.01) + (1 35.45) = 62.50
62.50
% atom economy = 100% = 63.2%
98.96

Exercises
24 Identify which of the options below best describes a thermoplastic material.

Interaction within chains Interaction between chains


A Strong covalent Strong van der Waals forces
B Strong covalent Weak van der Waals forces
C Strong van der Waals forces Weak covalent
D Weak covalent Weak covalent
Explain your answer.
25 (a) Draw a full structural formula showing the repeating unit in isotactic poly(propene).
(b) Poly(propene) can exist in isotactic and atactic forms. Sketch the structure and name the
stereoregular polymer.
(c) Explain why the more crystalline form can be used to make strong fibres for carpets.
(d) Deduce how many monomer units of propene could be joined together to make a polymer with
an average relative molecular mass of 2.1 106.
(e) Explain why only an average value can be given for the relative molecular mass.
26 The properties of polystyrene and PVC can be modified during the manufacturing process.
(a) Distinguish between two forms of PVC and explain the difference in properties.
(b) Distinguish between two forms of polystyrene and explain the difference in properties.
27 Melamine has the following structure:

NH2

N N

H2N N NH2
(a) It can be produced from urea in the following reaction.
6(NH2)2CO C3H6N6 + 6NH3 + 3CO2
Calculate the atom economy for the reaction.
(b) Melamine combines with a co-monomer methanol to form a resin. Suggest a structure for this
thermosetting plastic.
(c) Explain why thermoplastics such as poly(ethene) melt whereas thermosetting plastics such as the
melamine resin do not.
(d) Discuss the role of cross-linking in the structures of thermosetting plastics and elastomers.
28 (a) Explain the use of expanded polystyrene as a packaging material.
(b) Describe how the expanded form is produced.

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12 Option A: Materials

A.6 Nanotechnology

Understandings:
Molecular self-assembly is the bottom-up assembly of nanoparticles and can occur by selectively
attaching molecules to specific surfaces. Self-assembly can also occur spontaneously in solution.
Possible methods of producing nanotubes are arc discharge, chemical vapour deposition (CVD),

and high-pressure carbon monoxide (HIPCO).


Arc discharge involves either vaporizing the surface of one of the carbon electrodes, or discharging

an arc through metal electrodes submersed in a hydrocarbon solvent, which forms a small rod-
shaped deposit on the anode.

Applications:
Distinguishing between physical and chemical techniques in manipulating atoms to form
molecules.
Description of the structure and properties of carbon nanotubes.

Explanation of why an inert gas, and not oxygen, is necessary for CVD preparation of carbon

nanotubes.
Explanation of the production of carbon from hydrocarbon solvents in arc discharge by oxidation

at the anode.
Deduction of equations for the production of carbon atoms from HIPCO.

Discussion of some implications and applications of nanotechnology.

Explanation of why nanotubes are strong and good conductors of electricity.

Guidance
Possible implications of nanotechnology include uncertainty as to toxicity levels on a nanoscale,
unknown health risks with new materials, concern that human defence systems are not effective
against particles on the nanoscale, responsibilities of the industries and governments involved in this
research.
Conductivity of graphene and fullerenes can be explained in terms of delocalization of electrons. An

explanation based on hybridization is not required.

In 1959 the Nobel Prize winning physicist Richard Feynman gave a ground breaking
talk about the physical possibility of making, manipulating, and visualizing things on
a small scale and arranging atoms the way we want. Feynman challenged scientists to
develop a new field where devices and machines could be built from tens or hundreds
of atoms. This field is now called nanotechnology, which has been described as the
science of the very small with big potential.

Richard Feynman (1918


1988). His article Theres
plenty of room at the bottom
made predictions about
nanotechnology before it was
practically possible.

Individual silicon atoms


(yellow) can be positioned
to store data. This data
can be written and read
using a scanning tunnelling
microscope.

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Nanoscience research has rapidly grown internationally since the 1990s and it is It is theoretically possible
now widely accepted that it will play an important role in the development of future to store the information in
technologies. all the books of the world
in a cube of material the
size of the barest piece of
dust that can be made out
Nanotechnology involves structures in the 1100 nm by the human eye.
range
Nanotechnology is defined as the research and technology development in the
1100 nm range. Nanotechnology creates and uses structures that have novel
properties because of their small size. It builds on the ability to control or manipulate
matter on the atomic scale.
Nanotechnology is an interdisciplinary subject which covers chemistry, physics,
Before you become too
biology, and material science. To the chemist, who is familiar with the world of entranced with gorgeous
molecules and atoms, 1 nm (109 m) is relatively large, whereas 1 mm (106 m) is gadgets let me remind
considered small on an engineering scale. There are two general ways that are available you that information is not
knowledge, knowledge is
to produce nanomaterials. The top-down approach starts with a bulk material and
not wisdom (Arthur C
breaks it into smaller pieces. The bottom-up approach builds the material from Clarke)
atomic or molecular species. It is important to understand that, on the nanoscale, What is the difference
materials behave very differently to their bulk properties. The rules are very different between knowledge and
from those that apply to our everyday world. The electron, for example, behaves more information?
like a wave on the nanoscale scale and is less localized in space and can tunnel through
what should be impenetrable barriers. Substances that are insulators in bulk form
might become semiconductors when reduced to the nanoscale. Melting points can
change due to an increase in surface area. These quantum effects and the large surface-
area-to-volume ratios can lead to the same material having a range of size-dependent
properties. The colour of a material, for example, can depend on its size.

NATURE OF SCIENCE
Science is an exciting and challenging adventure involving much creativity and imagination as
well as exacting and detailed thinking and application. Richard Feynman was well known for
flashes of intuition and the pleasure he took in finding things out. He likened the scientific
endeavour to understand the natural world to someone trying to understand the rules of chess
by observation alone. You might discover after a bit, for example, that when theres only one
bishop around on the board that the bishop maintains its colour. Later on you might discover the
law for the bishop as it moves on the diagonal which would explain the law that you understood
before that it maintained its colour and that would be analogous to discovering one law
and then later finding a deeper understanding of it. Then things can happen, everythings going
good, and then all of a sudden some strange phenomenon occurs in some corner, so you begin
to investigate that its castling, something you didnt expect. It is things we dont understand that
are the most interesting. The direct influence of Feynman on nanotechnology is open to debate,
but it is notable that Feynmans vision of atomically precise fabrication was cited by Bill Clinton
during his presidential address when he proposed financial backing for scientific research in
nanotechnology in January 2000. All science has to be funded, and political and economic
factors are important factors in determining where the money goes. Science is a human activity
and Nobel laureates have more political influence than their less experienced colleagues.

Individual atoms can be visualized and manipulating


using the scanning tunnelling and atomic force
microscopes
One significant step in the bottom-up approach to the subject was the development
of the scanning tunnelling microscope (STM) (see page 92) and the atomic force
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12 Option A: Materials

Nanotechnology
microscope (AFM), which can visualize and manipulate individual atoms in a physical
involves research way due to the interactions between the atoms of the probe and the atoms of the
and technology material under scrutiny.
development in the
1100 nm range.
It creates and uses
structures that have
novel properties
because of their small
size and builds on
the ability to control
or manipulate on the
atomic scale. One
nanometre is 0.000 000
001 m. It can be written
as 1 nm or 1 109 m.

Coloured atomic force


micrograph (AFM) of
molecules of yttrium oxide
(Y2O3) on a thin film of
yttrium. A thin probe is moved
across the surface and its
movements as it follows the
Self-assembly can occur spontaneously in solution due
contours of the surface are to intermolecular interactions
translated into an image.
Although ionic crystals naturally grow in solution as the opposite charged ions
organize themselves into a lattice structure, the self-assembly of covalent structures is
more complex.
Simple molecules such as water and glucose, for example, are just below 1 nm in
size. The synthesis of nanoscale materials, which are 10100 times larger, from such
molecules is difficult using conventional chemical methods. It would involve large
numbers of molecules spontaneously self-assembling. The process does, however,
occur in nature where highly complex molecular structures such as proteins are
built from the simple building blocks of 20 amino acids. This is possible as the amino
molecules recognize and bind to each other by intermolecular interactions such as
hydrogen bonding and van der Waals forces. DNA-assisted assembly methods can
be used in a similar way to make nanoscale materials. Strands of the molecule act as an
intelligent sticky tape allowing only certain base pairings to occur. Molecules can only
bind to bases of the DNA when specific hydrogen bonding interactions occur. The field
has developed in many directions, with chemists synthesizing ever more complex and
finely tuned super-molecules.

NATURE OF SCIENCE
The top-down perspective of Richard Feynman contrasts with the bottom-up approach first
advocated by Eric Drexler, who envisaged molecular machines manoeuvring things atom
by atom. Drexlers views are controversial and have been criticized by Nobel Laureate Rick
Smalley who has argued that fundamental physical principles would prevent them from ever
being possible. Smalley believes that Drexlers speculations of molecular assemblers have
threatened the public support for development of nanotechnology as some are concerned that
these molecular assemblers could somehow get out of control. An understanding of science is
vital when society needs to make decisions involving scientific issues but how does the public
judge such issues? As experts in their particular fields, scientists have a role in answering such
questions responsibly.

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Nanowires are used in electronic
devices
Two examples of nanotechnology which are of
interest are nanowires and nanotubes. Scientists
hope to build tiny transistors from nanowires
which can be as small as 1 nm in diameter, for use in
computer chips and other electronic devices. These
are generally constructed in a bottom-up approach
in which atoms are organized on a surface by
growing the nanowires on a donor substrate.

Carbon nanotubes are Coloured scanning tunnelling


micrograph of nanowires. Just
made from pentagons 10 atoms wide, these wires
and hexagons of could be used in computers
operating at the limits of
carbon atoms miniaturization.
The structure of
buckminsterfullerene, C60, was
discussed in Chapter 4. The
inclusion of pentagons into the Figure 12.34 C60 has a
hexagonal structure of graphite structure consisting of
interlinking hexagonal and
allows the carbon atoms to form
pentagonal rings that form a
a closed spherical cage (Figure hollow spherical shape similar
12.34). The discovery of C60 was to a soccer ball.
one of the key developments in
nanochemistry.
The discovery of C60 led to the discovery of a whole family of structurally related
carbon nanotubes. These resemble a rolled-up sheet of graphite, with the carbon
molecules arranged in repeating hexagons. The tubes, which have a diameter of 1 nm,
can be closed if pentagons are present in the structure (Figure 12.35).

Figure 12.35 The carbon


nanotube is capped owing to
the presence of pentagons at
the ends of the structure.

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12 Option A: Materials

Single-walled carbon nanotubes (SWNTs) and multi-


walled carbon nanotubes (MWNTs ) can be made
A whole series of molecules, including structures with multiple walls of concentric
tubes, have been produced. Carbon nanotubes have proved to have very useful
properties.
Bundles of carbon nanotubes have tensile strengths between 50 and 100 times that of
In 1996 scientists at the iron, as there is strong covalent bonding within the walls of the nanotube.
IBM Research Laboratory
in Zurich built the worlds Different tubes have different electrical properties because, at the nanoscale, the
smallest abacus. Individual behaviour of electrons is very sensitive to the dimensions of the tube. The electron
C60 molecules could be
behaves more like a wave than a particle at these dimensions, and its electrical
pushed back and forth
by the ultra-fine tip of properties are determined by the relationship between the wavelength of the electron
a scanning tunnelling and the tube length. Some tubes are conductors and some are semi-conductors.
microscope.
Their properties can also be altered by trapping different atoms inside the tubes. Silver
chloride, for example, can be inserted into a tube and then decomposed to form an
The worlds smallest test
tube has been made from
inner coat of silver. The resulting tube is a thin metallic electrical conductor.
a carbon nanotube. One As tubes have large surface areas and specific dimensions, they have the potential to be
end of the tube is closed
by a fullerene cap that very efficient and size-selective heterogeneous catalysts. Their mechanical (stiffness,
contains both pentagons strength, toughness), thermal, and electrical properties allow a wide variety of
and hexagons. The tube applications, from batteries and fuel cells, to fibres and cables, to pharmaceuticals and
has a volume of 1024 dm3. biomedical materials.

Graphene is a single atomic plane of graphite


The 2010 Nobel Prize for Physics was awarded to Andre Geim and Konstantin
Novoselov for their groundbreaking experiments regarding the two-dimensional material
graphene.
Graphene is the thinnest material known and yet it is also one of the strongest.
It conducts electricity as efficiently as copper as there is extensive delocalization
of electrons throughout the structure and it out performs all other materials as a
conductor of heat. Graphene is almost completely transparent, yet so dense that even
the smallest atom, helium, cannot pass through it. All these properties are quantum
effects related to the single atom thickness of its structure.

Graphene is composed of
hexagonally arranged carbon Carbon nanotubes are made by arc discharge,
atoms (spheres) linked by
strong covalent bonds. It
chemical vapour deposition (CVD), and high-pressure
transports electrons highly carbon monoxide (HIPCO)
efficiently and may one day
replace silicon in computer Open carbon nanotubes are generally formed when gaseous carbon atoms aggregate
chips and other technology to form hexagonal arrangements with the same chicken wire structure as graphite.
applications. Closed tubes are formed if the conditions allow for the additional formation of carbon
pentagons. The techniques used differ in the source of the carbon atoms, the method
used to vaporize the carbon atoms, and the type of tubes generated. The carbon atoms
need to be produced in an oxygen-free atmosphere so as to prevent combustion to
carbon dioxide.
MWNT are easier to produce in high volume quantities than SWNT.

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Source of
Method Details Product
carbon

Arc discharge Graphite A large electric discharge is passed between two graphite A complex mixture is
electrodes in an inert atmosphere of low pressure helium produced which requires
or liquid nitrogen. The carbon atoms condense at the further purification to
cathode and form carbon nanotubes. This was the method separate the CNTs from
used to first make C60. the soot and the residual
catalytic metals present in
Hydrocarbon An electric arc is discharged between metal electrodes the crude product.
solvent submersed in a hydrocarbon solvent. A small rod-shaped
deposit is formed on the anode.

Laser ablation Graphite A high-powered laser atomizes a high-temperature SWNT are produced.
graphite target in an inert atmosphere.

Chemical Hydrocarbon A hydrocarbon gas is passed over heterogeneous metal Both MWNT and MZNT
vapour gas catalysts in a silica or zeolite support. Nanotubes form on can be made, depending
deposition the catalysts surface as the carbon atoms condense from on the temperature.
(CVD) the atomized hydrocarbon.

High-pressure Carbon An iron/carbon monoxide complex Fe(CO)5 breaks up to SWNT tubes are
carbon monoxide produce iron nanoparticles, which act as a catalyst for the produced.
monoxide disproportionation of carbon monoxide:
(HIPCO) CO(g) + CO(g) C(s) + CO2(g)
process
This allows the carbon nanotubes to form on the surface
of the iron particles.

Implications of nanotechnology
Nanotechnology has the potential to provide significant advances over the next 50
years. Applications will be broad, including healthcare, medicine, security, electronics,
communications, and computing.

Area Current and potential uses

agriculture nanoporous zeolites for slow release of water and fertilizers

healthcare/medicine biological nanosensors as diagnostic tools

energy nanoscale catalyst-enhanced fuels for better efficiency


nanomaterials for fuel cells/batteries/solar cells

electronics carbon nanotube electronic components

ICT at panel exible displays using nanotechnology


high-density data storage using nanomagnetic effects
faster processing using quantum computers Quantum dot nanoparticle
probes, used to target and
water treatment nanomembranes for water treatment image tumours through the
incorporation of antibodies
that bind to the target cancer
Nanotechnology will have an impact on the ethical, legal, and political issues that face the cells.
international community in the near future. It is important that international bodies such as
UNESCO promote a dialogue between the public and the scientific communities.

While scientists are very excited about the potential of nanotechnology, there are
some concerns about the problems that the new technologies might cause. New
technologies always carry new risks and concerns. There are unknown health effects
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12 Option A: Materials

Some people are


and concerns that the human immune system will be defenceless against nanoscale
concerned about the particles. As they have very different properties from their related bulk materials, they
possible implications of need to be handled differently. The toxicity of the materials, for example, depends
nanotechnology. How on the size of particles. Many applications only require very small numbers of
do we evaluate the
nanoparticles, so this reduces risks considerably. However some uses involve large
possible consequences of
future developments in quantities, for example sunscreens. Large-scale manufacture can lead to explosions.
technology? Do the public The small particle size and large surface area increase the rate of reactions to
have enough knowledge dangerous levels. Like any new chemical products, a full risk assessment is required,
to make an informed
both for the production of new materials and for their subsequent uses. It is the
decision or should we rely
on the authority of expert responsibility of scientists to carry out these trials, assess the risks, and engage in
opinion? debate with the public to ensure that concerns are addressed and the scientific facts of
the technology are communicated.

Exercises
29 Carbon atoms can be constructed into various shapes, including balls, tubes, and pipes.
(a) A carbon nanotube has a diameter of 1 nm and is 10 m long. How many diameters does this
length represent?
(b) These tubes are believed to be stronger than steel. Explain the tensile strength of the tubes on a
molecular level.
(c) One problem in the synthesis of nanotubes is that a mixture of tubes with different lengths and
orientations is produced. Suggest why this is a problem.
(d) Suggest two reasons why carbon nanotubes could be effective catalysts.
(e) Describe and explain the effect of the length of a carbon nanotube on its electrical conductivity.
30 The wavelength of UV light is in the range 1400 nm. Many modern sunscreens contain nano-sized
particles of titanium dioxide which do not absorb ultraviolet radiation.
(a) Suggest how these nanoparticles are able to protect the skin from ultraviolet radiation.
(b) Suggest a reason why it is difficult to regulate for the toxicity of nanoparticles.
31 A Boy and His Atom is the worlds smallest movie. The boy in the picture is made up from about 130
atoms of carbon and oxygen.

(a) Estimate the height of the boy in the picture.


(b) Suggest a method used to move the atoms to make the animation.

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A.7 Environmental impact: plastics

Understandings:
Plastics do not degrade easily because of their strong covalent bonds.
Burning of poly(vinyl chloride) releases dioxins, HCl gas, and incomplete hydrocarbon combustion
products.
Dioxins contain unsaturated six-membered heterocyclic rings with two oxygen atoms, usually in

positions 1 and 4.
Chlorinated dioxins are hormone disrupting, leading to cellular and genetic damage.

Plastics require more processing to be recycled than other materials.

Plastics are recycled based on different resin types.

Guidance
Dioxins do not decompose in the environment and can be passed on in the food chain.
Consider polychlorinated dibenzodioxins (PCCD) and PCBs as examples of carcinogenic chlorinated

dioxins or dioxin-like substances.

Applications:
Deduction of the equation for any given combustion reaction.
Discussion of why the recycling of polymers is an energy intensive process.
Discussion of the environmental impact of the use of plastics.

Comparison of the structures of polychlorinated biphenyls (PCBs) and dioxins.

Discussion of the health concerns of using volatile plasticizer in polymer production.

Distinguish possible resin identification code (RIC) of plastics from an IR spectrum.

Guidance
House fires can release many toxins due to plastics (shower curtains, etc.). Low smoke zero halogen
cabling is often used in wiring to prevent these hazards.
Consider phthalate esters as examples of plasticizers.

Resin identification codes (RIC) are in the IB data booklet in section 30.

Structures of various materials molecules are in the IB data booklet in section 31.

Health concerns of using volatile plasticizer in polymer


production
Plasticizer molecules have molecular covalent structures and so are generally volatile.
Although they are trapped within the polymer structure, they are not chemically
bonded to it and so can easily be released into the environment when a plastic ages and
breaks down. There is some concern of the health effects of human exposure to the
phthalate plasticizers. Many different phthalates exist with different properties, uses,
and health effects. There is some evidence that phthalates effect the development of the
male reproductive system in laboratory animals and phthalates are often classified as
endocrine disruptors or hormonally active agents because of their ability to interfere
with the endocrine system in the body. Experiments on laboratory animals have
shown that they are potential carcinogens. The relatively high exposure of children to
phthalates is of particular concern as PVC is present in many toys and childcare items.
Levels are controlled in some countries to below 0.1% by mass. The evidence of adverse
effects on human health is limited and more research is needed in this area.

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12 Option A: Materials

Plastics do not degrade easily because of


their strong covalent bonds
As most plastic products have a short life cycle plastics account for
about 10% by mass of our total waste and about 25% by volume.
This leads to two problems:
plastics are produced from crude oil which is non-renewable;
most plastics are not biodegradable and waste placed in landfill
does not degrade for hundreds of years.
Polymers are not broken down naturally as bacteria do not have
the enzymes needed to breakdown the strong covalent C C bond
found in synthetic polymers.
Much of our plastic waste has been used to landfill disused
quarries. However, suitable sites are becoming harder to find and
reducing the amount of plastic dumped into landfills is a high
priority.
Some poly(ethene) plastic bags, with added natural polymers
Plastic waste is not such as starch, cellulose, or protein, however, can be made to
biodegradable and persists biodegrade. The bacteria in the soil decompose the natural
for a long time, causing
polymer and so the bag is broken down into smaller pieces. The
environmental problems.
synthetic polymer chains that remain have an increased surface
area which speeds up the rate of decay further. One problem
with biodegradability is that conditions in a landfill are often not
suitable. The need to make sites watertight to prevent soluble
products leaking into the environment also limits the supply of
oxygen, preventing the bacteria from acting.

Incineration of plastics reduces bulk,


releases energy but produces air pollution
As the addition polymers are made up from mainly carbon and
hydrogen, they are a concentrated energy source. Waste plastic can
be burned and used as a fuel but there are problems.

Landfill sites are used to


dispose of about 90% of the
worlds domestic waste.

Biodegradable plastics are produced using plant-based


starch. These bioplastics break down much faster than
petroleum plastics and also produce little, if any, toxic by-
products when burned.

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Carbon dioxide is a greenhouse gas.
Carbon monoxide produced during incomplete combustion is poisonous.
The combustion of PVC poses a particular problem as the hydrogen chloride
produced causes acid rain. It must be removed from the fumes before they are
released into the atmosphere.

Worked example
Complete combustion of PVC produces water, carbon dioxide, and hydrogen
chloride (HCl).
Deduce an equation for the reaction using (CH2CHCl)n as the molecular formula of
the polymer.
Solution

The unbalanced equation:


(CH2CHCl)n + O2 CO2 + H2O + HCl
1 Balancing carbon and chlorine: there are 2nC and nCl on the left use this
information on the right:
(CH2CHCl)n + O2 2nCO2 + H2O + nHCl
2 Balancing the hydrogens: there are 3nH on the left again, use this information
on the right:
(CH2CHCl)n + O2 2nCO2 + nH2O + nHCl
3 Balancing the oxygens: there are 5nO on the right use this information on the
left:
5n
(CH2CHCl)n + O 2nCO2 + nH2O + nHCl
2 2

Chemical waste incinerator,


where toxic chemicals
are broken down by high
temperatures into harmless or
non-toxic products.

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12 Option A: Materials

Incomplete combustion of PVC produces dioxins


The complete combustion of plastics is rarely possible in reality, and dioxins can be
unintentionally generated as by-products, depending on the incineration conditions.
Dioxins contain unsaturated six-member heterocyclic rings with two oxygen atoms,
usually in positions 1 and 4.

1.4-dioxin polychlorinated dibenzo-p-dioxin


O O
Clm
O Cln O

Each benzene ring can have up to four chlorine atoms.


They are 10 000 times more poisonous than the cyanide
ion and they disrupt the action of hormones and can cause
cellular and genetic damage. The molecules do not readily
decompose in the environment and so can be passed on
in the food chain. Dioxins persist in fat and liver cells.
Symptoms of dioxin poisoning are cirrhosis of the liver,
damage to heart and memory, concentration problems,
and depression. The skin disease chloracne is a result of
the body attempting to remove the poison through the
skin. Dioxin can cause malfunctions in fetuses. It was
one of the herbicides present in the defoliant called Agent
Orange used during the Vietnam War.

Environmentalists investigating
dioxin contamination of soil at
Times Beach, Missouri. Polychlorinated biphenyls (PCBs) and polychlorinated
dibenzofurans are dioxin-like substances and are also
carcinogenic
The polychlorinated biphenyls have a high electrical resistance and are used in
electrical transformers and capacitors. The structure is shown below. They contain a
number of chlorine atoms attached to two connected benzene rings (biphenyl).

Clm

Cln

They are released into the environment from poorly maintained hazardous waste
sites and the incomplete burning of waste from industrial incinerators. PCBs can
accumulate in the leaves and above-ground parts of plants and food crops. They are
also taken up into the bodies of small organisms and fish. As a result, people who ingest
fish may be exposed to PCBs that have bioaccumulated in the fish they are ingesting.
The polychlorinated dibenzofurans, shown below, are a group of toxic compounds
associated with PCBs. They are produced in incinerators and are also carcinogenic.

O
Clm

Cln
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House res can release many toxins when plastic
objects burn
The combustion products of plastics are a serious concern in the event of a house
fire. Although PVC is often used for its fire-retarding properties, we have seen that
it produces a nasty cocktail of dangerous gases, including the dioxins and hydrogen
chloride, when it does burn. The hydrogen chloride reacts with any water present to
form hydrochloric acid.
One possible solution to this problem is to use low-smoke zero-halogen cabling made
from plastics such as poly(propene). These give off only limited amounts of smoke and
no hydrogen chloride. They are particularly used in underground areas where smoke
Do animals have the
levels can build up. These materials also have a reduced environment impact if they are same rights as human
incinerated after use. beings? Is experimenting
on rats more acceptable
NATURE OF SCIENCE than experimenting with
There is some dispute over the carcinogenic properties of the phthalates. Testing the chemicals monkeys? What criteria
on animals raises many ethical issues and the only data available are based on tests on rats and have you used to justify
mice. It may be true that what causes cancer in humans also causes cancer in rodents, but the your answer?
reverse is not necessarily true. The IB has a strict animal experimentation policy.

Plastics require more processing to be recycled than


other materials
Ideally materials should be reused so that no waste is produced. If this is not possible,
the best alternative is recycling as it reduces:
the use of raw materials
energy costs
The recycling symbol on the
the level of pollutants
bottom of a bleach bottle
the need of land for waste disposal. indicates that the plastic is
high-density poly(ethene).
One challenge is the separation and purification of the materials. Although methods Different plastics can be
of mechanical separation have been developed, ideally the plastics should be collected identified by different numbers.
separately to reduce costs. Plastics are recycled based on different resin types and the This assists in sorting plastics
resin identification codes are listed in section 30 of the IB data booklet. Recycled before they are recycled.

materials tend to be of a lower grade quality than new materials due to the problems of
purification.
Brooms made from recycled
As thermoplastics can be melted down and remoulded they can be recycled plastic.
mechanically. This is the simplest and cheapest method: the used
plastics are cut into small pieces, separated according to their
relative density in a floating tank, and heated and extruded to form
new shapes.
Chemical methods involve depolymerization. The used plastics
are heated in the absence of air and split up into their monomers
in a process known as pyrolysis. The products are separated
by fractional distillation and used as chemical feedstock by the
petrochemical industry to make other products including plastics.
There are energy costs in both processes.
For recycling to be successful and self-sustainable, the costs of
recycling must be less than those needed to produce new materials.
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12 Option A: Materials

Unfortunately, plastics require more processing to be recycled than other materials.


There are costs in collecting and sorting the different used plastics. There are often
lots of additives in plastic products, such as reinforcements, fillers, and colorants
and mixtures of plastics are much weaker than the individual plastics so the recycled
product is often of lower quality than the original with only a limited range of uses.

Plastics can be identied from their IR spectrum


As recycling companies dont usually know exactly what it is they are getting, it is
important that they are able to identify plastics and process them appropriately. The
plastics are first ground into little pellets and then passed on a conveyer belt where they
are identified by a spectrometer which triggers the sorting process.
As discussed in Chapter 11, the positions of absorption bands in the IR spectrum gives
information about the presence or absence of specific functional groups in a molecule.
The whole spectrum constitutes a fingerprint that can be used to identify the plastic.
Although the IR spectra for poly(ethene) and poly(propene) are very similar (as they
both made up from C C and C H bonds), they are not identical. As discussed in
Chapter 11, the vibrations of the individual bonds are not independent as it is the
whole molecule that vibrates. These differences are sufficient to distinguish between
the two isomers.
The IR spectrum of PVC is shown in Figure 12.36. The absorption band between 600
and 700 cm1 due to the presence of the C Cl bond is a key feature of the spectrum.
100
% transmittance

50

Figure 12.36 The IR spectrum


0
of PVC. Note the absorption 4000 3000 2000 1500 1000 500
band at 600700 cm1. wavenumber/cm1

IR spectroscopy can also be used to test the quality of the materials during all stages of
the manufacturing process.

Worked example
The infrared spectrum of a compound shows a strong absorption at 10001400
cm1 but no absorption between 2850 and 3090 cm1. Deduce the structure of the
polymer using information in section 26 of the IB data booklet.
Solution

Absorption 10001400 cm1: CF present


No absorption 28503050 cm1: no CH present

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( )
F F CHALLENGE
It has the structure C C YOURSELF
3 Explain why the absorption
F F n of CX bonds for the
halogens occurs at such
The polymer is called poly(tetrafluoroethene) or Teflon.
wavenumbers compared to
the CH stretch.
NATURE OF SCIENCE
It is said that the American space programme would have floundered without Teflon because
the material was used to make so many things, from space suits to the bags used to hold One aspect of caring
samples of moon rock. It is now used to make non-stick pans, Gore-Tex fabric, and hip joint in the IB Learner profile
replacements. Science has been used to solve many problems and improve human life, but it is to show a personal
can also inadvertently cause environmental problems. Risk benefit analyses, risk assessments, commitment to service
and the precautionary principle are all parts of the scientific way of addressing the common and act to make a
good. positive difference to
The discovery of the addition polymers poly(ethene) and Teflon both included some elements the environment. What
of luck. The significance of serendipity in scientific discovery was discussed on page 617. impact do your actions
make on your local
environment? Are there
Different countries have different recycling policies. For recycling to be successful, economic
ethical obligations for
and political factors need to be considered. If it is not economical to recycle plastic at the
humanity to treat the
moment perhaps we should bury the plastics separately so that future generations could
natural environment in a
recover it later. Plastic disposal is a global problem with local solutions.
certain way?

Exercises
32 (a) Plastics have replaced many traditional materials. Suggest two properties which make plastic more
suitable than wood for making childrens toys.
(b) Increased use of polymers has led to problems of waste disposal. State one method of waste
disposal and discuss issues other than cost associated with its use.
(c) Explain why synthetic polyalkenes are not generally biodegradable.
(d) Explain how a poly(ethene) bag can be made more biodegradable.
33 Discuss the advantages and disadvantages of incineration as a method of disposal compared with
landfill sites.
34 Discuss the advantages and challenges of recycling plastics.
35 The general structure of the some pollutants is given in section 31 of the IB data booklet.
(a) State the range of permissible values for n and m for the polychlorinated biphenyls.
(b) State the range of permissible values for n and m for the polychlorinated dibenzofurans.
36 Compare the IR spectra of ethene and its polymer.

Superconducting metals and


A.8 X-ray crystallography
Understandings:
Superconductors are materials that offer no resistance to electric currents below a critical
temperature.
The Meissner effect is the ability of a superconductor to create a mirror image magnetic field of an

external field, thus expelling it.


Resistance in metallic conductors is caused by collisions between electrons and positive ions of the

lattice.
The BardeenCooperSchrieffer (BCS) theory explains that below the critical temperature electrons

in superconductors form Cooper pairs which move freely through the superconductor.
Type 1 superconductors have sharp transitions to superconductivity whereas Type 2

superconductors have more gradual transitions.

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12 Option A: Materials

X-ray diffraction can be used to analyse structures of metallic and ionic compounds.
Crystal lattices contain simple repeating unit cells.
Atoms on faces and edges of unit cells are shared.

The number of nearest neighbours of an atom/ion is its coordination number.

Guidance
Only a simple explanation of BCS theory with Cooper pairs is required. At low temperatures the
positive ions in the lattice are distorted slightly by a passing electron. A second electron is attracted to
this slight positive deformation and a coupling of these two electrons occurs.
Operating principles of X-ray crystallography are not required.

Only pure metals with simple cubic cells, body centred cubic cells (BCC), and face centred cubic cells

(FCC) should be covered.

Applications:
Analysis of resistance versus temperature data for Type 1 and Type 2 superconductors.
Explanation of superconductivity in terms of Cooper pairs moving through a positive ion lattice.
Deduction or construction of unit cell structures from crystal structure information.

Application of the Bragg equation, n = 2dsin, in metallic structures.

Determination of the density of a pure metal from its atomic radii and crystal packing structure.

Guidance
Perovskite crystalline structures of many superconductors can be analysed by X-ray crystallography
but these will not be assessed.
Braggs equation will only be applied to simple cubic structures.

Resistance in metallic conductors is caused by


collisions between electrons and the positive ions in
thelattice
As discussed in Chapter 4, a solid piece
+ e + e
+ of metal, at room temperature, consists
of a regular lattice of metal ions with the
Figure 12.37 A piece of metal e e e delocalized valence electrons moving in
which does not have current
flowing through it. The arrows the spaces (Figure 12.37). The motion of
represent the random thermal
+ e + e + the free electrons is random.
motion of the electrons
(their average speed at room e e e When a power source such as a battery is
temperature is hundreds of connected to the metal another motion
km s1). + e + e + is added to the random thermal motion
of the electrons. This is more regular and
results in a general drift of electrons
through the metal from the
+ e + e + negative terminal of the power
source to the positive terminal
e e e (Figure 12.38). A typical drift
+ e + e + + velocity for electrons in metals
is 1 mm s1.
Figure 12.38 When a metal is
connected to a battery there e e e The resistance of a piece of
is a general drift of electrons
from the negative terminal
metal is due to collisions
+ e + e + between the delocalized
of the power source to the
positive terminal. electrons and the positive ions
electron drift which get in their way and

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impede their movement through the metal. During a collision, some of the electrons
kinetic energy is transferred to the ion, which increases the amplitude of their lattice
vibrations. This increases the average kinetic energy of the ions and therefore the
temperature of the metal.
The resistance of metals generally increases with temperature as the ions are vibrating
with larger amplitude and so they get more in the way of the moving electrons. By
contrast, the resistance of semi-conductors decreases with an increase in temperature
as more electrons have sufficient energy to be free from individual atoms and available
for conduction. Type 1 superconductors are exceptional in that their resistance falls to
zero at low temperature (Figure 12.39).
(The temperature dependence of Type 2 superconductors will be discussed in more
detail later.)

semiconductor
resistance

superconductor (type 1)

metal
0 Figure 12.39 The variation of
resistance with temperature for
0
temperature/K different materials.

Superconductors are materials that offer no resistance A superconductor is a


to electric currents below a critical temperature material that conducts
electricity without
The resistance of metals generally decreases with temperature. Superconductors show resistance.
extreme properties in that the resistance falls to zero at a critical temperature. The
effect was first observed by the Dutch physicist Heike Kamerlingh Onnes in 1811 and
it was completely unexpected. The fact that a coil of wire made from a superconductor
could carry an electric current round and round forever without needing a power
source defied explanation.

NATURE OF SCIENCE What role do personal


disagreements play in the
Onnes work in low temperature physics would not have been possible without his team of
pursuit of knowledge?
expert glassblowers and technicians needed to build and maintain the delicate equipment
needed for such work. He had the best equipped and best organized laboratory in the world
at the time. His original goal was to be the first to make liquid helium, which was the last gas
to be liquefied, needing a temperature of 4 K. His success can be contrasted to the work of his
British competitors, Dewar and Ramsey, which was hampered by the personal enmity between
the pair. Ramsey, for example, had access to all the helium in Britain but would not share this
precious resource with Dewar. Science is a human activity and scientists need to work in a
team to be effective.

We now believe that the current in a Type 1 superconductor is carried by a Cooper


pair of electrons. The formation of a Cooper pair is illustrated in Figure 12.40.

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12 Option A: Materials

Superconductivity was first observed as a low temperature effect, when the positive
ions have low vibrational energy. The presence of an electron, at such temperatures,
distorts the lattice structure locally and attracts the oppositely charged positive ions.
Figure 12.40 The formation of The positive ions become more closely packed and a region of high positive charge
Cooper pairs. density is formed. A second electron is then attracted into the same region, and the
two electrons form a Cooper pair.

+ + + + +

+ +
+ + +
A second electron is attracted into the distorted region where

the positive ions are more densely packed. It forms a Cooper
+ + + + + pair with the electron that was responsible for the original
distortion.
+ + +
+ + An electron attracts positive ions and so distorts the local
structure of the lattice. The positive ions are more closely
packed within this region.
+ + + + +

The electron pair is more difficult to impede than a single electron, in the same way
that a pair of people holding hands would be harder to stop than an individual, and
Cooper pairing is a the Cooper pair passes through the crystal lattice unimpeded and the material has
quantum effect. Electrons no resistance.
have a spin of and are
fermions which follow
Paulis exclusion principle.
A Cooper pair has a spin
of +1 or 0 and behaves as
a boson. Bosons do not
follow Paulis exclusion
principle.

Leon N. Cooper (born 1930),


giving a lecture. He shared
the 1972 Nobel Prize in
Physics with Bardeen and
Schrieffer for their work
on superconductivity. The
theory is known as the BCS
superconductivity theory,
after their initials. The theory
involves electron pairs, which
are named Cooper electron
pairs in his honour.

The best conductors at room temperature are gold, silver, and copper. They do not
show any superconducting properties as they have the smallest lattice vibrations
and so cannot be distorted in a way that allows for the formation of a Cooper pair.
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The Meissner effect is the ability of a superconductor to
create a mirror image magnetic eld of an external eld,
thus expelling it
The German physicist, Walther Meissner, showed that superconductors were perfect
diamagnets: they move away when placed in an external magnetic field. There is no
magnetic field in the interior of the material as the external magnetic field induces eddy
currents around the exterior which produces a magnetic field equal and opposite to
the external field that originally induced them (Figure 12.41). The currents screen the
interior of the material from the external magnetic field which is forced to pass around
the superconductor.

external magnetic magnetic


field field

induced eddy
currents in
superconductor

magnetic field Figure 12.41 There is no


produced by external field in the interior of
induced eddy a superconductor, as illustrated
by the shaded circle.
currents

Type 1 superconductors
have sharp transitions
to superconductivity
opposing magnetic field
produced by induced

opposing magnetic field =


whereas Type 2 external magnetic field
currents

superconductors have
more gradual transitions
Superconductors can be classified as
Type 1 or Type 2 according to their
behaviour in an external magnetic
field. Type 1 materials lose their
perfect diamagnetic properties once external magnetic field critical magnetic field
the magnetic field exceeds a critical
value (Figure 12.42). They dont behave as superconductors at higher magnetic fields Figure 12.42 The response of
Type 1 superconductors to an
which eventually rip apart the Cooper pair needed for superconductivity.
external magnetic field.
Type 2 superconductors lose their magnetic properties more gradually (Figure 12.43).

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12 Option A: Materials

A Type 2 superconductor is said to exist in


opposing magnetic field

a mixed state in regions between the critical


produced by induced

opposing magnetic
field = external
value Bc and B0. Under these conditions,
magnetic field regions of the magnetic field thread through
current

Bc the bulk material which then loses its


opposing magnetic superconducting properties in these regions.
field falls gradually The superconductivity of the bulk material
above critical value is thus reduced and will eventually fall to
B0 zero at B0 when the magnetic field passes
critical magnetic value Bc magnetic field when
through the whole material.
external magnetic field opposing magnetic
field falls to zero

Figure 12.43 The response of


Type 2 superconductors to an
external magnetic field.
Type 1 and Type 2 superconductors
Type 1 superconductors are metals and metalloids
The Type 1 category of superconductors mainly consists of metals and metalloids
that show some conductivity at room temperature. The variation of resistance for a
Type 1 superconductor was shown in Figure 12.42 it falls sharply to zero at a critical
temperature.
The critical temperatures of some Type 1 superconductors are shown in the table.

Material Material type Tc / K

Ti metal 0.40

Zn metal 0.88

Al metal 1.19

Cr metal 3.00

Sn metal 3.72

Hg metal 4.15

Figure 12.44 The variation of Type 1 superconductors have been of limited practical use as the critical magnetic
resistance with temperature
fields and temperatures are so low that they can only be maintained using expensive
for the Type 2 superconductor
YBa2Cu3O7. liquid helium.
Type 1 superconductors are sometimes called
soft superconductors.

Type 2 superconductors are


metallic compounds and alloys
resistance

Type 2 superconductors are generally made


up from metallic compounds and alloys. Their
resistance does not fall so sharply to zero as the
temperature is lowered (Figure 12.44).
0
0 50 100 150 200 250 The recently discovered superconducting
temperature/K perovskites (metal-oxide ceramics that
normally have a ratio of 2 metal atoms to every

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3 oxygen atoms) belong to this Type 2 superconductor group. They achieve higher
critical temperatures than Type 1 superconductors by a mechanism that is still not CHALLENGE
completely understood, although it is thought to be linked to the planes of CuO4 units YOURSELF
within the structure.
4 The mineral perovskite has
Type 2 superconductors are also known as the hard superconductors. the formula CaTiO3. Deduce
the oxidation state of Ti in
the mineral.
All high-temperature superconductors are Type 2 5 One copper oxide
superconductor has
semiconductors the formula YBa2Cu3O7.
One of the first high-temperature superconductors was lanthanum barium copper Assuming that Y is in
oxide, discovered in 1987, which has a critical temperature of 30 K. Other copper oxide the +3 state, deduce the
oxidation number of Cu and
superconductors were soon discovered. Superconductors with a critical temperature comment on your answer.
above 77 K are particularly useful as this is the boiling point of liquid nitrogen which
is a very inexpensive compared to the liquid helium needed for the low temperature
superconductors. High-temperature superconductors are Type 2 conductors.

Material Material type Tc / K

YBa2Cu3O7 ceramic 90

TlBaCaCuO ceramic 125

Molecular computer
graphic showing the crystal
structure of one of the
new generation of high-
temperature superconductors;
this is yttrium barium
copper oxide (YBa2Cu3O7).
Discovered in 1987, the new
superconducting ceramic
materials are expected to lead
to a technological revolution.
The picture highlights the
square-pyramidal (red)
and square-planar (green)
coordination of copper
by oxygen ions in this
orthorhombic structure.
Yttrium ions are the yellow
spheres, and barium ions the
blue spheres.

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12 Option A: Materials

Demonstration of magnetic
levitation of one of the
new high-temperature
superconductors yttrium
barium copper oxide
(YBa2Cu3O7). The photograph
shows a small, cylindrical
magnet floating freely
above a nitrogen-cooled,
cylindrical specimen of a
superconducting ceramic
(made by IMI Ltd). The
glowing vapour is from liquid
nitrogen, which maintains
the ceramic within its
superconducting temperature
range.

Superconducting magnets NATURE OF SCIENCE


played a crucial role in The technical development of high-temperature superconductors poses a number of
the hunt for the Higgs problems. It is a multi-disciplinary problem and the skills of the chemist are needed to
boson at the Large Hadron synthesize ceramics of different composition. One problem is that ceramic materials are too
Collider in CERN. A large brittle to be produced on a large scale. The skills of the physicist are needed to investigate and
magnetic field is needed explain their unusual properties. There is still quite a lot of dispute about the mechanism of
to steer the elementary Type 2 conductivity and material scientists and engineers need to apply the unusual properties
particles around the of superconductors to new technologies.
27km long circular tunnel
under the FrenchSwiss
border. Operations
had to be halted at an The structure of solids
earlier stage for a year as
several tonnes of helium, The structures of many solids can be understood using a simple model in which atoms
needed to maintain the are represented by spheres. In many pure metal structures these spheres are packed
low temperatures for densely in a cubic structure.
superconductivity, had
leaked into the tunnel.
The cubic close-packed crystal
structure has a coordination
A number of 12
B In the cubic close-packed structure one layer of
atoms (A) is arranged in a closely packed layer
C so that each sphere is surrounded by a hexagon
of other spheres. A second layer (B) is then
placed on top of the second layer by inserting
the atoms in the holes between the atoms in
the layer below it. A third layer of atoms (C) is
then added with the atoms similarly placed in
the holes of the second layer so that they do not
overlap with the first layer. The ABC pattern is
Figure 12.45 A cubic close- then repeated, which leads to a close-packed cubic structure (Figure 12.45). The atoms
packed crystal structure. have a maximum coordination number of 12 (six atoms in the same plane, three above
and three below), and are as tightly packed together as possible. The spheres fill 74% of
The coordination
number of an atom is the available space. This arrangement of atoms is favoured by several metals, including
the number of nearest gold and silver.
neighbours it has.

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C

Figure 12.46 A unit cell of a


A cubic close-packed face-
centred cubic, crystal lattice.
B Note the close-packed layers
do not correspond to the sides
A of the cube.

A close-packed structure
is one in which atoms
This structure is also described as a face-centred cubic cell (FCC), as the atoms can occupy the smallest total
be thought of occupying the corners and centres of each face of the cube, as seen in volume with the least
empty space.
the expanded structure shown in Figure 12.46. This represents a unit cell; the whole
crystal structure can be built up by stacking these together in the same way that a wall
A unit cell is the smallest
is built from bricks. unit that when stacked
together repeatedly,
reproduces the entire
A body-centred cubic cell crystal.
(BCC) crystal structure has a
coordination number of 8
Some metals do not have a close packed
structure. One common form is the body-
centred cubic structure in which one atom is
placed at the centre of a cube of eight nearest
atoms.
Figure 12.47 A unit cell of a
Sodium, potassium, and iron have a body- body-centred cubic crystal
centred cubic crystal structure. lattice.

Counting the number of atoms in a unit cell


The coordination number of an atom in a body-centred structure is 8, as can be seen Atoms on the corner of
by focusing attention on the atom in the centre of the cube shown in Figure 12.48. All each cube are shared
the atoms, however, have the same coordination number. Each atom on the corner is by eight unit cells. Each
a member of eight other unit cells and so has eight nearest neighbours in the centre of atom contributes an
eighth of an atom to a
each of these eight unit cells. unit cell.
Similarly, the coordination number of atoms 1
in a face-centred cubic structure can be
determined by focussing on one of the atoms
Figure 12.48 The yellow
in a corner. In Figure 12.48 this atom is shaded sphere has three neighbouring
in yellow; it has three neighbouring atoms spheres on the faces within the
on the faces within the unit cell as closest 2 unit cell but twelve overall as it
neighbours, but twelve overall as it is part of is a member of eight other unit
cells. Each face atom can be
eight unit cells.
thought of as being equivalent
The atoms at the centre of a face are shared 3 to a sphere (3 8 = 12).
by two unit cells and so can be thought of as
equivalent to half an atom.
The same result is obtained by focussing attention on an atom in the centre of a face,
shown in pink in Figure 12.49. This atom is bonded to four atoms in the corner of the
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12 Option A: Materials

same face, and four atoms on faces above and below,


again giving a coordination number of 12.
F We have seen that the atom in the centre of a cube
Figure 12.49 The pink sphere C C
has four neighbouring spheres belong exclusively to one unit cell, whereas atoms
on the corners and four on the
F F on the corner are shared by eight other unit cells
faces above and below. and so contribute 1 8 of an atom to a unit cell, and
C F C atoms on a face are shared by two other unit cells
Atoms on the face of and so contribute an atom. These results can be
each cube are shared by extended: atoms on the edge of a cube are shared by
two unit cells. Each atom four units cells and so contribute a of an atom.
contributes half of an
atom to a unit cell.
Position of an atom in cubic unit cell Contribution to unit cell

centre 1

corner 1
8

face

edge

Worked example
Calculate how many atoms there are in a body-centred cubic (BCC) unit cell.
Solution

Location of
Number of atoms Contribution Total atoms
atoms

centre 1 11 1

corner 8 8 8
1
1

total = 1 + 1 = 2
There are two atoms.

Worked example
Calculate how many atoms there are in a face-centred cubic (FCC) unit cell.
Solution

Location of Number of atoms Contribution Total atoms


atoms

centre of face 6 6 3

corner 8 8 18 1

total = 1 + 3 = 4
There are four atoms.

Calculating the density of a metal


The density of a metal is an intensive property it is independent of the size of the
sample and can be determined by considering a unit cell of the material.
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Worked example
The atomic radius of copper is given in section 9 of the IB data booklet. Copper has a
face-centred cubic structure.
(a) Calculate the length of a unit cell.
(b) Determine the density of the metal.
Solution

(a) The diagonal of a face has three atoms connected together.

2 (face diagonal)

1 (length of unit cell)

the diagonal of the cube = r(M)+ 2r(M) + r(M) = 4r(M)


4 r(M)
the length of a unit cell =
2
122
=4 1012 m
2
= 345 1012 m
(b) the volume of a cube = (3.45 1010)3 m3
number of atoms = 4
63.55
mass of individual atom = g
6.02 10 23
CHALLENGE
63.55
mass of unit cell = 4
6.02 10 23
g YOURSELF
63.55 6 Calculate the percentage
4 occupied by the atoms in a
density = 6.02 10 23 g m3 FCC unit cell.
(3.45 10 10 )3
= 10 300 g m3
= 10.3 kg m3

Worked example
The atomic radius of sodium is given in section 9 of the IB data booklet.
(a) Calculate the length of a unit cell.
(b) Determine the density of the metal.

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12 Option A: Materials

Solution

(a) The diagonal of cube has three atoms connected together.

atom on bottom face


atom in centre 2 (face diagonal) 3 (cube diagonal)
atoms on top face

1 (length of unit cell)

the diagonal of the cube = r(M) + 2r(M) + r(M) = 4r(M)


4 r(M)
the length of a unit cell =
3
4 160 10 12
= m
3
= 370 1012 m
(b) the volume of a cube = (3.70 1010)3 m3
number of atoms = 2
22.99
mass of individual atom = g
6.02 10 23
22.99
mass of unit cell = 2 g
6.02 10 23
22.99
2
6.02 10 23
density = g m3
(3.70 10 10 )3
= 1500 kg m3

CHALLENGE YOURSELF
7 Calculate the percentage occupied by the atoms in a BCC unit cell.
8 A unit cell of the mineral perovskite is shown. Deduce the formula of the mineral.

Ca
Ti
O

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The structure of solids is determined by X-ray diffraction
As discussed in Chapter 11, one of the best ways of determining the structure of a solid
is X-ray diffraction. A crystal can produce a diffraction pattern with bright spots being
produced by the constructive interference of X-rays at certain angles. Constructive
interference occurs when the path difference between parallel rays is equal to an
integer number of wavelengths (Figure 12.50).
X-rays are in scattered X-rays have travelled different
phase as they distances so may be out of phase
enter the crystal
Figure 12.50 The scattered
at an angle
X-rays from different layers

path difference
of a crystal travel different
d d distances. Constructive
d
interference occurs when
the path difference is equal

to an integer number of
path difference wavelengths.

The angle at which constructive interference occurs is related to the wavelength


and distance between the atoms. We see from the right-angled triangle in Figure 12.51
that:
path difference = d sin
path difference = n = 2d sin
This is known as the Bragg equation and is given in section 2 of the IB data booklet.

Researcher using X-ray


diffraction crystallography
equipment to determine
a crystal structure. A beam
of monochromatic X-rays
is generated and directed
at the crystal (held in the
apparatus at the back of the
photograph). The repeated
pattern of the crystal lattice
acts as a diffraction grating,
diffracting the beam in a
way which depends on the
lattices arrangement and
spacing. The scattered rays
then strike a detector plate;
the intensity at each point is
recorded on X-ray sensitive
photographic film, or else, as
here, by electronic equipment
Worked example which digitizes the data for
analysis and presentation on a
X-rays of wavelength 150 1012 m are scattered by a sodium crystal lattice. Bright
computer.
spots occur at angles of 13.68 and 28.25. Determine (a) the interatomic distance
and (b) the atomic radius of sodium.
Solution

(a) n = 2d sin
with n = 1 and = 13.68

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12 Option A: Materials


d=
2sin
150 10 12
= m
2 sin13.68
= 317 1012 m
The scale at which we with n = 2 and = 28.25
can investigate the
2
world depends on d=
the wavelength of the 2sin
radiation we use to 2 150 10 12
gather information. How =
2 sin28.25
reliable is our knowledge
of the microscopic world = 317 1012 m
compared to what we
The interatomic distance is 317 pm.
know at the macroscopic
level? Can we ever get (b) Assuming the atoms are touching:
a complete picture of
d
the world if we only r = = 158.5 1012 m
use a selection of the 2
wavelengths available? The atomic radius of sodium is 158.5 pm.

Exercises
37 The resistance of two metals at low temperature is shown on the graph below.

0.02
A
electrical resistance/ohms

0.015
B
0.01

0.005

0
0 5 10 15 20 25
temperature/K
(a) Identify which of the graphs refers to a superconductor.
(b) Explain the different behaviour of the two materials with reference to their
conduction mechanism.
38 Explain why the temperature of a metal rises as an electric current is passed through it.
39 Distinguish between Type 1 and Type 2 superconductors.
40 The unit cell of a primitive cube is shown.

Calculate how many atoms there are in a unit cell of this structure.

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41 Potassium has a body-centred cubic close-packed structure. The atomic radius of potassium is
220nm.
(a) Calculate the length of a unit cell.
(b) Determine the density of the metal.
42 Gold has a face-centred cubic close-packed structure. The atomic radius of gold is 144 pm.
(a) Calculate the length of a unit cell.
(b) Determine the density of the metal.
43 X-rays of wavelength 150 1012 m are scattered by a copper crystal lattice. A bright spot occurs at an
angle of 17.9. Determine the interatomic distance and the atomic radius of copper.

A.9 Condensation polymers

Understandings:
Condensation polymers require two functional groups on each monomer.
NH3, HCl, and H2O are possible products of condensation reactions.
Kevlar is a polyamide with a strong and ordered structure. The hydrogen bonds between O and N

can be broken with the use of concentrated sulfuric acid.

Applications:
Distinguish between addition and condensation polymers.
Completion and descriptions of equations to show how condensation polymers are formed.
Deduction of the structures of polyamides and polyesters from their respective monomers.

Explanation of Kevlars strength and its solubility in concentrated sulfuric acid.

Guidance
Consider Green Chemistry polymers.

Condensation polymers can be formed from monomers


with two functional groups
Condensation polymers can be formed when monomers, with two functional groups,
undergo a condensation reaction with neighbouring monomers on both sides. A long
chain is formed in the same way as a human chain can be formed when people link
hands. Small molecules such as H2O, NH3, and HCl are released during the process.

PET is a polyester
A polyester is formed when the acid monomer has two COOH groups and the
alcohol monomer has two OH groups. The chain can extend in both directions,
forming a polyester. When describing these reactions it is sometimes helpful to think
about the functional groups sticking out in both directions as if from a box, with the
box representing the rest of the molecule. For example:

HOOC COOH 1 HO OH

HOOC C O OH 1 H2O
ester link

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12 Option A: Materials

Focusing on the functional groups in this way enables us to deduce the repeating unit
for any specified monomers.
Polyethylene terephthalate (PET) is formed when the two monomers ethane-1,2-diol
and benzene-1,4-dicarboxylic acid (terephthalic acid) are heated to a temperature
of 200 C. The carboxylic acid and hydroxyl groups combine to form an ester in a
condensation reaction:

H H H H

HO C C OH 1 HO C C OH H2O 1 HO C C O C C OH

O O H H O O H H

As the ester produced has a COOH group at one end and an OH group at the
other, it can react further and form a polymer chain with the release of one water
molecule at each stage, as shown below.

H H H H

HO C C O C C OH 1 HO C C O C C OH

O O H H O O H H

H H

O C C O C C 1 (2n21)H2O
The use of PET bottles
instead of glass for H H O O
n
containers of soft drinks
increases the volume
of drink transported by The resulting polymer is a polyester with many ester functional groups. Polyesters
60% as less packaging is can be used as fibres to make clothing. They have high tensile strength due to their
needed. crystalline structure and the relatively strong intermolecular forces between the chains
because of the polarity of the ester groups. Polyester fabrics were revolutionary when
A tube made of PET is about they first appeared in the 1950s because they do not crease.
to be inserted within the
weakened section of the As PET resembles glass in its crystalline clarity and its impermeability to gases, it is
blood vessel. also used to make bottles for soft drinks. It has the additional advantages that is has low
density, does not shatter when dropped, and is recyclable.
PET is unreactive and non-toxic, which makes it ideal as
tubing used to repair damaged blood vessels in heart bypass
operations. It is also used as a skin substitute for people who
have suffered severe burns.

Nylon is a polyamide
Most synthetic polyamides are formed when one monomer
has two COOH groups and the other monomer has two
NH2 groups. Amide links form between the molecules
and the chain can extend in both directions. We can describe
these reactions in a similar way to the formation of polyesters,
focusing on the functional groups as shown above.
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HOOC COOH 1 H2N NH2

HOOC C N NH2 1 H2O

H
amide link

The most common form of nylon is known as 6,6-nylon because both its monomers
have six carbon atoms. They are 1,6-diaminohexane and hexanedioic acid:

H2N (CH2)6 NH2 1 HOOC (CH2)4 COOH

H O
H O
N (CH2)6 N C (CH2)4 C 1 H2O
H OH

Thus, the repeating unit is:

H H O O

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

The more reactive acid chloride, hexanedioyl chloride, is generally used instead of the
di-acid. In this reaction, hydrogen chloride is the other condensation product.

O O

H2N (CH2)6 NH2 1 Cl C (CH2)4 C Cl

H H O O

N (CH2)6 N C (CH2)4 C 1 (2n21)HCl


n Laboratory preparation of
nylon. The polymer forms
at the interface between the
upper aqueous layer and the
Nylon was discovered in 1935 by Wallace Carothers and his team working for the DuPont
lower non-polar layer and can
Company. He had earlier invented a synthetic rubber, neoprene, and was looking to make a
be wrapped around a glass rod
synthetic fibre to replace silk. The supply of silk from Japan was vulnerable to the worsening
and drawn out of the solution.
trade relations with America. Commercial production of nylon began in 1939, just before the
start of World War II but sadly, Carothers did not live to see the development of his invention.
He took his own life by cyanide poisoning due to depression in 1937. Nylon was heralded Condensation polymers
as being as strong as steel, as fine as a spiders web. One of the earliest major products was form between
womens stockings 64 million pairs were sold during the first year. Nylon was used in the war monomers which each
to make parachutes and tents as well as in surgical stitching. Seventy-five years later, nylon is have two functional
still one of the most common polymers in use worldwide. groups to react. Addition
polymers form between
unsaturated monomers
that break their double
bond as they react.

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12 Option A: Materials

CHALLENGE Kevlar is a polyamide


YOURSELF Kevlar is a plastic that can stop a bullet. It is another condensation polymer and has
a structure similar to nylon-6,6 with the carbon chain replaced by benzene rings, as
9 Suggest a reason why the
shown below.
polyesters (condensation
polymers) are biodegradable
whereas addition polymers HO C C OH 1 HN NH
formed from substituted H H
alkenes are not. O O

C C NH NH 1 H2O

O O

As the polymer consists of a long chain of benzene rings interconnected by hydrogen


bonds it has a very regular structure. The chains line up parallel to one another allowing
hydrogen bonds to form between the NH2 groups from one chain and the C=O groups
from the next when they have the correct relative orientation (Figure 12.17).

Phenol and methanal form a condensation polymer


A phenolmethanal polymer is made by adding acid or alkali to a mixture of the
monomers. The phenol and methanal react together to form a condensation polymer.
The reaction is more complex than the previous examples as the monomers do not
have two functional groups at either ends. The initial reaction involves a substitution
reaction in the 2 or 4 position of the benzene ring, as shown:

OH
OH OH
H
CH2
1 C O

H
OH

CH2 OH

A 0.22 calibre bullet hitting The products now react with another benzene ring in a condensation reaction with the
Kevlar. The bullet is travelling release of one molecule of water, as shown below:
at 220 m s1.
OH OH

OH
OH
H
CH2 OH CH2 1 H2O

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As both benzene rings have reactive 2, 4 and 6 positions, a network structure can be
built up through a series of similar reactions (Figure 12.33).
Bakelite has a hard rigid structure. It is a thermosetting plastic it does not melt
once it has been heated and set. It is a good electrical and thermal insulator and was
previously used in a wide variety of applications such as telephone and radio casings
before it was generally replaced by PVC. Phenolmethanal resins are still used in many
machine and electrical components.

Green Polymers
Green Chemistry aims to reduce the demand for resources and energy, decrease waste,
and reduce environmental pollution.
Principles of green polymer production include:
high resource effectiveness and high atom economy
clean production processes, which prevent waste and reduce greenhouse gas In the long term, the
move to biomass as the
emissions
raw material for plastics
use of renewable resources and renewable energy production is probably
low carbon footprint. unavoidable. Oil reserves
are finite. Any country
can grow plants, while oil
Although green polymers are not exclusively biomaterials and many existing addition is distributed unevenly
polymers and polymerization processes could be argued to meet the demands of around the world. In the
Green Chemistry, many are biopolymers. shorter term, the pace
of the changeover will
The crude oil that is the raw material for many addition polymers will run out, and the depend on the price of
technology to produce plastics from crop plants is steadily improving. Carbohydrates, oil, and unpredictable
political factors that affect
proteins, and polyesters are prominent condensation polymers that are chemically
oil production.
modified to meet the demands of polymer processing and applications. In 2011, the
worlds largest beverage company announced a plan to make PET bottles from only Technology and new
bio-based material. materials are developed
to improve the quality of
NATURE OF SCIENCE human life. How do we
An age is often defined by its key materials. We have had the Stone Age, Iron Age, and Bronze measure the quality of
Age and perhaps today could be characterized as a time of plastics. The materials of the human life? What happens
future will be based on future technological developments, but the need to manage our finite when technologies are
resources and reduce human impact on the environment are key factors in determining the developed which have an
direction of future research. These are political as well as scientific choices. Ideally we would adverse effect on human
like to use solar power to convert the greenhouse gases carbon dioxide and water into biomass life? Can the genie ever be
by photosynthesis, which can then serve as a feedstock for biofuels and bioplastics. The reality put back in the bottle?
is not that simple. Land is also needed for food production for example.
Biopolymer production.
A microbiologist (left) and
molecular biologist (right)
monitoring bacterial growth
and production of a biopolymer
for use in plastics and other
products. The bacteria
are growing in a nutrient
broth containing glycerol,
a co-product of biodiesel
production. A biopolymer is a
polymer produced by a living
organism.

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12 Option A: Materials

Worked example
Poly(ethylene furanoate) (PEF) is a green polymer made from bio-based monomers.

O O O H H
C C O C C O
H H

Deduce the structure of the two monomers from which it is made.


Solution

Find the ester link and break it to form an acid and an alcohol.

O O O H H
C C O C C O
H H

O
HOOC COOH HO CH2 CH2 OH

Exercises
44 Nylon-6,10 is made from the monomers 1,6-diaminohexane and decanedioic acid. Draw the
repeating unit of this polymer.
45 PLA has been called the first carbon neutral plastic. It has the structure below.

O C
C
H CH3 n

Deduce the structure of the monomer.


46 Draw the structures of the polymers and any by-products formed from the following pairs of
monomers.
(a) HO CH2 CH2 CH2 OH 1 HO CO CH2 CH2 CO OH
(b) H2N CH2 (CH2)4 CH2 NH2 1 Cl CO CH2 CH2 CO Cl
47 This compound is a monomer for a condensation polymer.

NH2

COOH

(a) Identify the functional groups in the monomer which allow it to act as a monomer.
(b) Deduce the by-product of the polymerization reaction.
(c) Deduce the structure of the resulting polymer. You should include at least three monomer units in
your answer.
(d) Kevlar is a polymer produced from monomers which have functional groups in the 1,4 positions
of the benzene ring. Explain the strength of the polymer in terms of the orientation of the two
functional groups.
(e) Explain why Kevlar has a lower density than steel.

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48 The structures of three polymers are shown below. Deduce the structural formula of the monomers in
each case.
(a) H CH3 H CH3 H CH3

C C C C C C

H H H H H H
(b) CH3 O CH3 O

O CH C O CH C O

( )
(c) H CH3

C C

H CO2CH3 n

Environmental impact: heavy


A.10 metals
Understandings:
Toxic doses of transition metals can disturb the normal oxidation/reduction balance in cells
through various mechanisms.
Some methods of removing heavy metals are precipitation, adsorption, and chelation.

Polydentate ligands form more stable complexes than similar monodentate ligands due to the

chelate effect, which can be explained by considering entropy changes.

Applications:
Explanation of how chelating substances can be used to remove heavy metals.
Deduction of the number of dative coordinate bonds a ligand can form with a central metal ion.
Calculations involving K as an application of removing metals in solution.
sp
Compare and contrast the Fenton and HaberWeiss reaction mechanisms.

Guidance
Ethane-1,2-diamine acts as a bidentate ligand and EDTA4 acts as hexadentate ligand.
K values can be found in section 32 of the IB data booklet.
sp
The HaberWeiss reaction generates free radicals naturally in biological processes. Transition metals

can catalyse the reaction, with the iron catalysed (Fenton) reaction being the mechanism for
generating reactive hydroxyl radicals.

Heavy metals are toxic


Heavy metals are serious water pollutants because they are poisonous. Heavy metal
ions have large densities and are thought to interfere with the normal functioning of
key enzymes which normally bond to other necessary ions in the body such as Ca2+,
Mg2+, or Zn2+. Heavy metal ions disturb the normal oxidation/reduction balance in
cells through various mechanisms. Even very small traces of heavy metals can have
very significant harmful effects. The phrase as mad as a
hatter originates from
Mercury ions have a particular attraction for sulfur atoms, and will bond to certain the fact that people
amino acids in enzymes and thus make them ineffective. The enzyme which acts as a who made hats were
sodium pump in the workings of the central nervous system is particularly sensitive routinely exposed to high
to high mercury concentrations. concentrations of mercury
ions which were present in
the salts used to treat felt.

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12 Option A: Materials

Lead is absorbed into the bloodstream where it deactivates the enzymes that make
haemoglobin. This results in a build-up of aminolaevulinic acid (ALA) that causes the
symptoms of lead poisoning.
Cadmium mimics the action of zinc and replaces it in enzymes, which make them
ineffective.
The sources of each of these pollutants and their possible health and environmental
hazards are summarized in the following table.

Mercury Lead Cadmium

Source paints lead pipes metal plating


batteries lead paint and glazes rechargeable batteries
agriculture tetraethyl lead in petrol pigments
by-product of zinc refining

Health hazard the most dangerous of the burning pains in the mouth replaces zinc in enzymes
metal pollutants; causes and digestive system making them ineffective
serious damage to the nerves followed by constipation or itai-itai disease makes bones
and the brain diarrhoea brittle and easily broken
symptoms of mercury in severe cases there is a kidney and lung cancer in
poisoning result from failure of the kidneys, liver, humans
damage to the nervous and heart which can lead to
system: depression, coma and death
irritability, blindness and can cause brain damage,
insanity particularly in young children
Minamata disease
Environmental reproductive system failure toxic to plants and domestic toxic to fish
hazard in fish animals produces birth defects in
inhibits growth and kills fish biological magnification in mice
biological magnification in the food chain
the food chain

CHALLENGE YOURSELF
10 The names and structural formulas of the amino acids are given in section 33 of the IB data
booklet. Identify the amino acid which is likely to bond to Hg2+ ions.

Ion exchange can be used to remove metal ions


Resins or zeolites can be used to exchange the metal ions in polluted water with
hydrogen ions. Y is used to show the resin or zeolite in the following equations:
H+YH+(ion exchange) + M2+(aq) YM2+(ion exchange) + 2H+(aq)
The H+ ions can then combine with OH ions released from the resin as it absorbs
negative ions to form water:
H+(aq) + OH(aq) H2O(l)

Metal ions can be removed by chemical precipitation


Heavy metal ions such as cadmium, lead, and mercury are easily removed by
precipitation as sulfide salts, as their solubility in water is very low. Carefully
controlled amounts of hydrogen sulfide gas are bubbled through a solution containing
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heavy metal ions, which are precipitated as sulfides and which can then be removed by
filtration. For example, for cadmium ions:
Cd2+(aq) + H2S(g) CdS(s) + 2H+(aq)
The excess hydrogen sulfide (being acidic) can then be easily removed.
The insoluble sulfides can also be formed when a soluble sulfide is added. For example,
with lead ions:
Pb2+(aq) + S2(aq) PbS(s)
Similarly, some metals can be removed as insoluble hydroxides on the addition of
aqueous sodium hydroxide:
Cr3+(aq) + 3OH(aq) Cr(OH)3(s)
Some metals can be removed as insoluble phosphates:
Al3+(aq) + PO43(aq) AlPO4(s)

Metal ions can be removed from solution by chelating


agents
We saw in Chapter 3 (page 124) that transition metal ions can form complex ions with
ligands. The ligand will donate a lone pair to form a dative covalent bond with a metal
ion in a Lewis acidbase reaction (Figure 12.51).

L L
Mn1 1 6L Mn1
Figure 12.51 Mn+ forms
L L
a complex ion with six
L monodentate (single-toothed)
ligands.
EDTA4 (old name ethylenediaminetetraacetic acid) is a molecule which has six atoms
(two nitrogen atoms and four oxygen atoms) with lone pairs available to form dative
covalent bonds to a central transition ion (Figure 12.52).

C O2
Figure 12.52 The polydentate
H2C O ligand EDTA4 can take the
place of six monodentate
O2 N CH2 CH2 C ligands as it has six lone pairs
available.
C CH2 H2C N O2
O CH2
2O C
O
A chelate is a complex
4
containing at least one
EDTA is thus equivalent to six monodentate ligands and is described as a polydentate ligand. The
hexadentate (six-toothed) ligand. It can occupy all the octahedral sites and grip the name is derived from
central ion in a six-pronged claw called a chelate. the Greek word for claw.

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12 Option A: Materials

A molecular model of a molecule of EDTA4. The atoms of


the molecule are colour-coded: carbon (black), nitrogen
(blue), hydrogen (turquoise) and oxygen (red). As a
chelating agent, EDTA4 can bind with positive metal ions
(cations) using nitrogen and oxygen atoms to form up to
six bonds.

CHALLENGE YOURSELF
11 Assuming the transition metal ion, Mn+, is originally
surrounded by water molecules, the ligand replacement
reaction can be represented as:
[M(H2O)6]n+ + EDTA4 [M(EDTA)]n4 + 6H2O
Predict the entropy change for this reaction and explain the
stability of the chelate formed.

Worked example
The structure of ethane-1,2-diamine is shown in section 16 of the IB data booklet. It
is generally represented as en.
(a) Deduce the number of dative coordinate bonds the en ligand can form with a
central metal ion.
(b) Deduce the coordination number and the oxidation state of the central metal ion
in the complex [Ni(en)2Br2]+
Solution

(a) The ligand has two N atoms which can form dative coordinate bonds . It is a
bidentate ligand.
(b) Each en ligand forms two bonds and each Br ion forms one bond. The
coordination number is 6.
There are two Br ligands but en is neutral. Overall the complex has a 1+ charge. The
charge on the central nickel ion is 3+. Check: +3 + (2 1) = +1.
Oxidation no = +3.

The solubility product is a measure of the solubility of an


ionic compound
The above discussion is a simplification; no ionic substance is completely insoluble. A
dynamic equilibrium is set up between insoluble solid and the aqueous ions. Consider,
for example, mercury sulfide:
HgS(s) s Hg2+(aq) + S2(aq)
The equilibrium constant for this reaction, Kc, can be deduced from the equilibrium
law:
[Hg 2+ (aq)] [S2 (aq)]
Kc =
[HgS(s)]

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This differs from the examples discussed in Chapter 7 in that it is a heterogeneous
equilibrium. As the molar concentration of a pure substance [HgS(s)] is constant, we
can simplify this expression further to give a new equilibrium constant, known as the
solubility product, Ksp:
Ksp = [Hg2+(aq)] [S2(aq)]
As the Ksp for a compound is an equilibrium constant, it changes only with
temperature.
Solubility products give a measure of the solubility of an ionic compound.
The relationship between solubility as measured by the concentration of a saturated
solution, and the solubility product is investigated in the following worked example.
Ksp values are listed in section 32 of the IB data booklet.

Worked example
CHALLENGE
State an expression for solubility product of Cu(OH)2 and deduce an expression for
Ksp in terms of its solubility s.
YOURSELF
12 Calculate the concentration
Solution of pure water and outline
how the concentration of
Cu(OH)2(s) s Cu2+(aq) + 2OH(aq) other pure substances can
be calculated.
If the solubility is s then [Cu2+(aq)] = s and [OH(aq)] = (2s)
Ksp = [Cu2+(aq)] [OH(aq)]2
Consider the
= s (2s)2 equilibrium formed by a
metal ion M+ and a non-
= 4s3
metal X:
Solids with low solubility have small Ksp values. The value of Ksp can be used to predict MX(s) s M+(aq) + X(aq)
the concentrations of solutions needed for chemical precipitation to occur. If the Ksp = [M+] [X] is called
product of the ionic concentrations exceeds the solubility product, the solid will be the solubility product
precipitated. constant. Ksp depends
only on temperature.

CHALLENGE YOURSELF
13 Use the equilibrium law discussed in Chapter 7 to deduce a more general expression for the
solubility product, Ksp, of compound MpXq(s) in terms of its solubility, s. Given the equilibrium
formed by a metal M and a non-metal X:
MpXq(s) s pMm+(aq) + qXn(aq)

Worked example
Zinc(II) ions (Zn2+) can be removed by bubbling hydrogen sulfide through polluted
water.
The solubility product of zinc sulfide is 1.60 1024 mol2 dm6 at 25 C.
(a) Calculate the concentration of Zn2+ ions in a saturated solution of zinc sulfide.
(b) Suggest how the addition of hydrogen sulfide solution reduces the concentration
of Zn2+ ions in a saturated solution.

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12 Option A: Materials

Solution

(a) In a saturated solution: ZnS(s) s Zn2+(aq) + S2(aq)


Ksp = [Zn2+(aq)] [S2(aq)] = 1.60 1024
When no other ions are present: [Zn2+(aq)] = [S2(aq)]
1.60 1024 =[Zn2+(aq)]2
[Zn2+] = 1.60 10 24
= 1.26 1012 mol dm3
(b) As the product of the ion concentrations is constant, an increase in [S2] will
lead to a decrease in [Zn2+] and the zinc will be precipitated out of solution.

The common ion effect


In the worked example above, we saw that an increase in the concentration of sulfide
ions led to a decrease in the solubility of the zinc ions in solutions. This is a general
result known as the common ion effect.
Consider, for example, the solubility of calcium phosphate:
Ca3(PO4)2(s) s 3Ca2+(aq) + 2PO43(aq)
An increase in the concentration of either phosphate ions or calcium ions, that is ions
common to the compound and the added solution, will according to Le Chateliers
Principle shift the equilibrium to the left and decrease the solubility of the compound.

Harmful hydroxyl free radicals can be formed in the


body from hydrogen peroxide
The way in which toxic doses of transition metals disturb the normal oxidation/
reduction balance in cells is illustrated by the Fenton and HaberWeiss reactions,
which both involve the production of hydroxyl free radicals from the hydrogen
peroxide produced enzymatically in the body. The mechanisms by which metals exert
their toxicity in living organisms are complex but can be related to the formation of
the hydroxyl free radical and other reactive oxygen species which have the potential to
induce damage in biological systems. The hydroxyl radical is one of the most reactive
oxidants that can be formed in a biological system.
Iron(II) and other transition metal ions such as cobalt and copper, for example, react
with hydrogen peroxide and produce hydroxyl free radicals in a Fenton reaction:
Fe2+ + H2O2 Fe3+ + OH + OH
The optimal pH for the reaction occurs between 3 and 6. If the pH is too high the
iron(III) ions react with hydroxide ions to form a precipitate of iron(III) hydroxide and
the hydrogen peroxide decomposes to give oxygen.

The HaberWeiss reaction generates free radicals


naturally in biological processes
The HaberWeiss reaction is another reaction route which explains how the highly
reactive and toxic hydroxyl radical (HO) can be generated from hydrogen peroxide,
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this time by its reaction with the superoxide ion (O2), which is a normal cellular
metabolite.
O2 + H2O2 O2 + OH + OH
The reaction is very slow under normal conditions but can be catalysed by transition
metal ions in what can be described as a superoxide-driven Fenton reaction.
Fe(III) ions are first reduced by superoxide ions to iron(II) ions:
O2 + Fe3+ O2 + Fe2+
The hydrogen peroxide is then oxidized by iron(II) in a Fenton reaction:
H2O2 + Fe2+ Fe3+ + OH + OH

NATURE OF SCIENCE Will we ever directly


observe a reaction
The Fenton reaction generally occurs in chemical and biological systems as well as in the
mechanism? What
natural environment. Its importance has been long recognized, among other places, in food
evidence would confirm
chemistry, in material ageing, and in environmental science. It is, however, the case that the
to you that a reaction
simple reaction (of Fe2+ ions with H2O2), observed by Fenton over a century ago, continues
mechanism is correct?
to be the subject of controversy. It is perhaps paradoxical that a reaction that is successfully
Which ways of knowing
applied in environment protection is thought to be a factor in the ageing process and the
are you using here?
development of a variety of diseases, but chemistry is guided by thermodynamics not a moral
compass. Our knowledge of the Fenton reaction is based on indirect evidence which is still
developing as our technology develops.

Exercises
49 Describe briefly how heavy metal ions function as poisons.
50 The structure of the oxalate ion, C2O42, is shown in section 16 of the IB data booklet. It is generally
represented as ox.
(a) Deduce the number of dative coordinate bonds the ligand can form with a central metal ion.
(b) Deduce the coordination number and the oxidation state of the central metal ion in the complex
[Fe(ox)3]3.
51 The solubility product of nickel sulfide is 2.0 1026 mol2 dm6. Calculate the solubility of nickel sulfide.
52 Deduce an expression for the solubility product of the following compounds:
(a) PbS (b) Cu2S (c) AlPO4 (d) Ni(OH)2
53 Silver ions (Ag+) can be removed by mixing sodium chloride solution with polluted water. The
solubility product of silver chloride is 1.6 1010 mol2 dm6 at 25 C.
(a) Calculate the concentration of Ag+ ions in a saturated solution of silver chloride.
(b) Calculate the concentration of the Ag+ ion in a 0.100 mol dm3 solution of sodium chloride.
54 Deduce an expression relating the solubility product constant Ksp to the solubility s for the following
ionic compounds:
(a) AgBr (b) Ni(OH)2 (c) Hg2S
(d) Ca3(PO4)2 (e) Cr(OH)3
55 Lead(II) ions (Pb2+) can be removed from polluted water by adding sodium sulfide and water. The
solubility product of lead sulfide is 1.30 1028 at 25 C.
(a) Deduce an expression for the solubility product of lead(II) sulfide.
(b) Calculate the concentration of Pb2+ ions in a saturated solution of lead sulfide.
(c) Suggest how the addition of sodium sulfide solution reduces the concentration of Pb2+ ions in a
saturated solution.
56 When excess iron(II) is mixed with hydrogen peroxide, quantitative oxidation of Fe2+ ions by H2O2
occurs. Explain this result with reference to the Fenton reaction.
57 (a) State the equations for the two steps of the HaberWeiss reaction when it is catalysed by Fe3+
ions.
(b) Identify the step which is a Fenton reaction.
(c) Identify the oxidation state of oxygen in the superoxide ion and deduce the number of electrons
transferred when the superoxide ion is oxidized in the HaberWeiss reaction.

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12 Option A: Materials

Practice questions
1 Aluminium and its alloys are widely used in industry.
(a) Aluminium metal is obtained by the electrolysis of alumina dissolved in molten cryolite.
(i) Explain the function of the molten cryolite. (1)
(ii) State the half-equations for the reactions that take place at each electrode. (2)
(b) Outline two different ways that carbon dioxide may be produced during the production of
aluminium. (2)
(Total 5 marks)
2 (a) Explain why iron is obtained from its ores using chemical reducing agents but aluminium is
obtained from its ores using electrolysis. (2)
(b) Both carbon monoxide and hydrogen can be used to reduce iron ores. State the equations
for the reduction of magnetite, Fe3O4, with
(i) carbon monoxide (1)
(ii) hydrogen. (1)
(Total 4 marks)
3 Alloys are important substances in industries that use metals.
(a) Describe an alloy. (1)
(b) Explain how alloying can modify the structure and properties of metals. (2)
(Total 3 marks)
4 Compare the modes of action of homogeneous and heterogeneous catalysts. State one
example of each type of catalysis using a chemical equation and include state symbols.
(Total 4 marks)
5 (a) Name a thermotropic liquid crystal. (1)
(b) Explain the liquid crystal behaviour of the thermotropic liquid crystal named in part (a), on
the molecular level. (4)
(Total 5 marks)
6 Poly(vinyl chloride) (PVC) and poly(ethene) are both polymers made from crude oil.
(a) Explain why PVC is less flexible than poly(ethene). (2)
(b) State how PVC can be made more flexible during its manufacture and explain the increase
in flexibility on a molecular level. (2)
(c) PVC can exist in isotactic and atactic forms. Draw the structure of the isotactic form
showing a chain of at least six carbon atoms. (1)
(Total 5 marks)
7 Landfill sites are used to dispose of about 90% of the worlds domestic waste, but incineration
is being increasingly used in some countries.
(a) State one advantage of each method. (2)
(b) Suggest why some biodegradable plastics do not decompose in landfill sites. (1)
(Total 3 marks)
8 (a) State the materials used for the positive and negative electrodes in the production of
aluminium by electrolysis. (2)
(b) Aluminium is one of the most abundant elements found on Earth. Discuss why it is
important to recycle aluminium. (2)
(Total 4 marks)

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9 Nano-sized test-tubes with one open end, can be formed from carbon structures.
(a) Describe these test-tubes with reference to the structures of carbon allotropes. (2)
(b) These tubes are believed to be stronger than steel. Explain the strength of these test-tubes
on a molecular level. (1)
(c) Carbon nanotubes can be used as catalysts.
(i) Suggest two reasons why they are effective heterogeneous catalysts. (2)
(ii) State one potential concern associated with the use of carbon nanotubes. (1)
(Total 6 marks)
10 The structure of 4-pentyl-4-cyanobiphenyl, a commercially available nematic crystalline material
used in electrical display devices, is shown below.

C5H11 CN

(a) Explain how the three different parts of the molecule contribute to the properties of the
compound used in electrical display devices.
(i) CN
(ii) C5H11

(iii) (3)

(b) Describe and explain in molecular terms the workings of a twisted nematic liquid crystal. (4)
(Total 7 marks)
11 Liquid crystal displays are used in digital watches, calculators, and laptops.
Describe the liquid crystal state, in terms of molecular arrangement, and explain what happens
as temperature increases.
(Total 3 marks)
12 Several monomers are produced by the oil industry and used in polymer manufacture. Examples
include propene, styrene, and vinyl chloride.
(a) (i) Draw the structural formula of propene. (1)
(ii) Isotactic poly(propene) has a regular structure, while atactic poly(propene) does
not.Draw the structure of isotactic poly(propene), showing a chain of at least six
carbonatoms. State and explain how its properties differ from those of atactic
poly(propene). (3)
(b) Styrene can be polymerized to polystyrene, which is a colourless, transparent, brittle
plastic.Another form of the polymer is expanded polystyrene. Outline how expanded
polystyrene is produced from polystyrene, and state how its properties differ from those of
polystyrene. (4)
(c) Many plastic materials are disposed of by combustion. State two disadvantages of disposing
of poly(vinyl chloride) in this way. (2)
(Total 10 marks)
13 Poly(ethene) is the most commonly used synthetic polymer. It is produced in low-density and
high-density forms. Identify which form has the higher melting point. Explain by reference to its
structure and bonding.
(Total 4 marks)

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12 Option A: Materials

14 (a) The properties of poly(vinyl chloride), PVC, may be modified to suit a particular use. State the
main method of modifying PVC and the effect this has on its properties. (2)
(b) Outline two disadvantages of using polymers such as poly(propene) and PVC, and give one
disadvantage that is specific to PVC. (3)
(Total 5 marks)
15 The diagram below represents a section of a polymer.

H CH3 H CH3 H CH3 H CH3

C C C C C C C C

H H H H H H H H
(a) Draw the structure of the monomer from which this polymer is manufactured. (1)
(b) Polymers A and B both have the structure shown above, but the average chain length is
much greater in A than in B. Suggest two physical properties that would be different for A
and B. (2)
(c) Polymers A and B both have isotactic structures. Polymer C is manufactured from the same
monomer but is not isotactic. State the name used to describe this different structure and
outline how the structure differs. (2)
(Total 5 marks)
16 Identify two raw materials mixed with the iron ore in a blast furnace. In each case, outline its
purpose and write an equation to show what happens to it in the blast furnace.
(Total 5 marks)
17 Polymers have replaced more traditional materials such as metal and wood. Suggest one
polymer property, different in each case, that makes polymers more suitable than traditional
materials.
(Total 2 marks)
18 Kevlar is a condensation polymer that is often used in liquid crystal displays. A section of the
polymer is shown below.

H H H

N N C C N

O O

(a) Describe the liquid crystal properties of Kevlar. (3)


(b) Explain the strength of Kevlar in terms of its structure and bonding. (2)
(c) Explain why a bullet-proof vest made of Kevlar should be stored away from acids. (2)
(Total 7 marks)
19 Industrial effluent is found to be highly contaminated with silver and lead ions. A sample of
water contains 8.0 103 mol dm3 Ag+ and 1.9 102 mol dm3 Pb2+. On the addition of
chloride ions both AgCl (Ksp = 1.8 1010) and PbCl2 (Ksp = 1.7 105) precipitate from the
solution. Determine the concentration of Cl needed to initiate the precipitation of each salt and
deduce which salt precipitates first.
(Total 5 marks)

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20 (a) Heavy metal ions can be removed from waste water by adding hydroxide ions. When
hydroxide ions are added to a solution containing nickel ions, a precipitate of nickel(II)
hydroxide, Ni(OH)2, is formed. The solubility product of nickel(II) hydroxide is 6.50 1018
at 298 K. Determine the mass of nickel ions that remains in one litre (1.00 dm3) of water at
298 K with a pH of 7 after the precipitation reaction has occurred. (4)
(b) Suggest, with an explanation, a chemical method by which this amount of nickel dissolved in
the water could be reduced even further. (2)
(Total 6 marks)

To access weblinks on
the topics covered in this
chapter, please go to www.
pearsonhotlinks.com and
enter the ISBN or title of
this book.

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