CHM Notes PDF

CHEMISTRY
HKDSE CHEMISTRY – A MODERN VIEW

COURSEBOOK 1
SUPPLEMENTARY INFORMATION
Contents
PART I PLANET EARTH

Chapter 1 Fundamentals of chemistry
⚫ The scientific method 1
⚫ Kinetic theory of matter 2
Chapter 2 The atmosphere
⚫ A simple experiment to determine the percentage of oxygen 4
in air
Chapter 3 Oceans
⚫ Folding filter paper in fluted form 6
PART II MICROSCOPIC WORLD I
Chapter 5 Atomic structure
⚫ Alchemy atomic symbols and Dalton’s atomic symbols 8
⚫ What is an orbital? 9
⚫ Discovery of electron, proton and neutron 12
Chapter 7 Chemical bonding: ionic bonding
⚫ Evidence of ions from electrolysis 16
Chapter 9 Structures and properties of substances
⚫ Hydration of sodium chloride 19
⚫ Allotropy 20
PART III METALS
Chapter 10 Occurrence and uses of metals
⚫ Alloys 21
Chapter 12 Reacting masses
⚫ Combustion analysis of organic compounds 23
© Aristo Educational Press Ltd. 2009

HKDSE CHEMISTRY ⎯ A Modern View (Chemistry)
PART I PLANET EARTH
Chapter 1 Fundamentals of Chemistry
Supplement to The scientific method

Coursebook p.3
To study chemistry, we should have some ideas of how scientists work.
Scientists work by following the scientific method (Figure S1.1):
scientific facts from observation
of nature or experiments
law
further modified or
hypothesis
experiments new theory
predictions from
theory
theory
Figure S1.1 The scientific method.
1. Look for scientific facts by the observation of nature or

experiments. (A scientific fact is an observation that is so
consistently repeatable that there is no doubt about it.)
2. Compare and classify a large number of scientific facts.
3. Try to find patterns within a group of related scientific facts. (An
important pattern is called a law.)
4. Try to think of a possible explanation for the pattern (or law). The
suggested explanation is called a hypothesis. The hypothesis should
enable scientists to make predictions.
5. Design new experiments to test the hypothesis. If the observation of
nature or the predictions fail, the hypothesis is modified.
6. A well-tested and widely accepted hypothesis becomes a theory.
7. Predictions based on a theory are tested by further experiments. If a
theory cannot always make correct predictions, it should be
modified until it can. If this cannot be done, scientists have to look
for a new theory. Thus, the process is in fact a never ending one.
Supplement to Kinetic theory of matter
Coursebook
© Aristo p.5 Ltd. 2009
Educational Press 1
It is shown by the Brownian movement experiment that particles are

continually moving. Ideas about the movement of particles in matter are
summarized in the kinetic theory of matter:
1. All matter is composed of tiny particles, with spaces between them.
2. (a) Particles are in constant, random motion and so have kinetic
energy.
(b) The average kinetic energy of particles in a substance increases
with temperature.
Example S1.1
Explaining diffusion in terms of the kinetic theory of matter
A gas jar of air is inverted over a gas jar of brown nitrogen dioxide gas, with a glass plate separating
them (Figure S1.2a). When the glass plate is removed, the brown gas gradually diffuses into the jar
of air (Figure S1.2b). Explain this in terms of the kinetic theory of matter.
gas jar
air remove glass plate
and allow gas jars
to stand
glass plate
nitrogen dioxide
gas
(a) (b)
Figure S1.2 Diffusion of nitrogen dioxide gas into air.
Solution
air particles in
random motion
air
remove glass plate
and allow gas jars
to stand
glass plate
nitrogen dioxide
gas
nitrogen dioxide particles in
random motion (a) (b)
According to the kinetic theory of matter, everything is made up of particles. Air is made up of tiny
moving particles; nitrogen dioxide is also made up of tiny moving particles.
© Aristo Educational Press Ltd. 2009 2

Air is colourless and nitrogen dioxide is reddish brown. After the glass plate is removed, it appears
that the reddish brown gas spreads into the upper gas jar. In fact, the particles gradually become
evenly mixed in the two gas jars.
Applying kinetic theory to different states of matter

The kinetic theory of matter can be applied to the three states of matter ⎯
solid, liquid and gas (Figure S1.3). In each case, the arrangement and
movement of particles are different (Figure S1.4).
Figure S1.3 We can ‘see’ the
three states of matter at this
beach.
Solid Liquid Gas

Figure S1.4 The arrangement and movement of particles in solids, liquids and gases are
different.
1. In solids
Particles are tightly packed with little spaces among them. Therefore, a
solid has a fixed volume and is almost incompressible. Particles in it have
low kinetic energy and are arranged in a fixed pattern. Although they can
vibrate about their fixed positions, they cannot move from one place to
another. A solid therefore has a definite shape.
2. In liquids
Particles are packed fairly close together, though not so close as in solids.
Spaces between particles are still very little. Therefore, a liquid has a fixed
volume and it is difficult to compress a liquid. Particles in it have higher
kinetic energy than in solids. Because the particles can move freely, they
are not arranged in a fixed pattern. A liquid therefore has no fixed shape of
its own (Figure S1.5).

P
Figure S1.5 A liquid has no fixed shape. It takes up whatever shape of the container.
P 3. In gases
The particles are widely separated with a lot of empty space between them.
Thus, it is easy to compress a gas. The particles have very high kinetic
energy and move freely at great speeds. They spread into any available
Figure S1.6 Gas pressure (P) is
space, filling the whole container. The particles hit the inner wall of the
caused by gas particles
container continually, exerting a force. The force on each unit area of the
continually hitting the inner wall of
wall is called the gas pressure (Figure S1.6).
the container. The gas pressure is
the same on every part of the
container.
Chapter 2 The atmosphere
Supplement to A simple experiment to determine the percentage of oxygen in

Coursebook p.34 air
We can perform a simple experiment to find the percentage (by volume) of
oxygen in air. Consider heating copper in air. Copper reacts with oxygen:
copper + oxygen → copper(II) oxide

reddish brown black
This reaction can be used to serve our purpose, in a set-up as shown

in Figure S2.1.

air reddish brown
copper turnings
(a)
plunger
syringe A syringe B
strong heat
hard-glass tube
copper turnings
turn black
(b)
syringe B
syringe A air left
Figure S2.1 A set-up used to determine the percentage (by volume) of oxygen in air.
1. Pack a hard-glass tube with copper turnings.

2. Connect the glass tube to two gas syringes A and B.
3. Syringe A contains 100 cm3 of air and syringe B has no air (Figure
S2.1a).
4. (a) Heat the copper turnings strongly.
(b) At the same time, push and pull the plungers several times, to
pass air back and forth over the heated copper.
(c) With no air in syringe B, take down the new volume reading in
syringe A.
5. Repeat step 4 until the volume reading does not drop any further.
6. Let the set-up cool to room temperature.
7. Take down the final volume of ‘air’ left in syringe A.
Example S2.1 shows how the percentage (by volume) of oxygen can
be worked out from the experimental results.
Example S2.1
Determining the percentage of oxygen in air
In an experiment to determine the percentage of oxygen in air (Figure S2.1), the copper turnings
turned black. The results are as follows:
Total volume of air in the syringes before heating = 100 cm3
Final volume of ‘air’ left in the syringes after heating and then cooling = 79 cm3
(a) Why should the set-up be allowed to cool to room temperature before the final volume reading
is taken?

(b) How much oxygen (in cm3) was removed by the copper turnings?
(c) Calculate the percentage by volume of oxygen in air.
Solution
(a) Air expands on heating and this would affect the accuracy of the readings. Thus, volumes
should be measured at the same temperature (room temperature).
(b) Volume of oxygen removed by the copper turnings
= volume of air before heating – volume of air after heating and then cooling
= 100 – 79 cm3
= 21 cm3
(c) Percentage by volume of oxygen in air
Volume of oxygen removed by the copper tur nings
= Original volume of air  100%
21
= 100  100%
= 21%
Chapter 3 Oceans
Supplement to Folding filter paper in fluted form

Coursebook p.47 ‘Fluted’ filter paper is used when you wish to separate a liquid and a solid,
keeping the liquid and discarding the solid. This arrangement of folds in
the filter paper will allow the liquid to pass through it very quickly. It
provides a lot of surface area for collecting the solid ‘impurity’.
To fold the filter paper in fluted form, we do the following:

1. Fold the large circle of filter paper in half, then in quarters.
2. Take the straight edge on one side and fold back to the centre fold
(Figures 2a and 2b). Do the same on the other side. Open the ‘fan’ up
with the centre fold going away from you (Figure 2c).

(a) (b) (c)
3. Starting at one side, fold the straight edge up towards the first fold
(Figure 3a). Fold back along the preformed fold and then fold again
towards the centre fold (Figure 3b).
(a) (b)
4. Continue folding back and forth until you get another smaller-sized
fan.
5. Open the ‘fan’ and look for the two areas called the ‘boxes’. Pinch the
paper to make another fold between the two folds in each box. Then
invert the filter paper before you place it in the filter funnel.

PART II MICROSCOPIC WORLD I
Chapter 5 Atomic structure
Supplement to Alchemy atomic symbols and Dalton’s atomic symbols

Coursebook p.94 In 300 B.C.–A.D. 1500, many scientists focused on alchemy and had invented
a set of symbols to represent different elements, as shown in Figure S5.1.
Platinum Gold Silver
Copper Iron Lead
Magnesium Mercury Phosphorus
Figure S5.1 Some of the Alchemy symbols.
After that, John Dalton invented a set of symbols, some of which are
shown in Figure S5.2.

Figure S5.2 Some of the Dalton’s atomic symbols. A few of ‘Dalton’s elements’ are not
elements at all.
John Dalton used the above symbols to represent different elements.

However, they were not commonly used by chemists and were later
replaced by a better system suggested by the Swedish chemist Berzelius in
1811. He introduced a simpler system of symbols based on letters instead
of signs.
Supplement to
What is an orbital?
Coursebook p.95
Orbitals and orbits
In the textbook, when we are talking about an atom, we usually describe it
as electrons moving around a nucleus. This situation is just like planets
moving around the Sun. The circular path of the electrons is called the
orbit.
However, the situation is very different in reality. For example, if we

could plot the locations of the electron of a hydrogen atom at different
instants, the resultant pattern will look like that in Figure S5.3. You may
Figure S5.3 When the locations find that the pattern looks quite different from that you have learnt from
of the electron of a hydrogen atom the textbook. The movement of an electron cannot be represented by an
at different instants are plotted, orbit. We can only describe the location of an electron in terms of the
the above pattern is obtained. probability of finding it in a certain position. The term orbital or atomic
(The electron cloud model of a orbital is used to represent a region within which there is a high
hydrogen atom.) probability of finding an electron (usually 90% of the time).

The atomic orbital can be represented by an electron cloud model.

Figure S5.3 shows the electron cloud model of a hydrogen atom. The
probability of finding an electron within a spherical space around the
nucleus is about 90%. You may notice that further away from the nucleus,
the electron density becomes smaller.
Do you know?
In the past, many scientists had proposed their own ‘atomic models’. The evolution
of atomic models can be briefly summarized in the figure below:
John Dalton (1805) J.J. Thomson (1904)
(positive and negative charges)
Ernest Rutherford (1911)
(the nucleus) Niels Bohr (1913)
(energy levels)
Schrödinger (1926)
(electron cloud model)
Learning tip Classification of orbitals

The electrons occupy 1. s orbitals
different orbitals according Figure S5.4 shows the 1s, 2s and 3s orbitals. The left one is the 1s orbital.
to their energy status. The ‘1’ represents the fact that the orbital is in the first energy level. That
Electrons with higher means it is closest to the nucleus. The ‘s’ gives information on the shape of
energy occupy orbitals that the orbital. All s orbitals are spherical in shape. The distribution of electron
are further away from the density in 2s and 3s orbitals is similar to that in the 1s orbital.
nucleus.

z z z
y y y
x x x
1s 2s 3s
Figure S5.4 The shapes of the s orbitals.
2. p orbitals
Figure S5.5 shows the p orbitals. With different orientations, p orbitals can
be further classified as px, py and pz orbitals. It should be noticed that the p
orbitals are all dumb-bell shaped.
z
z z
y y y
x x x
2px 2py 2pz
Figure S5.5 The shapes and orientations of different p orbitals.
3. d orbitals
Figure S5.6 shows the d orbitals. With different orientations, d orbitals can
be further classified as dyz, dxz, dxy, dx2−y2 and dz2.
z z z z z
y y y y y
x x x x x
3dyz 3dxz 3dxy 3dx2−y2 3dz2
Figure S5.6 The shapes and orientations of different d orbitals.
Table S5.1 shows the orbitals present in each energy level and the
maximum number of electrons each energy level can accommodate. It
should be noticed that:

 For the first energy level, there is only one type of orbital labelled as
1s.
 For the second energy level, there are two types of orbitals labelled
as 2s and 2p.
 For the third energy level, there are three types of orbitals labelled as
3s, 3p and 3d.
 For the fourth energy level, there are four types of orbitals labelled
as 4s, 4p, 4d and 4f.
Energy level Orbitals present Maximum number of electrons

accommodated
1 s 2
2 s, p 8
3 s, p, d 18
4 s, p, d, f 32
Table S5.1 Orbitals present and maximum number of electrons accommodated in different energy levels.
Electronic configuration of an element

As we have learnt before, the electronic configuration of fluorine is 2,7.
You may now realize that for the first energy level, there are two electrons
filling the s orbitals. For the second energy level, two electrons fill the s
orbitals and the rest five electrons fill the p orbitals. The electrons in a
fluorine atom are distributed among its 1s, 2s and 2p orbitals. The
electronic configuration of fluorine can be represented as 1s22s22p5.
Supplement to
Discovery of electron, proton and neutron
Coursebook p.96
John Dalton suggested that atoms are tiny ‘solid’ spheres which could
never be divided (Figure S5.7). This idea was first shown to be wrong
when a particle smaller than the atom, called the electron, was discovered
during a study of cathode rays by J.J. Thomson in 1897.
Figure S5.7 Dalton’s model of an atom – the solid indivisible atom.

Discovery of electron
Rays consisting of electrons (or cathode rays) are produced when a high
voltage (above 5000 V) is put across two metal electrodes at very low gas
pressure (about 0.0001 atmosphere) in a discharge tube.
Cathode rays can be detected by zinc sulphide screen, which emits

visible light when hit by electrically charged particles. If a metal cross is
placed in the path of the rays as in Figure S5.8, a sharp shadow is projected
on the screen. This shows that cathode rays travel in straight lines.
anode (+) metal cross

zinc sulphide screen
cathode ray
cathode (−)
shadow
gas at very low pressure
high voltage
Figure S5.8 A metal cross in the cathode ray tube obstructs cathode rays and casts a
sharp shadow.
If the rays are made to pass between a pair of charged plates as in

Figure S5.9, they will be deflected by the electric field. They move away
from the negatively charged plate towards the positively charged plate.
They can also be deflected by a magnetic field. Thus, cathode rays cannot
be rays of light; they are in fact a stream of negatively charged particles.
zinc sulphide screen
electric field
anode (+)
cathode (−)
cathode ray
high voltage
Figure S5.9 Cathode rays are attracted by the positively charged plate.

Thomson found that exactly the same particles (electrons) are

produced irrespective of the gas present or the materials used to make the
tube and the electrodes. Further experiments show that they are in fact a
fundamental constituent of all atoms.
Discovery of proton
An atom does not have an overall electric charge. It is said to be
electrically neutral. Since electrons are negatively charged and are
present in all atoms, there must be some positive charges present in atoms
to maintain overall electrical neutrality. If all atoms contain positive and
negative charges, then how are they arranged inside an atom?
Thomson suggested that an atom was like a ‘raisin pudding’ (Figure

S5.10). In his view, the negatively charged electrons stick into a sphere of
positive charges, just like raisins in a pudding. The mass and charge are
distributed among the structure of the atom.
sphere of positive charge
electrons spread
throughout the
atom
Figure S5.10 Thomson’s model of an atom.
Thomson’s idea about the atoms was put to test by Ernest Rutherford
(Thomson’s student) and his research workers in 1911. In the Rutherford’s
gold foil scattering experiment, small positively charged particles, called
alpha particles, were shot at a very thin gold foil at high speed (Figure
S5.11). Most of the alpha particles passed through the gold foil without
changing direction or were only slightly deflected. But surprisingly, a few
were deflected through large angles and a very few even rebounded back!

evacuated glass vessel
vacuum pump
thin gold foil
beam of alpha particles rotatable fluorescent screen
alpha particle source
lead shield
rotatable microscope
deflected beams of
alpha particles
Figure S5.11 Set-up for Rutherford’s gold foil scattering experiment.
The experimental results indicated that only a few alpha particles had
hit a positively charged centre which is very small in size but very
concentrated in mass. This finding could never be explained by using
Thomson’s model. See Figure S5.10 again.
To explain the observed results, Rutherford proposed another model

for the atom (Figure S5.12). He suggested that an atom consists of a
central, minute nucleus where the mass and positive charges of the whole
atom are concentrated. The negatively charged electrons occupy the
remaining space in the atom, revolving around the nucleus.
electrons revolving
around the nucleus

minute, positively
empty space
charged nucleus
Figure S5.12 Rutherford’s atomic model.
Look at Figure S5.13 and see how Rutherford’s atomic model

explains the results of the Rutherford’s gold foil scattering experiment.

gold atoms
a stream of positively charged alpha most alpha particles
particles enters the thin gold foil pass through the thin
gold foil undeflected
a very small number of alpha particles a few alpha particles
approach a nucleus so closely that come close enough
they are rebounded to a nucleus to be
deflected
Figure S5.13 Explaining the results of Rutherford’s gold foil scattering experiment.
Rutherford and other scientists found that the positive charge of the
nucleus was due to positively charged particles called protons. Each
proton carries one unit of positive charge, exactly balancing the negative
charge on one electron.
Discovery of neutron
In the nucleus of a helium atom, there are two protons, but its mass is very
nearly four times that of a hydrogen atom. To explain this, Rutherford
suggested that the helium nucleus should also contain two uncharged
particles. Each of these particles has the same mass as a proton.
In 1932, Chadwick, one of Rutherford’s collaborators, succeeded in

detecting such a particle. It is called neutron.
Chapter 7 Chemical bonding: ionic bonding
Supplement to Evidence of ions from electrolysis

Coursebook p.141 Electrolysis of molten lead(II) bromide
Solid lead(II) bromide does not conduct electricity. However, molten lead(II)
bromide conducts electricity. See Figure S7.1. Reddish brown bromine vapour
is liberated at the anode (positive electrode in this case). A silvery grey
substance (lead) is deposited at the cathode (negative electrode in this case).
Molten lead(II) bromide is thus decomposed to the two elements lead and
bromine. The whole process is called electrolysis (meaning ‘decomposition
by electricity’).
6 V battery

light bulb
positive electrode negative electrode
(anode) (cathode)
molten lead(II) bromide
heat
Figure S7.1 Electrolysis of molten lead(II) bromide.
When electricity is passed through molten lead(II) bromide, there is

chemical decomposition. But why does molten lead(II) bromide conduct
electricity, and why does the decomposition take place at the electrodes?
Molten lead(II) bromide conducts electricity. It must therefore consist

of charged particles that are free to move. These particles are called ions.
As shown in Figure S7.2, positively charged lead(II) ions move to the
cathode (negative electrode in electrolysis). They gain electrons there to
become lead. Negatively charged bromide ions move to the anode (positive
electrode in electrolysis). They lose electrons there to become bromine.
Thus, electric current is carried through molten lead(II) bromide by mobile
(freely moving) ions. 6 V battery
electron flow
anode cathode
Figure S7.2 The movement of particles during electrolysis of molten lead(II) bromide.

Lead(II) bromide does not conduct electricity in the solid state. This is
because ions in solids are not mobile (i.e. unable to move freely) due to
strong attractions among ions. When solid lead(II) bromide is heated until
it melts, the ions present become mobile. Therefore, molten lead(II)
bromide conducts electricity.
Electrolysis of aqueous copper(II) chloride solution

A simple set-up for investigating electrolysis of aqueous copper(II)
chloride solution is shown in Figure S7.3.
6 V battery
carbon anode carbon cathode
chlorine gas bubbles

copper
copper(II) chloride solution
Figure S7.3 Electrolysis of aqueous copper(II) chloride solution.
Aqueous copper(II) chloride solution conducts electricity. During

electrolysis, copper(II) chloride is decomposed to form copper (reddish
brown solid) at cathode and chlorine gas (with smell of swimming pool) at
anode.
Learning tip
Electrolytes are compounds
We can also explain the electrolysis of aqueous copper(II) chloride
which allow electricity to
solution in terms of ions.
pass through them only
when molten or in aqueous
Electrolytes and ions
solution. There is chemical
Lead(II) bromide is a compound made up of a metal (lead) and a
decomposition during the
non-metal (bromine). Copper(II) chloride is a compound made up of a
conduction.
metal (copper) and a non-metal (chlorine). They do not conduct electricity
in the solid state. However, they conduct electricity when melted (molten)

or dissolved in water, with chemical decomposition. They are electrolytes.

Most electrolytes are compounds made up of metals and non-metals.
Electrolysis experiments show that mobile, charged particles exist in

molten and in aqueous electrolytes. These charged particles, called ions,
are responsible for conduction of electricity in electrolytes.
Chapter 9 Structures and properties of substances
Supplement to Hydration of sodium chloride

Coursebook p.197 Why is sodium chloride soluble in water? When sodium chloride is added
to water, Na+ ions in the crystal are attracted by negative ends of polar
water molecules; Cl− ions are attracted by positive ends of water molecules.
The ions are thus ‘pulled away’ from the giant ionic structure and go into
solution. See Figure S9.1.
polar molecule
hydrated chloride ion
dissolution
hydrated sodium ion
=
chloride ion
sodium ion
Figure S9.1 Water dissolving the ionic solid sodium chloride.
In solution, each sodium ion has a number of water molecules

attached to it; sodium ions are said to be hydrated. The same happens to
the chloride ions. Hydrated sodium and chloride ions are represented by
Na+(aq) and Cl−(aq) respectively.
Some solid ionic compounds (e.g. barium sulphate) are insoluble in

water. This is because the attraction between ions in the crystal is greater

than that between the ions and water molecules.
Ionic solids are insoluble in non-polar solvents. This is because the

non-polar molecules have little attraction for the ions. Therefore, the giant
ionic structures do not break up.
Supplement to Allotropy
Coursebook p.198 Different forms of an element in the same state, such as diamond and
graphite, are called allotropes. The element is said to exhibit allotropy.
Allotropy is the existence of an element in more than one form in the

same state. Allotropes always have different physical properties due to
different structures, but they often have similar chemical properties. Other
elements which show allotropy include phosphorus (e.g. yellow
phosphorus and red phosphorus) and tin (e.g. white tin and grey tin).
Note that the term ‘polymorphism’ is different from ‘allotropy’.

Polymorphism refers to the existence of an element or compound in more
than one form in the same state, so it has a broader sense than allotropy.
The different forms are called polymorphs. Zinc oxide is a compound
exhibiting polymorphism. It is white in colour at room temperature, but
becomes yellow when hot, owing to a change in crystal structure.

PART III METALS
Chapter 10 Occurrence and uses of metals
Supplement to Alloys
Coursebook p.223 We have discussed the properties and uses of some common metals. The most
common metal iron is seldom used in pure form. Most of it is used to make
steel, which is an alloy. In fact, many other metals are used in making alloys,
which have different properties (and therefore uses) compared with the pure
metals.
copper atoms
What is an alloy?
An alloy is a homogeneous mixture composed of a metallic element mixed
Zn
with one or more other elements (mostly metals). A few alloys contain small
Zn amounts of non-metals. An alloy is made by mixing a metal in molten state
Zn and one or more other elements together. The mixture is then allowed to
solidify. For example, brass is an alloy of copper and zinc (Figure S10.1).
zinc atom
Although about 60 metals are commonly used, there are thousands of

a brass saxophone
possible alloys. An alloy has properties different from its components. It is
usually designed to have properties that are more desirable than those of its
Figure S10.1 Brass is an alloy
components. Alloys have suitable properties for making many many things,
of copper and zinc.
from a paper clip to a space shuttle.
Common alloys and their compositions

The properties of some common alloys are shown in Table S10.1.
Alloy Approximate composition (by mass)
Mild steel 99.8% iron
0.2% carbon
Stainless steel 73% iron
18% chromium
8% nickel
1% carbon
Brass 70% copper
30% zinc
Bronze 95% copper
5% tin
Nickel-brass 70% copper

(a coinage metal) 24.5% zinc
5.5% nickel
Cupro-nickel 75% copper
(a coinage metal) 25% nickel
Duralumin 95% aluminium
3% copper
1% magnesium
1% manganese
Solder 67% lead
33% tin
18-carat gold 75% gold
25% silver and/or copper
Table S10.1 Compositions of some common alloys.
We should note that only a few alloys are mentioned in the above
table. In fact, a large variety of alloys are in use today. Besides, there are
variations within the same type of alloy. For example, the brass (70%
copper, 30% zinc) mentioned here is only the best known brass. There are
many other different brasses, each with somewhat different compositions
and properties.
Common properties of alloys and pure metals

In a pure metal, all the atoms are of the same size. They are arranged
regularly in layers. When an external force is applied, the layers slip over
one another quite easily. Thus, pure metals have good malleability and
ductility.
In an alloy, atoms of another element have been added to the pure

metal. The addition of these different-sized atoms distorts the original
regular crystal structure. As a result, slipping of layers now becomes
difficult. This makes the alloy stronger, harder, less malleable and less
ductile. See Figure S10.2.

atoms of original metal atoms of other added elements
Figure S10.2 Layers of atoms cannot slip over one another easily in an alloy.
The melting point of a solid depends very much on the packing of

atoms. A regularly packed solid has a higher melting point than an
irregularly packed solid. An alloy, with an irregular structure, usually has a
lower melting point than the metals from which it is made. Besides,
alloying usually hinders the free movement of delocalized electrons. This
lowers the electrical conductivity and thermal conductivity.
In general, compared with pure metal, an alloy

 is stronger and harder,
 is less malleable and ductile,
 has a lower melting point,
 has lower electrical and thermal conductivities.
Chapter 12 Reacting masses
Supplement to Combustion analysis of organic compounds

Coursebook p.284 When we determine the empirical formula of an organic compound, we are
usually provided with data like the masses of water and carbon dioxide
produced during combustion of the organic compound. How do the data come
from? Actually, the data are obtained from combustion analysis.
During combustion analysis, the sample is weighed and then burned in

excess oxygen mixed with helium (Figure S12.1). After combustion, carbon
dioxide, water vapour, nitrogen oxides and other compounds are produced.
Compounds of sulphur, phosphorus and the halogens are absorbed by specific

chemicals. The resultant mixture of gases is then allowed to pass through a hot
mesh of copper. The hot copper mesh removes the excess oxygen and reduces
the nitrogen oxides to nitrogen. The remaining gases are carbon dioxide, water
vapour, nitrogen and helium.
copper mesh to remove excess O2
and reduce nitrogen oxides
CO2 + H2O +
O2 + He
N2 + He
Remove CO2
weighed sample of chemicals to absorb compounds of

heat
unknown compound S, P and the halogens H2O + N2 + He
electrodes
N2 + He Remove H2O
Figure S12.1 A simplified diagram for combustion analysis.
These gases are then allowed to pass through a tube containing a mixture
of sodium hydroxide and calcium hydroxide to remove the carbon dioxide.
Then the remaining gases are allowed to pass through another tube filled with
magnesium perchlorate (Mg(ClO4)2) to remove the water vapour. The tubes
are weighed before and after the absorption process in order to find out the
masses of carbon dioxide and water produced.

CHEMISTRY

COURSEBOOK 2
Contents
PART IV ACIDS AND BASES

Chapter 14 Introduction to acids and alkalis
⚫ Defining acids and bases 1
⚫ Manufacture of sulphuric acid by Contact process 4
⚫ More about concentrated sulphuric acid 7
Chapter 16 Indicators and pH
⚫ Autoionization of water and pH 11
⚫ More about acid-base indicators 12
Chapter 19 Volumetric analysis involving acids and alkalis
⚫ Primary standard 14
⚫ Titration curves 18
⚫ Choice of indicators 22
PART V FOSSIL FUELS AND CARBON COMPOUNDS

Chapter 21 Consequences of using fossil fuels
⚫ LPG and town gas 25
⚫ Air pollution problems in Hong Kong 26
Chapter 24 Addition polymers
⚫ Condensation polymerization 30
⚫ Thermosetting plastics 37

HKDSE CHEMISTRY ⎯ A Modern View (Chemistry) Supplementary information
PART IV ACIDS AND BASES
Chapter 14 Introduction to acids and alkalis
Supplement to Defining acids and bases

Coursebook p.9
It should be noted that acid-base concept is very useful because it helps
relate large amounts of chemical reactions which were originally
considered to be very different. There are different definitions of acids and
bases. Here, we focus on the Arrhenius definition, the Brønsted-Lowry
definition and the Lewis definition.
Arrhenius definition
The Arrhenius definition of acids and bases is sometimes referred to as the
Learning tip
‘aqueous’ concept. It defines an acid as any substance that can give
The hydroxonium ion is a
hydroxonium ion (or hydronium ion), H3O+ (Figure S14.1) and its
hydrated hydrogen ion,
corresponding negative ions in aqueous solution.
which is often simply
called hydrogen ion, H+.
or
Figure S14.1 The structure of a hydroxonium ion, H3O+.
It defines a base as any substance that can give hydroxide ion, OH−
and its corresponding positive ions in aqueous solution. For example, HCl
is an Arrhenius acid because it reacts with water according to the
equation,
HCl(g) + H2O(l) → H3O+(aq) + Cl−(aq)
acid hydroxonium ion
Similarly, CO2 is an Arrhenius acid because it reacts with water to

form carbonic acid, H2CO3,
CO2(g) + H2O(l) ⇌ H2CO3(aq)
which then undergoes further reaction to give H3O+ and HCO3−.

H2CO3(aq) + H2O(l) ⇌ H3O+(aq) + HCO3−(aq)
An example of an Arrhenius base is sodium hydroxide, which is an

ionic compound containing Na+ and OH− ions. In water, it undergoes
dissociation.
NaOH(s) + water → Na+(aq) + OH−(aq)
base hydroxide ion
Another example of an Arrhenius base is ammonia which reacts with

water to give OH− ions.
NH3(aq) + H2O(l) ⇌ NH4+(aq) + OH−(aq)
Brønsted-Lowry definition
The Arrhenius definition only allows the discussion of acid-base behaviour
in aqueous solutions. How about reactions occurring in solvents other than
water?
In 1923, a Danish chemist, J.N. Brønsted and a British chemist, T.M.

Lowry defined an acid as a substance that can donate a proton (i.e.
hydrogen ion, H+) to some other substance(s). They also defined a base as
a substance that can accept a proton from an acid. In other words, an acid
is a proton donor and a base is a proton acceptor.
In the following example, HCl is a Brønsted-Lowry acid because it

reacts with water and donates a proton to a water molecule forming the
hydroxonium ion. Water, on the other hand, acts as a Brønsted-Lowry
base by accepting a proton from the acid.
HCl(g) + H2O(l) → H3O+(aq) + Cl−(aq)
acid base
(proton (proton
donor) acceptor)
Another example of Brønsted-Lowry acid-base reaction occurs in the

aqueous solution of ammonia.

base acid
(proton (proton
© Aristo Educational Press Ltd. 2009 acceptor) donor) 2
Here, water acts as an acid by giving up a proton to NH3, which acts

as a base. On the other hand, the reverse reaction also gives another
example of Brønsted-Lowry acid-base reaction. NH4+ is a Brønsted acid
which donates a proton to OH− while OH− is a Brønsted base which
accepts a proton from NH4+.
NH3 and NH4+ are related to one another by the loss or gain of a
single proton and are considered as a conjugate acid-base pair. We say
that NH4+ is the conjugate acid of the base, NH3, and similarly that NH3 is
the conjugate base of the acid, NH4+. There is another conjugate acid-base
pair in the solution — H2O (acid) and OH− (base).

base acid conjugate acid conjugate base
of NH3 of H2O
Or the other way round,
NH4+(aq) + OH−(aq) ⇌ NH3(aq) + H2O(l)

acid base conjugate base conjugate acid
of NH4+ of OH−
The Brønsted-Lowry definition is more commonly used than the

Arrhenius definition because it is not limited to the cases in aqueous
solutions. For example, when HCl and NH3 gases are mixed, they react
immediately to form the white ionic solid, NH4Cl. Since a proton is
transferred from HCl to NH3, this is clearly an acid-base reaction under the
Brønsted-Lowry definition. As hydroxonium ion and hydroxide ion do not
appear in the reaction, this is not an acid-base reaction under the Arrhenius
definition.
Lewis definition
The Brønsted-Lowry definition still has limitations. Many reactions are
nowadays classified as acid-base reactions although they are not counted
under the Brønsted-Lowry definition. The Lewis definition further extends
the acid-base concept to include more reactions. It defines a base as a
substance that donates a pair of electrons in a reaction. An acid is a
substance that accepts a pair of electrons in a reaction.

Consider the fundamental acid-base reaction of H+ with OH− to give

H2O. The oxygen atom in the hydroxide ion has three unbonded electron
pairs around it. During the course of the reaction, one of those electron
pairs is donated to the hydrogen ion, making a chemical bond. Thus, OH−
donates a pair of electrons and is regarded as the Lewis base, whereas H+
accepts a pair of electrons and, therefore, is regarded as the Lewis acid.
The Lewis definition of acids and bases is much broader than the
previous two definitions. Consider the reaction between boron trifluoride,
BF3 and ammonia, NH3.
NH3 acts as the Lewis base and BF3 acts as the Lewis acid. (Why?) A
dative covalent bond is formed between them. However, in this case,
neither the Arrhenius definition nor the Brønsted-Lowry definition is
applicable.
Supplement to Manufacture of sulphuric acid by Contact process

Coursebook p.27
Sulphuric acid is made by the Contact process. The process involves three
stages:
(1) Preparation and purification of sulphur dioxide
(2) Catalytic oxidation of sulphur dioxide to sulphur trioxide (Catalytic
oxidation means oxidation in the presence of a catalyst.)
(3) Conversion of sulphur trioxide to sulphuric acid
(1) Preparation and purification of sulphur dioxide

Sulphur dioxide is often prepared by burning sulphur in air. See Figure
S14.2.
S(s) + O2(g) → SO2(g)
It can also be obtained by roasting sulphide ores such as iron pyrite

(FeS2) or zinc blende (ZnS) in air. See Figure S14.3.
4FeS2(s) + 11O2(g) → 2Fe2O3(s) + 8SO2(g)
2ZnS(s) + 3O2(g) → 2ZnO(s) + 2SO2(g)

Figure S14.2 Sulphur to be used in a Contact process plant. Figure S14.3 A sulphur-containing ore — iron pyrite.
Sulphur dioxide and air are first purified and dried. This is to remove
impurities which would ‘poison’ (making it useless) the catalyst used in
the next stage.
(2) Catalytic oxidation of sulphur dioxide to sulphur trioxide

A mixture of sulphur dioxide and excess air is passed to a catalytic
converter in the Contact process plant (Figure S14.4). Sulphur dioxide and
oxygen react exothermically according to the equation:
2SO2(g) + O2(g) ⇌ 2SO3(g) H = −196 kJ mol−1
Figure S14.4 A Contact process At room temperature and pressure, the reaction is very slow. The
plant. reaction rate can be increased by passing sulphur dioxide and air mixture
along hot pipes containing vanadium(V) oxide (V2O5) catalyst at 450C
and 1 atm. (Note: Platinum would be a more effective catalyst, but it is
easily ‘poisoned’ by impurities. Also, platinum is much more expensive
than vanadium(V) oxide.)
It is the close contact of reacting gases with vanadium(V) oxide

which gives the Contact process its name.
(3) Conversion of sulphur trioxide to sulphuric acid

Sulphur trioxide cannot be added directly to water to form sulphuric acid.
It is because the reaction is highly exothermic and uncontrollable. Acidic
vapour or mists are formed instead of a liquid. The sulphur trioxide formed
is then dissolved in concentrated sulphuric acid (98% H2SO4 by mass) in

the absorption tower to form oleum (also called fuming sulphuric acid).
H2SO4(l) + SO3(g) → H2S2O7(l)
oleum
Oleum is added to the correct amount of water so that concentrated

sulphuric acid is formed again.
H2S2O7(l) + H2O(l) → 2H2SO4(l)
Some of the concentrated sulphuric acid is used for absorbing more

sulphur trioxide. The rest of the acid is stored up.
Figure S14.5 shows a flow diagram for the Contact process.
sulphur
dioxide PURIFIER
AND
DRIER
water
preheated
SO2 and air CATALYTIC SO3 oleum
CONVERTER ABSORPTION
(450C and 1 TOWER
atmosphere)
98%
98% H2SO4
air PURIFIER H2SO4
AND
DRIER storage
Figure S14.5 A flow diagram for the manufacture of sulphuric acid by the Contact process.

Supplement to More about concentrated sulphuric acid

Coursebook p.27
(1) Dehydrating properties
 Action on hydrated salt
Concentrated sulphuric acid has a very strong affinity for water. It can
remove water of crystallization from hydrated salts. For example, it
changes blue crystals of copper(II) sulphate-5-water to the white
anhydrous form of the salt (Figure S14.6).
conc. H2SO4
CuSO4•5H2O(s) ⎯⎯⎯⎯⎯⎯→ CuSO4(s) + 5H2O(l)
blue white
hot conc. H2SO4
Figure S14.6 Dehydration of copper(II) sulphate crystals by hot concentrated sulphuric
acid.
 Action on sugar
Concentrated sulphuric acid can even remove the elements of water (i.e.
hydrogen atoms and oxygen atoms in the ratio of 2:1) from various
compounds. Water is formed as one of the products.
For example, when we mix sucrose (cane sugar) C12H22O11 with

concentrated sulphuric acid, the mixture turns brown and then almost black.
The black spongy mass of charcoal swells and rises. Steam is given out
(the removed water changing into steam because of the great heat evolved)
(Figure S14.7).
conc. H2SO4
C12H22O11(s) ⎯⎯⎯⎯⎯⎯→ 12C(s) + 11H2O(l)
white black

sugar
charcoal
sugar
Figure S14.7 The dehydrating action of concentrated sulphuric acid on sugar.
The above examples show that concentrated sulphuric acid can

remove water of crystallization or the elements of water from other
compounds. It thus acts as a dehydrating agent. For example, it
dehydrates paper, wood, cloth and the skin. This explains the highly
corrosive nature of concentrated sulphuric acid.
 Dilution of concentrated sulphuric acid

Dilute sulphuric acid used in the laboratory is obtained by dilution of
concentrated acid. Concentrated sulphuric acid reacts vigorously with
water, liberating a lot of heat. Thus to dilute concentrated sulphuric acid,
add the acid slowly to a lot of water with constant stirring. In doing so, the
heat evolved will be spread throughout the whole volume of liquid (Figure
S14.8a).
Never add water to concentrated sulphuric acid. If water is added to

Learning tip
the much denser acid, the water would float on top. The large amount of
The boiling points of
heat given out at the junction of the liquids causes almost immediate
water and ordinary
boiling of the water. The sudden and violent expansion of steam would
concentrated sulphuric
cause acid spray to spurt out of the container (Figure S14.8b). Also, the
acid are 100C and
large quantity of heat might break the glass container, resulting in a splash
338C respectively.
of the acid. All of these dangers can result from one mistake!

water
concentrated
sulphuric acid
water
concentrated
sulphuric acid
(a) YES (b) NO!
Figure S14.8
(a) Correct way to dilute concentrated sulphuric acid.
(b) Incorrect way to dilute concentrated sulphuric acid.
(2) Hygroscopic properties

A hygroscopic substance is a compound which absorbs water vapour from
air. Concentrated sulphuric acid is hygroscopic. It absorbs water vapour if
left to stand in air, diluting itself (Figure S14.9).
(a) (b)
Figure S14.9 Concentrated sulphuric acid is hygroscopic. Expose concentrated sulphuric
acid to air:
(a) At the start

(b) Two weeks later

Concentrated sulphuric acid is often used as a drying agent. It is used

Learning tip
for drying neutral or acidic gases (e.g. hydrogen, oxygen, chlorine, carbon
To dry ammonia gas,
dioxide, sulphur dioxide and hydrogen chloride). See Figure S14.10.
we can use calcium
However, it is not used to dry alkaline gases (e.g. ammonia) and a few
oxide.
other gases (e.g. ethanol), because chemical reactions may occur.
wet gas dry gas
conical flask
concentrated
sulphuric acid
Figure S14.10 Concentrated sulphuric acid can be used to dry many gases.

Chapter 16 Indicators and pH
Supplement to Autoionization of water and pH

Coursebook p.51
Ionic product of water, Kw
Although water is a covalent compound, it undergoes autoionization as
follows:
H2O(l) + H2O(l) ⇌ H3O+(aq) + OH−(aq)
Hydroxonium ions and hydroxide ions are formed.
As this is an equilibrium, we can write an equilibrium expression as

follows:
[H 3O + (aq)][ OH − (aq)]
Kc = [H 2 O(l)][ H 2 O(l)]
The molarity of water, which appears in the denominator of the

expression, is almost constant ( 55.6 M), in both pure water and in dilute
aqueous solutions. Hence, [H2O(l)]2 can be incorporated into the
equilibrium constant, Kc, of the expression. Then we would write
Kc[H2O(l)]2 = [H3O+(aq)][OH−(aq)]
Using Kw (the ionic product of water) to replace Kc[H2O(l)]2, we have

Kw = [H3O+(aq)][OH−(aq)]
The equation for the autoionization of water is often simplified as

follows:
H2O(l) ⇌ H+(aq) + OH−(aq)
Then the expression for the ionic product of water can be written simply as
Kw = [H+(aq)][OH−(aq)]...........(Equation 1)
The autoionization of H2O is present in all aqueous solutions, and

Equation 1 must always be fulfilled regardless of what other equilibria
may occur in the solutions. The ionic product of water at 25C has been
found to be 1.0  10−14 mol2 dm−6 and can be used to calculate the molar
concentrations of both the H+ and OH− ions in pure water at 25C.
From the stoichiometric equation, 1 mole of H2O ionizes to give 1

mole of H+ and 1 mole of OH−. Thus, at equilibrium, [H+(aq)] = [OH−(aq)],

and the solution is said to be neutral. Substituting this into the expression
for the ionic product of water, Kw = 1.0  10−14 mol2 dm−6 =
[H+(aq)][OH−(aq)], we have 1.0  10−14 mol2 dm−6 = [H+(aq)]2,
 [H+(aq)] = 1.0  10 −14 mol dm−3

= 1.0  10−7 mol dm−3
In pure water at 25C, [H+(aq)] = [OH−(aq)] = 1.0  10−7 mol dm−3.

To calculate the pH of pure water, we use the equation
pH = −log [H+(aq)]
pH = −log (1.0  10−7)
= 7.0
In other aqueous solutions, Kw is still a constant. That is to say, the

product of [H+(aq)] and [OH−(aq)] is always equal to 1.0  10−14 mol2 dm−6.
In summary,
 in neutral solutions, [H+(aq)] = [OH−(aq)]
 in acidic solutions, [H+(aq)] > [OH−(aq)]
 in alkaline solutions, [H+(aq)] < [OH−(aq)]
More about acid-base equilibrium

More about weak acid and base

Class Work
(a) Calculate the pH value of a 0.5 M solution of ammonia, given Kb of
ammonia is 1.8 × 10-5 mol dm-3 .
(b) Determine the dissociation constant, Ka , of ammonium ion NH4 +
More about buffer solutions

Buffers are solutions which resists changes in pH on addition of small
amount of acid or alkali.

Class Work
(a) Calculate the change in pH when 0.1 cm3 of 1.0 M HCl is added to 1
dm 3 of pure water at 298 K.
(b) Calculate the pH of the resulting solution when 300 cm3 0.1 M
CH3COOH is mixed with 100 cm 3 0.1 M CH3COONa.
Supplement to More about acid-base indicators

Coursebook p.53 Acid-base indicators are usually weak organic acids or bases that change
colour when going from an acidic medium to a basic medium. However,
not all indicators change colour at the same pH.
The indicators are either acids or bases whose conjugate bases or

conjugate acids have colours different from those of the indicators
themselves. Let us take phenolphthalein (Figure S16.1) as an example. The
indicator (the weak acid in this case) can be represented as HIn, which is
colourless. The conjugate base formed after ionization can be represented
Figure S16.1 The structure
as In−, which is pink in aqueous solution. When the indicator is added to
of phenolphthalein.
water, the following equilibrium is established:
HIn(aq) ⇌ H+(aq) + In−(aq)

weak acid conjugate base
(colourless) (pink)
In an acidic solution, there is an excess of H+(aq). By applying Le

Châtelier’s Principle, the equilibrium position shifts to the left. Then HIn is
the dominant species in the solution. The colour of HIn(aq) will be shown
(i.e. colourless).

On the other hand, in an alkaline solution, the equilibrium position

shifts to the right because H+(aq) ions are removed by the following
reaction:
H+(aq) + OH−(aq) → H2O(l)
Then In−(aq) is the dominant species in the solution. The colour of In−(aq)
will be shown (i.e. pink).
Therefore, HIn is said to be the ‘acid form’ and In− the ‘basic form’ of
the indicator. The ability of HIn to work as an indicator is based on the fact
that the acid and basic forms differ in colour. It should be noted that both
the acid form and basic form of the indicator are present in the solution.
The resultant colour observed depends on the ratio of the two forms.
It is found that for most indicators, the ratio of the two forms must be
Learning tip
1 10
Remember that the [H+(aq)] 10 or 1 before a colour change is apparent to the human eyes. Taking
of the original solution will
[HIn (aq)]
not be affected by the 1
phenolphthalein as an example, when the ratio [In − (aq)] = 10 , the
addition of any indicators
[HIn (aq)]
which are weak organic 10
solution appears pink; when the ratio [In − (aq)] = 1 , the solution
acids or bases.
appears colourless.

More about salt hydrolysis
More about solubility product

Chapter 19 Volumetric analysis involving acids and

alkalis
Supplement to Primary standard

Coursebook p.107 A primary standard is a substance which can be used to prepare a
standard solution directly. It means that it can be weighed out and made
into a solution of accurately known concentration. The solution can then be
used in titration to find, exactly, the concentration of another solution. To
be a good primary standard, the substance should have the following
properties:
 High purity
 Low reactivity (at least not affected by exposure to air, meaning that
it should not react with oxygen, carbon dioxide or water vapour)
 High solubility in water
 Not hygroscopic (‘hygroscopic’ means the ability of a substance to
attract water molecules from the surrounding environment)
 Not efflorescent (‘efflorescent’ means the loss of water of
crystallization from a hydrated salt to the atmosphere on exposure to
air)
 Involatile
 Readily available (not expensive)
 Non-toxic
 Environmentally friendly
In practice, very few substances make ideal primary standards and

compromises have to be made. In school laboratory, potassium hydrogen
phthalate (usually called KHP, formula: KHC8H4O4 and molar mass:
204.22 g mol−1) is a good example of acidic primary standard. Anhydrous
sodium carbonate is a good example of alkaline primary standard.
Supplement to
Titration curves
Coursebook p.113
During the course of an acid-alkali titration, the pH of the solution is
changing all the time. A titration curve is a curve that shows the changes
in pH during the process of a titration. There are four typical titration
curves:
 strong acid–strong alkali titration
 strong acid–weak alkali titration
 weak acid–strong alkali titration

 weak acid–weak alkali titration
Strong acid–strong alkali titration

The titration between hydrochloric acid and sodium hydroxide solution is a
typical example of the titration between a strong acid and a strong alkali.
When 25.0 cm3 of 0.10 M HCl is titrated with 0.10 M NaOH, the pH of the
solution after the addition of any quantity of NaOH to HCl can be
calculated as shown below:
The number of moles of H+(aq) present in the 25.0 cm3 HCl solution
25.0
= 0.10  1000 mol = 2.5  10−3 mol
When 10.00 cm3 of the 0.10 M NaOH are added, number of moles of
OH−(aq) added
10.00
= 0.10  1000 mol = 1.0  10−3 mol
The neutralization reaction H+(aq) + OH−(aq) → H2O(l) occurs, and the

amount of H+(aq) remaining
= 2.5  10−3 – 1.0  10−3 mol = 1.5  10−3 mol
Thus, the concentration of H+(aq) in the resultant solution
1.5  10 −3 mol
= = 4.3  10−2 mol dm−3
0.035 dm 3
The pH of the resultant solution = −log (4.3  10−2) = 1.4
The pH of the resultant solution after further additions of NaOH can be
calculated and summarized in Table S19.1 below.
Volume of Total
Volume of No. of moles of No. of moles of Concentration of ions
NaOH volume pH
HCl (cm )3 +
H (aq) (mol) − in excess (M)
OH (aq) (mol)
3 3
(cm ) (cm )
25.0 0.00 25.00 2.5  10−3 0 0.10 (H+) 1.0
25.0 10.00 35.00 2.5  10−3 1.0  10−3 4.3  10−2 (H+) 1.4
25.0 24.99 49.99 2.5  10 −3
2.499  10 −3
2.0  10 (H )
−5 + 4.7
25.0 25.00 50.00 2.5  10−3 2.50  10−3 0 7.0
25.0 25.01 50.01 2.5  10−3 2.501  10−3 2.0  10−5 (OH−) 9.3
25.0 26.00 51.00 2.5  10−3 2.60  10−3 2.0  10−3 (OH−) 11.3
25.0 50.00 75.00 2.5  10−3 5.0  10−3 3.3  10−2 (OH−) 12.5
Table S19.1 The pH of the resultant solution after additions of NaOH.
Learning tip
If a graph of pH against the volume of NaOH added is plotted, we
The equivalence point is
© Aristo
the point Educational
at which the Press
acid Ltd. 2009 19
and alkali have just

neutralized each other.
obtain the titration curve as shown in Figure S19.1 below. The curve not
only shows the change in pH of the resultant solution during the course of
titration, but also helps to determine the equivalence point of the
neutralization, which can be taken as the mid-point of the vertical/steepest
part of the curve.
equivalence point
Volume of 0.1 M NaOH added (cm3)
Figure S19.1 Titration curve for a strong acid–strong alkali titration.
For strong acid–strong alkali titration (such as the titration between

HCl(aq) and NaOH(aq) in this case), the pH changes slowly at first, then
very rapidly near the equivalence point. The equivalence point occurs at a
pH of 7. At the equivalence point, the solution is neutral.
Strong acid–weak alkali titration

Learning tip
For strong acid–weak alkali titration (such as the titration between HCl(aq)
Hydrolysis of NH4+:
and NH3(aq)), the change in pH near the equivalence point is not as drastic
NH4+(aq) + H2O(l)
as that in strong acid–strong alkali titration (Figure S19.2). The pH of the
→ NH3(aq) + H3O+(aq)
equivalence point is smaller than 7. This is due to the hydrolysis of the
cation (NH4+) of the salt that gives the solution an excess of H+(aq) ions.

pH
equivalence point

Volume of 0.1 M NH3 added (cm3)
Figure S19.2 Titration curve for a strong acid–weak alkali titration.
Weak acid–strong alkali titration

Learning tip
For weak acid–strong alkali titration (such as the titration between
Hydrolysis of CH3COO−:
CH3COOH(aq) and NaOH(aq)), the change in pH near the equivalence
CH3COO−(aq) + H2O(l)
point is not as drastic as that in strong acid–strong alkali titration (Figure
→ CH3COOH(aq) + OH−(aq)
S19.3). The pH of the equivalence point is greater than 7. This is due to
the hydrolysis of the anion (CH3COO−) of the salt that gives an excess of
OH−(aq) ions.
pH
equivalence point

Figure S19.3 Titration curve for a weak acid–strong alkali titration.

Weak acid–weak alkali titration

For weak acid–weak alkali titration (such as the titration between
CH3COOH(aq) and NH3(aq)), there is no sharp change in pH near the
equivalence point (Figure S19.4). Although the pH of the equivalence
point is 7 in this case, it will be quite different if other weak acids and
weak alkalis are used. The pH of the resultant solution depends on the
extent of hydrolysis of the cation or anion of the salt formed.
pH
equivalence point

Figure S19.4 Titration curve for a weak acid–weak alkali titration.
Supplement to
Choice of indicators
Coursebook p.115
Criteria for choosing a suitable indicator:
(1) The end point of the indicator (the point when the indicator changes
colour sharply) should coincide with the equivalence point of the titration.
In other words, the ‘working range’ of the indicator should fall on the
vertical part of the titration curve. See Table S19.2. Otherwise, the
indicator will change colour either before or after the equivalence
point.
(2) The end point should be sharp. The indicator should change colour
sharply at the equivalence point on adding a single drop (~0.02 cm3)
of acid/alkali.
Methyl orange is used to detect the end point of strong acid−weak

alkali titrations while phenolphthalein is used to detect the end point of

weak acid−strong alkali titrations. After studying the titration curves, you
should understand that both indicators are suitable for strong acid–strong
alkali titrations. However, no indicator is suitable for weak acid–weak
alkali titrations.
Strong acid–strong alkali titration pH
 The colour change regions of both

methyl orange (pH < 7) and phenolphthalein
phenolphthalein (pH > 7) fall on the
vertical part of the titration curve, so
both of them are suitable indicators. methyl orange
pH
Strong acid–weak alkali titration
 The colour change region of methyl

orange (pH < 7) falls on the vertical phenolphthalein
part of the titration curve, so it is a
suitable indicator.
methyl orange
Weak acid–strong alkali titration pH
 The colour change region of

phenolphthalein (pH > 7) falls on the phenolphthalein
vertical part of the titration curve, so it
is a suitable indicator.
methyl orange

pH
Weak acid–weak alkali titration
 The colour change regions of both

methyl orange (pH < 7) and phenolphthalein
phenolphthalein (pH > 7) do not fall on
any vertical part of the titration curve,
so both of them are not suitable
methyl orange
indicators.
Table S19.2 ‘Working ranges’ of methyl orange and phenolphthalein on different titration curves.

PART V FOSSIL FUELS AND CARBON COMPOUNDS
Chapter 21 Consequences of using fossil fuels
Supplement to LPG and town gas

Coursebook p.154
In Hong Kong, the most common household fuels are LPG (Liquefied
Petroleum Gas) and town gas. LPG is a fraction from refining of
petroleum and is a mixture of mainly propane and butane liquefied under
pressure (Figure S21.1). Town gas refers to any gaseous fuel supplied to
consumers through pipes from a central plant.
Hong Kong town gas

In Hong Kong, town gas was made from coal before 1960. Since then, all
town gas has been made from the oil fraction naphtha. There are several
reasons for the change:
(1) Naphtha nowadays is cheaper than coal.
Figure S21.1 An LPG tank.
(2) As a liquid, naphtha is easier to be transported and stored.
(3) Using naphtha as a raw material to produce town gas does not cause
air pollution.
Starting from 2006, natural gas is also used in the production of town
gas. Besides, in 2007, landfill gas (mainly methane) from landfill sites is
collected and used as a fuel to produce town gas.
Figure S21.2 shows the town gas plant in Tai Po Industrial Estate.
Figure S21.2 The town gas plant at Tai Po Industrial Estate in Hong Kong.

How is town gas manufactured from naphtha in Hong Kong?

 The raw material
Naphtha is a mixture of C5 to C10 alkanes, mainly pentane and
hexane.
 Steam reforming of town gas
Liquid naphtha is heated. The vapour produced is mixed with steam
and passed over a hot nickel catalyst (at 700C). Hydrogen, methane,
Gas % by volume
carbon dioxide and carbon monoxide are formed. The following are
Hydrogen 49.0 typical reactions:
Methane 28.5 C5H12(g) + 5H2O(g) → 5CO(g) + 11H2(g)
Carbon 19.5 2CO(g) + 2H2(g) → CO2(g) + CH4(g)
dioxide  Composition of town gas
Carbon 3.0 The typical chemical composition of Hong Kong town gas is shown
monoxide in Table S21.1. Town gas is very flammable and poisonous. An
Table S21.1 Typical composition odorant (very smelly substance) has been added to town gas, so that
of Hong Kong town gas. gas leakage can be easily detected.
Supplement to Air pollution problems in Hong Kong

Coursebook p.174
Air pollution is a serious problem in many densely-populated cities. Hong
Kong is no exception. In 2007, 774 tonnes of pollutants entered the
atmosphere of Hong Kong every day. It is estimated that about 68 100
tonnes of sulphur dioxide (SO2), 97 200 tonnes of nitrogen oxides (NOx),
72 000 tonnes of carbon monoxide (CO), 39 700 tonnes of volatile
organic compounds (VOCs) and 5640 tonnes of respirable suspended
particulates (RSP) entered the atmosphere in 2007.
As a result of various emission reduction measures implemented in

recent years, Hong Kong has achieved good progress in reducing the total
emissions of NOx, VOCs and RSP. See Table S21.2.
Pollutant 1997 emission 2007 emission Change in emission 2010 reduction target
(tonnes) (tonnes) (1997−2007) (reference to 1997)
SO2 66 200 68 100 +3% −40%
NOx 124 000 97 200 −21% −20%
VOCs 68 800 39 700 −42% −55%
RSP 11 500 5640 −51% −55%
Table S21.2 Progress in achieving the 2010 emission reduction targets.
The greatest source of air pollution in Hong Kong is motor vehicles

(Figure S21.3), followed by electric power stations, factories, construction

sites and incinerators.
Figure S21.3 Car exhaust is the greatest source of air pollutants.
Air pollution control in Hong Kong

Hong Kong has two main air pollution issues. One is street-level pollution
and the other is smog. Diesel vehicles are the main source of street-level
pollution. They are also a contributor to smog, which is caused by a
combination of pollutants from Hong Kong and the Pearl River Delta
region.
In Hong Kong, the Environmental Protection Department (EPD) is

in charge of air pollution control. Approaches include:
 Implementing a wide range of measures locally to control emissions
from motor vehicles, power stations, and industrial and commercial
processes.
 Working with Guangdong Provincial Authorities to establish a joint
plan to improve the air quality in the Pearl River Delta region.
A. Reducing emissions from vehicles

(1) Using unleaded petrol
 Most motor vehicles in Hong Kong are powered by petrol. From
1 April, 1999, only unleaded petrol is allowed for motor vehicles.
Figure S21.4 Sale of leaded See Figure S21.4.
petrol is banned with effect from  Benzene in unleaded petrol has been reduced from 5% to 1%
1 April, 1999. since April 2000.
(2) Using LPG instead of diesel
 Diesel taxi owners were encouraged in 2000 to switch to LPG
Figure S21.5 LPG public light

with one-off grants to help pay for the changeover.

 From 2001, all new taxis must run on LPG.
 By the end of 2003, nearly all (about 99.9%) taxis have switched
to LPG.
 By the end of 2008, about 60% of the registered public light
buses use LPG (Figure S21.5).
(3) Using particulate traps or catalytic converters
 Some diesel powered motor vehicles, such as vans, are required
to install particulate traps or catalytic converters to trap
pollutants and reduce emission.
(4) Adoption of tighter fuel and vehicle emission standards
 In 2000, the fixed penalty for smoky vehicles was increased
from $450 to $1000.
 EPD operates a Smoky Vehicle Control Programme that requires
smoky vehicles spotted by accredited spotters to undergo a
smoke test within a specific period.
(5) Promoting better vehicle maintenance and eco-driving habits
 Training sessions for vehicle mechanics on proper engine repair
and maintenance to reduce smoke emissions from diesel vehicles
are offered.
 Seminars that aim at promoting proper vehicle maintenance and
eco-driving practices are conducted.
B. Reducing emissions from power stations and industrial sources

(1) Control by legislation
 The Air Pollution Control Ordinance and its subsidiary
regulations control emissions from power stations, industrial and
commercial sources, construction activities, open-burning,
asbestos and dry-cleaning machines.
(2) Using fuels of lower sulphur content
 Ultra low sulphur diesel (ULSD) was introduced with a sulphur
content of 0.005%, one-tenth that of previous regular diesel.
Hong Kong is now the only place in Asia where ultra low
sulphur diesel is the only diesel available for vehicles, after the
government introduced a concessionary duty on ULSD in July
2000.
C. Tackling regional air pollution

Vehicles, power stations and industry in Hong Kong and the Pearl River
Delta area all contribute to a regional air pollution problem, commonly
seen as smog. The Hong Kong and Guangdong governments are working
together to reduce the total amount of emissions and improve air quality
for the whole region.
Monitoring air quality in Hong Kong

In Hong Kong, the concentrations of air pollutants are monitored (i.e.
checked constantly) by the EPD. 14 fixed monitoring stations, 3 roadside
and 11 general, have been installed to monitor concentrations of air
pollutants (Figure S21.6).
TAP MUN
YUEN LONG TAI PO
SHATIN
TSUEN WAN
KWAI CHUNG
SHAM SHUI PO
KWUN TONG
MONG KWOK
EASTERN
CENTRAL/WESTERN
TUNG CHUNG
CENTRAL CAUSEWAY BAY
ROADSIDE STATION
GENERAL STATION
Figure S21.6 The fixed air quality monitoring stations in Hong Kong.
Based on the measured results of air quality from monitoring stations,

the EPD is able to calculate an Air Pollution Index (API) for a region.
The API is a measure of air quality. Its value ranges from 0 to 500. A lower
value indicates better air quality.

Chapter 24 Addition polymers
Supplement to Condensation polymerization

Coursebook p.236
One type of chemical reaction is called condensation reaction.
Condensation is a type of reaction in which two or more molecules join

together to form a larger molecule, with the elimination of small molecules
(such as H2O or HCl).
Consider the following reactions:
carboxylic acid alcohol ester water (1)
amine amide water (2)

carboxylic acid
Both reactions (1) and (2) are condensation reactions. Two molecules
(carboxylic acid and another compound) join together to form a larger
molecule (ester or amide), with the elimination of a small molecule
(water).
In the above two examples, there are no reactive functional groups

left at either end of the product molecule (i.e. ester or amide molecule).
The product molecules cannot join with other reactant molecules. Thus, no
polymer can be formed. However, there is a special type of condensation
called condensation polymerization in which a polymer is formed.
Condensation polymerization is a reaction in which monomer molecules

join together to form polymer molecules, with the elimination of small
molecules (such as H2O or HCl).
Each monomer involved in condensation polymerization must be

Think about
© Aristo
Like the Educational
monomers of Press Ltd. 2009 30
addition polymers, the

monomers of condensation
polymers must contain
bifunctional. It has at least two functional groups, one at each end of its
molecule.
Examples of condensation polymers include poly(ethylene

terephthalate) (PET), nylon and urea-methanal.
Poly(ethylene terephthalate) (PET)

Formation
Terephthalic acid (IUPAC name: benzene-1,4-dicarboxylic acid) is a dioic
acid and ethane-1,2-diol is a diol. When they react in the presence of a
catalyst and at a low pressure and about 250°C, water is eliminated and an
ester is formed.
terephthalic acid ethane-1,2-diol ester

(a dioic acid) (a diol)
The ester molecule formed still has unreacted functional groups at

both ends. There is a carboxylic acid group at one end of the molecule and
a hydroxyl group at the other end. Repeated condensations thus lead to the
formation of a long polymer chain. The structure of the polymer chain is
shown below:
from dioic acid from diol from dioic acid from diol
The reaction involved is based on the esterification reaction as

represented by equation (1) on the previous page. The polymer formed
here is poly(ethylene terephthalate) or PET. PET is a kind of polyester
and the –COO– linkage in the polymer is called the ester linkage. PET is
also commercially known as Terylene or Dacron.
The whole polymer and the repeating unit of PET can be written
respectively as:
Polymer: Repeating unit:

Learning tip
© Aristo Educational
The repeating Press Ltd. 2009
unit of PET 31
is derived from one dioic

acid molecule and one
diol molecule.
terephthalate group ethylene group
The whole process of formation of PET can be represented by the

following equation:
Terylene (polymer)
Properties and uses

A polyester is strong, tough and smooth. It is also resistant to water and
chemicals. Thus, a polyester is suitable for making fibres and clothes.
Some clothes are made of 100% polyester. They are resistant to wrinkle
and can be dried quickly. On the other hand, some clothes are made of
100% cotton which are soft, comfortable and absorb sweat quickly. To
combine the advantages of both the polyester and cotton, some clothes are
made of a blend of both of them. See Figure S24.1.
Figure S24.1 Clothes made of (a) 100% polyester, (b) 35% polyester and 65% cotton, and (c) 100% cotton.
PET is used in making a variety of products. As PET is resistant to

chemicals and is easily washed, it is commonly used to make food
containers and bottles (Figure S24.2).

Everyday chemistry
Bedroom products made of polyester fibre
Polyester fibre is easy to clean and resistant to water-soluble stains like tea and
fruit juice. It is commonly used to make carpets, curtains and bedsheets. Some of
them are blended with other materials like cotton to produce fabrics of desirable
properties.
Carpet Curtain Bedsheet
House furnishings that are mainly made of polyester fibre.
Nylon
Formation
Nylon is a kind of polyamide. It is a condensation polymer formed
between a dioic acid (or a dioyl dichloride) and a diamine. For example,
nylon 6.6 is formed from the following two monomers:
or
hexanedioic acid hexanedioyl dichloride
and
hexane-1,6-diamine
Hexanedioyl dichloride and hexane-1,6-diamine can polymerize

according to the following:

Do you know
Have you experienced mild
electric shock when you take
repeated
−HCl condensations
off nylon clothing on a dry
day?
This is because nylon
contains electron-attracting
oxygen and nitrogen atoms amide linkage
in its polymer chains. These
atoms allow the nylon fabric
The formation of nylon 6.6 is based on the amide formation reaction
to pick up an electric charge
as represented by equation (2) mentioned before. It should be noted that
when the surfaces rub
the –CONH– linkage is called the amide linkage. During the formation of
together.
nylon 6.6, hydrogen chloride is eliminated in the reaction. In case
hexanedioic acid is used instead of hexanedioyl dichloride, water will be
eliminated.
Properties and uses

Nylon is tough, very strong and elastic. Besides, it is water-proof and
oil-proof. Nylon has a high tensile strength and its surface is usually very
smooth. Also, it is easy to wash and can be dyed in a wide range of
colours.
Nylon was synthesized as a substitute for silk. Its production was in a

much larger scale during the Second World War. It was used to make
parachutes, ropes and shoelaces for army boots at that time. Nowadays,
Figure S24.3 Common uses nylon is ideal for making ropes, fishing lines and fishing nets. It is also
of nylon in daily life. used as tennis racket strings and for making stockings (Figure S24.3).
Urea-methanal
Formation
Urea-methanal is a polyamide, which is a condensation polymer formed
from the following two monomers:
and
urea methanal
There are two stages in this condensation polymerization. During the

first stage, repeated condensations occur with the elimination of water

molecules. Long chains are formed.
repeated
−H2O condensations
Learning tip
During the second stage, further condensations occur. Many
The cross-links here are in
cross-links are formed between the polymer chains. This results in a hard,
fact strong covalent bonds.
rigid three-dimensional giant network.
further
−H2O
condensations
cross-links

The whole polymer and the repeating unit of urea-methanal can be

written respectively as:
Polymer: Repeating unit:
Urea-methanal can be prepared in a school laboratory. This can be

done by adding a little concentrated sulphuric acid to a solution of urea and
methanal. The mixture is then stirred continuously. Urea and methanal
polymerize to form a white viscous liquid. The liquid thickens and
eventually hardens to give a white solid (Figure S24.4).
white solid of
urea-methanal
after further
stir stirring
conc.
sulphuric acid
white
solution of viscous
urea and liquid
methanal
Figure S24.4 Laboratory preparation of urea-methanal.
Properties and uses

Urea-methanal is white in colour. Due to the cross-links formed between
polymer chains, urea-methanal is hard and rigid. It is an excellent
electrical and heat insulator. Moreover, it is resistant to chemical attack
and insoluble in any solvent. Upon heating, it does not change in shape or
melt. Under strong heating, it decomposes.
Urea-methanal is widely used in the electrical industry. It can be used

to make light-coloured electrical switches, plugs, sockets and casings for

electrical appliances (e.g. radios, vacuum cleaners and electric irons). See
Figure S24.5. It is also used in making ashtrays and handles of frying pans.
Learning tip
Condensation polymers may
be made from more than two
kinds of monomers. For
example, protein is made
from the condensation of a
number of amino acids. Figure S24.5 Urea-methanal is commonly used to make electrical plugs, sockets and
switches.
Supplement to Thermosetting plastics

Coursebook p.248
When a thermosetting plastic is moulded, cross-links (covalent bonds) are
formed between the polymer chains. A hard, rigid three-dimensional giant
network is formed (Figure S24.6).
cross-links between the

polymer chains
warm or pull
almost no change as the chains cannot move

relative to one another
Figure S24.6 The giant network structure of a thermosetting plastic after being set hard.
The polymer chains cannot slide over one another even when heated.
Thus, the finished article cannot be softened by heat. On very strong
heating, the article decomposes rather than softens. The decomposition
process releases carbon atoms, causing the plastic to turn black (charring,
see Figure S24.7b.)

(a) (b)
Figure S24.7 Urea-methanal (a thermosetting plastic) only chars when heated strongly. It
does not burn. (a) Before heating. (b) After strong heating.

CHEMISTRY

COURSEBOOK 3
Contents
PART VI MICROSCOPIC WORLD II

Chapter 25 Simple molecular substances with non-octet
structures and shapes of simple molecules
⚫ Dative covalent bond between NH3 and BF3 1
⚫ Valence Shell Electron Pair Repulsion (VSEPR) theory 2
Chapter 26 Bond polarity
⚫ Intermediate type of bonding 4
⚫ Explaining bond polarity using the ‘electron cloud’ concept 5
⚫ Measuring dipole moments 7
Chapter 27 Intermolecular forces
⚫ Explaining van der Waals’ forces using the ‘electron cloud’ concept 9
PART VII REDOX REACTIONS, CHEMICAL CELLS AND ELECTROLYSIS

Chapter 31 Redox reactions
⚫ The Stock system of naming 11
Chapter 33 Electrolysis
⚫ Flowing mercury cell for the electrolysis of brine 13
⚫ Membrane cell for the electrolysis of brine 14
⚫ Quantity of electricity and Faraday’s Laws of electrolysis 15
PART VIII CHEMICAL REACTIONS AND ENERGY

Chapter 35 Energy changes in chemical reactions
⚫ More about internal energy 17
⚫ Entropy and free energy 18
Chapter 36 Standard enthalpy change of combustion,
neutralization, solution and formation
⚫ Bond enthalpy 21

PART VI MICROSCOPIC WORLD II
Chapter 25 Simple molecular substances with

non-octet structures and shapes of
simple molecules
Supplement to
Dative covalent bond between NH3 and BF3
Coursebook p.5
A dative covalent bond is formed when both electrons in a shared pair
come from the same atom. This atom is called the donor atom, and the
two electrons it provides come from a lone pair on that atom. The atom
which receives the electron pair is the acceptor atom.
In boron trifluoride, the boron atom has only six outermost shell
electrons. It is described as ‘electron deficient’. It needs two more
electrons to attain the octet structure. When gaseous boron trifluoride and
gaseous ammonia react together, a white solid with the formula NH3BF3 is
formed. The nitrogen atom in ammonia has a lone pair. It acts as the donor
atom which provides the lone pair electrons to the boron atom. As a result,
a dative covalent bond is formed (Figure S25.1).
*A dative covalent bond is shown by an arrow pointing from the donor atom to the acceptor atom.
Figure S25.1 Formation of a dative covalent bond in NH3BF3.

Supplement to
Valence Shell Electron Pair Repulsion (VSEPR) theory
Coursebook p.14
In forming a chemical bond, not all electrons are involved. Those which
are involved are called valence shell electrons. For elements in main
groups, valence shell electrons are only those in the outermost shell (the
valence shell). The basic ideas of the Valence Shell Electron Pair
Repulsion (VSEPR) theory are:
 Each set of valence shell electrons on a central atom is significant.
 The sets of valence shell electrons on the central atom repel one
another.
 The sets of valence shell electrons are arranged about the central atom
so that repulsions among them are as small as possible.
Valence shell electrons are regions of high electron

concentration/density, or are regarded as electron domains. According to
the VSEPR theory, molecules are most stable when the regions of high
electron density on the central atom are as far apart as possible. For
example, two regions of high electron density are most stable on opposite
sides of the central atom (the linear arrangement). Three regions are most
stable when they are arranged at the corners of an equilateral triangle (the
trigonal planar arrangement).
The arrangement of these regions of high electron density around the

central atom is referred to as the electronic geometry of the central atom.
Table S25.1 shows the relationship between the numbers of regions of high
electron density and their corresponding electronic geometries.
Number of regions of Electronic geometry Bond angles

high electron density
2 Linear 180
3 Trigonal planar 120

4 Tetrahedral 109.5
5 Trigonal bipyramidal 90, 120,

180
6 Octahedral 90, 180
represents the region of high electron density about the central atom.
Table S25.1 Number of regions of high electron density about a central atom and the
corresponding electronic geometry.
However, the shape of a molecule does not refer to the electronic

geometry, but the molecular geometry. This is the spatial arrangement of
In NH3, H−N−H angle = 107 atoms around the central atom. For example, an ammonia molecule has
Figure S25.2 The electronic tetrahedral electronic geometry but trigonal pyramidal molecular
geometry (tetrahedral) and geometry (Figure S25.2). In ammonia, H−N−H bond angle is 107° (less
molecular geometry (trigonal than the expected 109.5°) because lone pair-bond pair repulsion is greater
pyramidal) of NH3. than the bond pair-bond pair repulsion.

Chapter 26 Bond polarity
Supplement to
Intermediate type of bonding
Coursebook p.21
In many cases, when a chemical bond is formed, the transfer of electrons is
not complete, or the sharing of electrons not equal. Therefore, pure ionic
bond and pure covalent bond are only two extremes in a continuous range
of bond types. There are many intermediate (‘in between’) types, i.e.
increasing polarization bonds can be partially ionic or partially covalent in character.
of anion by cation
Take the example of lithium chloride. Basically, the bonding is ionic.
However, there is evidence that some degree of electron sharing (and
hence covalent character) is present in the compound. The high charge
density of the very small Li+ ion causes it to distort the large Cl− ion. The
distortion attracts electron density from the Cl− ion to the region between it
and the Li+ ion, giving lithium chloride a higher degree of covalent
character than chlorides of other alkali metals.
In general, an ionic compound will have an appreciable covalent

character if
Figure S26.1 Polarization of the  the anion is large: more polarizable (Figure S26.1);
electron cloud in anions of  the cation is small: more polarizing;
different sizes.  either the cation or anion is highly charged.
Take another example, hydrogen chloride. Basically, the bonding is

covalent, but the chlorine atom attracts the shared pair of electrons more
than the hydrogen atom does. We can represent this as H Cl, with the
shared electrons nearer to the chlorine atom than to the hydrogen atom.
We would therefore expect the chlorine atom to have a small fraction of a
partial negative charge (−) on it, and the hydrogen atom a partial
Figure S26.2 A more accurate
positive charge (+) of equal magnitude (Figure S26.2). Since the H−Cl
representation of the covalent
covalent bond has some ionic character in it, it is an example of polar
bond in hydrogen chloride.
covalent bond.
Figure S26.3 below illustrates what has been said.

increasing ionic character
pure covalent bond pure ionic bond
(sharing of electrons equal) intermediate types of bond (transfer of electrons complete)
Cl−Cl H−Cl Li+Cl− Na+Cl−
increasing covalent character
Figure S26.3 The continuous range of bond types between pure ionic and pure covalent bonds.
Supplement to
Explaining bond polarity using the ‘electron cloud’ concept
Coursebook p.22
Electron cloud model
An electron bound to the nucleus of an atom is often thought of as orbiting
the nucleus like a planet orbiting the Sun in the solar system (Figure
electron
S26.4). However, this is not the actual situation.
proton
According to the principles of quantum mechanics, an electron can be
a wave or a particle, depending on what kind of measurement is made.
Because of its wave nature, we can never predict where an electron will be
found. We can only calculate the probability that it will be located at
Figure S26.4 An electron
certain points. The electron is therefore described in terms of its
orbiting the nucleus of a
probability distribution. This probability distribution does not have definite
hydrogen atom.
cut-off points. Its edges are somewhat fuzzy. Hence, an electron cloud
model is used to illustrate the distribution.
Figure S26.5 shows the atomic nucleus surrounded by an electron

cloud. The dense region indicates that the electron(s) is/are more likely to
be found there.
We may visualize a hydrogen atom and a chlorine atom as follows

Figure S26.5 An electron (Figure S26.6):
cloud model.

hydrogen chlorine
Figure S26.6 Electron cloud models for hydrogen (left) and chlorine (right).
When two hydrogen atoms share electrons to form a hydrogen

molecule, the two bonding atoms exert the same attractions on the shared
electrons. (This is because the two hydrogen atoms have the same
electronegativity.) The electron cloud is evenly distributed in this
homonuclear molecule at most of the time. See Figure S26.7.
Figure S26.7 The electron cloud model of a hydrogen molecule.
A similar situation occurs in a chlorine molecule (Figure S26.8).
Figure S26.8 The electron cloud model of a chlorine molecule.
The above covalent bonds, H−H and Cl−Cl, are said to be non-polar.
However, the situation is somewhat different in heteronuclear molecules.
For example, in hydrogen chloride, the more electronegative chlorine atom
attracts more strongly on the shared electrons. The electron cloud of the
hydrogen chloride molecule is unevenly distributed (or is distorted)
(Figure S26.9).

Figure S26.9 The electron cloud model of a hydrogen chloride molecule.
The covalent bond H−Cl is said to be polar. The hydrogen atom is

carrying a partial positive charge (+) and the chlorine atom is carrying a
partial negative charge (−).
Supplement to
Measuring dipole moments
Coursebook p.25
Whenever two electrical charges of equal magnitude but opposite signs are
separated by a distance, a dipole is established. The size of a dipole is
measured by its dipole moment, represented by μ. If two charges of equal
magnitude, q+ and q−, are separated by a distance r, the dipole moment is
the product of q and r.
μ = qr
According to the above relationship, the dipole moment will increase

as
 the quantity of charge that is separated increases,
 the distance between the charges increases.
Dipole moments of molecules are usually measured in debyes (D).

One debye is equal to 3.34 × 10−30 coulombmetres (C m). For covalent
molecules, we usually measure charge in units of the electronic charge e
(i.e. 1.60 × 10−19 C), and distance in Å (where 1 Å = 10−10 m).
Suppose the bond length of the HCl molecule is 1.27 Å and the
charges on the H and Cl atoms are +0.178 and −0.178 respectively. The
charge on each atom is the electronic charge, e: 0.178 × 1.60 × 10−19 C.

Hence, the dipole moment produced is:

μ = qr = (0.178 × 1.60 × 10−19 C)(1.27 Å)(10−10 m/1 Å)(1 D/3.34 ×
10−30 C m)
= 1.08 D
Measurement of the dipole moments of molecules can provide us

with useful information about the charge distribution in molecules. See
Table S26.1.
Compound Bond length (Å) Difference in Dipole moment

electronegativity (D)
H−F 0.92 1.9 1.82
H−Cl 1.27 0.9 1.08
H−Br 1.41 0.7 0.82
H−I 1.61 0.4 0.44
Table S26.1 Bond lengths, differences in electronegativity values and dipole moments of
the hydrogen halides.

Chapter 27 Intermolecular forces
Supplement to
Explaining van der Waals’ forces using the ‘electron cloud’
Coursebook p.35
concept
Dipole-dipole forces
If three polar molecules come close to each other, they are oriented so that
the oppositely charged ends are aligned as shown in Figure S27.1. It shows
the distorted electron clouds around three HCl molecules, each having a
permanent dipole. As HCl molecules approach each other, the end of one
molecule which has a lower electron density or partial positive charge (+)
is attracted to the end of the other molecule which is more electron-rich, or
has a partial negative charge (−). The attractive forces between HCl
molecules are known as dipole-dipole forces (or dipole-dipole
attractions). Dipole-dipole forces operate only between molecules with
permanent dipoles.
dipole-dipole forces dipole-dipole forces

+ − + −
H －Cl H －Cl H+－Cl−
Figure S27.1 Dipole-dipole forces exist between hydrogen chloride molecules.
Dispersion forces
There are no dipole-dipole forces between non-polar molecules. But there
is some kind of attractive forces between them. Now, we take helium atom
(monatomic molecule) as an example. The electrons are in constant motion
within the electron cloud around the helium nucleus. At any given instant,
the two electrons of a helium atom may get together at one side. This
results in a temporary distortion of the electron cloud at that given instant
(Figure S27.2).The higher electron density causes this side of the atom to
carry an instantaneous, slight negative charge. At the same time, the other
side is carrying an instantaneous, slight positive charge.
Figure S27.2 The temporary distortion of the electron cloud around a helium atom.

If two non-polar molecules approach each other, the negatively

charged electrons in one molecule are attracted to the positively charged
nuclei in the other molecule. But at the same time these electrons are
repelled by the electrons in the other molecule. This complex combination
of attraction and repulsion results in the temporary distortion of the
electron cloud around one molecule.
Figure S27.3 shows the temporary distortion of the electron cloud

around a helium atom as it approaches another helium atom. The motions
of the electrons in one helium atom influence the electrons in the other
atom. When an atom is carrying an instantaneous dipole, the
neighbouring atom will be affected and induced to have a dipole too
(forming induced dipole). These dipoles attract each other and the forces
are known to be dispersion forces.
dispersion forces
Figure S27.3 Dispersion forces exist between helium atoms as represented by the
electron cloud model.
Similarly, dispersion forces exist in other non-polar molecules such as

chlorine (Figure S27.4).
dispersion forces
Cl+－Cl− Cl+－Cl− Cl+－Cl−
Figure S27.4 Dispersion forces exist between chlorine molecules as represented by the
electron cloud model.

PART VII REDOX REACTIONS, CHEMICAL CELLS AND
ELECTROLYSIS
Chapter 31 Redox reactions

Supplement to
The Stock system of naming
Coursebook p.116
The Stock system of naming compounds is based on the oxidation number
concept.
Naming of cations
Some metals, usually transition metals, form cations with more than one
oxidation number. For each of these ions, we write a Roman numeral in
brackets after the name of the metal, to indicate its oxidation state. Thus,
we name FeCl2 as iron(II) chloride; FeCl3, iron(III) chloride; Cu2O,
copper(I) oxide; and CuO, copper(II) oxide.
Naming of polyatomic anions

The name of a polyatomic anion often ends in -ate, followed by the
oxidation state of the central element in brackets. See the examples given
in Table S31.1.
Compound Oxidation number of Common name Name by Stock system
certain element
Na2SO4 +6 Sodium sulphate Sodium sulphate(VI)
Na2SO3 +4 Sodium sulphite Sodium sulphate(IV)
AgNO3 +5 Silver nitrate Silver nitrate(V)
AgNO2 +3 Silver nitrite Silver nitrate(III)
KMnO4 +7 Potassium permanganate Potassium manganate(VII)
K2MnO4 +6 Potassium manganate Potassium manganate(VI)
K2Cr2O7 +6 Potassium dichromate Potassium dichromate(VI)
K2CrO4 +6 Potassium chromate Potassium chromate(VI)
NaClO4 +7 Sodium perchlorate Sodium chlorate(VII)
NaClO3 +5 Sodium chlorate Sodium chlorate(V)
NaClO2 +3 Sodium chlorite Sodium chlorate(III)
NaClO +1 Sodium hypochlorite Sodium chlorate(I)
Table S31.1 The names of some compounds. Note in particular the naming of polyatomic anions by the Stock system as
shown here.

It should be noted that in this Coursebook series, anions are not

named by the Stock system in most cases. Thus, Na2SO3 is called sodium
sulphite instead of sodium sulphate(IV). But in higher-level studies, we
name anions by the Stock system as well.

Chapter 33 Electrolysis
Supplement to
Flowing mercury cell for the electrolysis of brine
Coursebook p.177
In the flowing mercury cell (Figures S33.1 and S33.2), the electrolysis
takes place in a cell with a slightly sloping base. Mercury flows down the
floor of the cell, forming the cathode. Titanium, which is resistant to
corrosion, is used as the anode. (In some chlor-alkali plants, graphite is
used as the anode. However, it would be corroded.) Saturated brine flows
through the cell during electrolysis.
titanium anodes
chlorine
saturated brine used brine
flow of mercury
hydrogen
mercury cathode sodium
amalgam
water
Figure S33.1 Flowing mercury
sodium
cells in a chlor-alkali plant. mercury
hydroxide
recovered
Figure S33.2 Electrolysis of brine in a flowing mercury cell.
At the anode (titanium): 2Cl–(aq) → Cl2(g) + 2e– (oxidation)
Cl–(aq) ions are preferentially discharged (oxidized) to form chlorine

gas as the main product. Chlorine gas produced is led away through pipes.
It is then washed, dried, liquefied under pressure and stored in steel
cylinders.
At the cathode (mercury): Na+(aq) + e– → Na(s) (reduction)

Na(s) + Hg(l) → Na/Hg(l)
sodium amalgam
Na+(aq) ions are preferentially discharged (reduced) to form sodium

metal which immediately dissolves in the mercury cathode to give a
sodium/mercury alloy called sodium amalgam. This alloy is carried away

before it can react with water.
The sodium amalgam flows into another tank, where it reacts with
Learning tip
water to form hydrogen and sodium hydroxide solution. Mercury is
Sodium amalgam is a liquid
recovered and pumped back to the electrolytic cell. See Figure S33.2
alloy of sodium in mercury.
again.
It can be considered as a
2Na/Hg(l) + 2H2O(l) → 2NaOH(aq) + H2(g) + 2Hg(l)
solution of sodium metal in sodium amalgam
mercury.
However, mercury is poisonous. Serious environmental problems

arise if mercury leaks from the flowing mercury cell.
Supplement to
Membrane cell for the electrolysis of brine
Coursebook p.177
The membrane cell is an electrolytic cell in which an ion-permeable
membrane is used to separate the cathode and anode compartments. Nickel
Learning tip is used as the cathode while titanium is used as the anode. See Figures
The ion-permeable S33.3 and S33.4.
membrane is a polymer chlorine hydrogen
membrane. It works on the

ion-exchange principle, cathode
anode
allowing only cations to
saturated
pass through. brine water
Na+
Na+
Na+
titanium anode Cl– H+ nickel cathode

Cl– OH– H+
Cl–
OH–
used sodium
brine hydroxide
ion-permeable membrane
Figure S33.4 Electrolysis of brine in a membrane cell.
Figure S33.3 Membrane cells in

Cl–(aq) ions are preferentially discharged (oxidized) at the anode to
an ICI chlor-alkali plant in
form chlorine gas.
Malaysia.
At the anode (titanium): 2Cl–(aq) → Cl2(g) + 2e– (oxidation)
H+(aq) ions from water are preferentially discharged (reduced) in the

cathode compartment, forming hydrogen gas.

At the cathode (nickel): 2H+(aq) + 2e– → H2(g) (reduction)

or 2H2O(l) + 2e → H2(g) + 2OH–(aq)
–
In the membrane cell, brine enters the anode compartment and water
enters the cathode compartment. Then chlorine is formed at the anode and
hydrogen at the cathode. Chlorine and hydrogen are kept apart by the
ion-permeable membrane. This membrane is permeable to cations, but not
anions. It allows the passage of Na+(aq) ions but not that of Cl–(aq) or
OH–(aq) ions.
The used brine is simply removed from the anode compartment.

Therefore, the resultant sodium hydroxide solution in the cathode
compartment contains no sodium chloride impurity. It is composed of
about 30–35% sodium hydroxide by mass.
The membrane cell represents a more advanced technology than the

flowing mercury cell. It does not contain poisonous mercury and the
resultant solution is richer in sodium hydroxide. The membrane cell has
more economic and environmental advantages. It is the preferred one for
new chlor-alkali plants.
Supplement to
Quantity of electricity and Faraday’s Laws of electrolysis
Coursebook p.181
Quantity of electricity
The amount of a product formed in electrolysis is related to quantity of
electricity passed. Quantity of electricity (Q) is measured in coulombs
(abbreviation: C). Current (I) (rate of flow of electricity) is measured in
amperes (abbreviation: A). Time (t) is usually in seconds (abbreviation:
s).
By definition,
quantity of electricity = current  time
(coulombs) (amperes) (seconds)
i.e. Q = It
Example S33.1
Calculating the quantity of electricity passed
If a current of 0.3 A flows for 5 minutes, what is the quantity of electricity passed?

Solution
Q = It
= 0.3 A  (5  60) s
= 90 C
Faraday’s Laws of electrolysis

In the early 1830s, Michael Faraday (Figure S33.5) performed many
experiments on electrolysis. He discovered some relationships between
quantity of electricity passed and the amount of products formed. He
summarized these into two laws, known as Faraday’s Laws of
electrolysis:
1. Faraday’s First Law of electrolysis states that the mass of a
substance liberated at (or dissolved from) an electrode during
electrolysis is directly proportional to the quantity of electricity
passed through the electrolyte.
Figure S33.5 Michael Faraday
2. Faraday’s Second Law of electrolysis (expressed in modern terms)
(1791–1867), a great scientist in
states that the number of moles of different ions discharged by the
the 19th century.
same quantity of electricity is inversely proportional to their
respective ionic charges.
It has been found from experiments that 1 mole of electrons has a

total charge of 96 500 coulombs. This quantity of electricity is commonly
known as 1 faraday (abbreviation: F).
Charge of 1 mole of electrons = 1 F = 96 500 C
The value of 96 500 C mol–1 is called Faraday Constant.
Example S33.2
Calculating the charge of an electron
Calculate the charge (in coulombs) of an electron.
Solution
Charge of an electron
96500
= C
6.02  1023
= 1.60  10–19 C

PART VIII CHEMICAL REACTIONS AND ENERGY
Chapter 35 Energy changes in chemical reactions

Supplement to
More about internal energy
Coursebook p.222
The total internal energy of a system is the sum of all the kinetic and
potential energies for each particle in the system. The kinetic energy is
determined by the motion of particles (atoms/molecules/ions) and the
movement of electrons within particles. The potential energy is
determined by the attractions between electrons and nuclei, and repulsions
between electrons and between nuclei in individual particles, and the
interactions between particles. It is impossible to measure internal energy
but possible to measure the change in internal energy (E) by doing
experiments.
E = Efinal – Einitial
where E is the change in internal energy of the system,
Efinal is the final internal energy of the system,
Einitial is the initial internal energy of the system.
A system can exchange energy with its surroundings either by

transferring heat or by doing work. The most common type of work
encountered in chemical systems is the expansion work done as the result
of a volume change in the system. The work done (w) can be represented
as:
w = –PV
where P is pressure in the system,
V is the volume change in the system.
The heat transferred can be represented by the symbol q. During a

reaction, the change in internal energy of a system is equal to the sum of
heat transferred (released or taken in by the system) and the work done (by
or on the system). Therefore,
E = q + w
= q – PV
We can rearrange the above equation to represent the amount of heat

transferred as:

q = E + PV
where q has a positive sign if the system gains heat and a negative sign if
the system loses it.
For a reaction carried out in a closed container, V = 0. The heat

transferred at constant volume:
qv = E
Alternatively, for a reaction carried out at constant pressure in an open

flask, V  0. The heat transferred at constant pressure:
qp = E + PV
The heat transferred in a reaction carried out at constant pressure is known
as the enthalpy change of the reaction, H.
qp = E + PV = H
and it depends on the enthalpy of a system before and after a reaction:
H = Hproducts – Hreactants
The difference between E and H for a reaction can be deduced by

applying the equation,
H = E + PV
For reactions that involve only solid or liquid reactants and products,
the PV is so small that it is negligible. However, if gases are consumed or
produced in the reaction, H and E will be significantly different.
Supplement to
Entropy and free energy
Coursebook p.231
Entropy
It is generally thought that exothermic reactions are spontaneous as they
do not need any energy input while at the same time, give products of
relatively low energies. However, some spontaneous changes are
endothermic and some exothermic reactions do not take place easily at
room conditions. Scientists suggested that there is another driving force for
a physical or chemical change to occur called entropy, denoted by the
symbol S.
Entropy is a measure of the randomness or the degree of disorder of a

system. In general, the greater the disorder of the system, the greater is its
entropy. Gases have more randomness and higher entropy than liquids, and

liquids have more randomness and higher entropy than solids. See Figure
S35.1.
increase in entropy (S)
Solid Gas
Liquid
Figure S35.1 Increase in entropy from solid to liquid to gas.
When ice melts to form water, it absorbs energy. This spontaneous

change is an endothermic process. Exothermicity is not the driving force
for the process. The entropy of the system increases as ice melts to form
water. An increase in entropy is the driving force.
A change in entropy is represented as S.

S = Sfinal – Sinitial
If S is positive, the system has become more disordered (Sfinal > Sinitial). If
S is negative, the system has become less disordered (Sfinal < Sinitial). The
spontaneity of a physical or chemical change is favoured by an increase in
entropy (i.e. S is positive). However, to decide whether a process is
spontaneous, both enthalpy and entropy changes must be taken into
account.
Free energy
To take both enthalpy and entropy into account when deciding about the
spontaneity of a process, we define a quantity called the Gibbs free
energy, denoted by the symbol G. The change in the free energy of the
system is equal to the change in the enthalpy of the system minus the
product of the temperature and the change in the entropy of the system.
G = H – TS
The value of the free energy change (G) is a general criterion for the

spontaneity of a process. If G has a negative value, the process is

spontaneous; if G has a positive value, the process is non-spontaneous.
Table S35.1 shows how H and S affect the spontaneity of a process.
H S G = H – TS Spontaneous/non-spontaneous
–ve +ve –ve Spontaneous at all temperatures
+ve –ve +ve Non-spontaneous at any
temperature
Table S35.1 The way in which H and S affect the spontaneity of a process.
What happens if the process is favoured by H but not favoured by

S, or favoured by S but not favoured by H? In this case, we have to
compare the magnitudes of H and TS. See Table S35.2.
H S G = H – TS Spontaneous/
non-spontaneous
–ve –ve –ve at low temperatures Spontaneous
(favourable) (unfavourable)
+ve at high temperatures Non-spontaneous
+ve +ve +ve at low temperatures Non-spontaneous

(unfavourable) (favourable)
–ve at high temperatures Spontaneous
Table S35.2 Effects of magnitudes of H and TS on the spontaneity of a process.
According to the above table, an endothermic process that is

non-spontaneous at low temperature can become spontaneous at higher
temperature. Consider ice/water transition as an example. Below 0C,
nothing happens to the ice because H is larger than TS, making G
positive. Above 0C, the ice spontaneously melts because TS is larger
than H, making G negative.

Chapter 36 Standard enthalpy change of combustion,

neutralization, solution and formation
Supplement to
Bond enthalpy
Coursebook p.257
Most reactions involve the breaking and formation of bonds. When a bond
is broken or formed, a certain amount of energy is absorbed from or
released to the surroundings. The amount of energy associated with a
particular kind of covalent bond can be estimated by its bond enthalpy.
Bond enthalpy can be expressed in terms of bond dissociation enthalpy
and average bond enthalpy.
Bond dissociation enthalpy

The amount of energy required to break a particular bond in one mole of
gaseous substance is the bond dissociation enthalpy. Its value is always
positive. For example, the bond dissociation enthalpy of Cl2(g) is the
enthalpy required when one mole of Cl2(g) is dissociated into chlorine
atoms:
Cl－Cl(g) → 2Cl(g) H = +242 kJ mol–1
However, for more complicated molecules, a precise bond

dissociation enthalpy for a particular chemical bond depends to some
extent on the environment in the molecule where the bond exists. For
example, the O－H bond in water and CH3O－H bond in methanol have
different environments. Their bond dissociation enthalpies are +492 kJ
mol–1 and +435 kJ mol–1 respectively.
Average bond enthalpy

Since the energy required to break a particular bond varies from one
compound to another, an average value is usually used to generalize the
enthalpy of a bond. This average value is called the average bond
enthalpy.
For this reason, tables of bond enthalpy values are averaged over
those found in a large number of different compounds. The bond lengths
and average bond enthalpies of some common covalent bonds are listed as
follows (Table S36.1):

Bond Bond length (nm) Average bond enthalpy (kJ mol–1)

C–C 0.154 +347.0
C=C 0.134 +612.0
CC 0.120 +838.0
Cl–Cl 0.199 +243.4
Br–Br 0.228 +192.9
I–I 0.267 +151.2
H–F 0.092 +568.0
H–Cl 0.127 +432.0
H–Br 0.141 +366.3
H–I 0.161 +298.3
Table S36.1 Bond lengths and average bond enthalpies of some common covalent
bonds.
In general,
1. The order of bond enthalpy: triple bond > double bond > single bond
2. A shorter bond requires a larger amount of energy to break.
3. If Y represents a non-metal or semi-metal atom, the bond enthalpy of
H–Y usually decreases down a group in the Periodic Table, e.g. bond
enthalpies: H–F > H–Cl > H–Br > H–I.

CHEMISTRY

COURSEBOOK 4A
Contents
PART IX RATE OF REACTION
Chapter 39 Factors affecting rate of reaction
⚫ Browning of apples 1
⚫ Three major postulates of collision theory 2
Chapter 40 Molar volume of gases at room temperature and pressure (r.t.p.)
⚫ Ideal Gas Law 3
PART X CHEMICAL EQUILIBRIUM
Chapter 42 Equilibrium constants
⚫ Equilibrium constants for gases 5
⚫ Equilibrium positions and rate constants 6
Chapter 43 The effect of changes in concentration and temperature on chemical
equilibria
⚫ Reaction quotient and equilibrium constant 8
⚫ Van’t Hoff equation 9

PART IX RATE OF REACTION
Chapter 39 Factors affecting rate of reaction

Supplement to
Browning of apples
Coursebook p.34
What is browning of apples?
The browning of fruit tissues, which is a food spoilage phenomenon, is
especially noticeable in apples. This phenomenon is caused by an initial
enzymatic oxidation of phenols present in apples by atmospheric oxygen to
diquinones. The diquinones readily polymerize to give a brown product in
a short period.
The initial oxidative step is catalysed by enzymes (polyphenol

oxidase) present in the apple, but the subsequent polymerization requires
neither oxygen nor enzymes to take place. See Figure S39.1. This reaction
is also speeded up by the presence of iron (such as an iron or rusted knife)
or copper (such as a copper bowl).
oxygen in air /
brown polymer
enzyme
a phenol a diquinone
Figure S39.1 Reaction leading to the browning of apples.
Principles to prevent the browning of fruits:

1. Removing the supply of oxygen,
2. Inhibiting the enzymatic activity in the initial stage of the reaction.
For example,
1. storing the fruits under water, sugar or salt solution in order to reduce
oxygen supply to the fruit tissues; if the sugar or salt solution is
concentrated, the enzyme responsible for the browning process may
be denatured.
2. using antioxidants such as sulphur dioxide and vitamin C to prevent
the atmospheric oxidation of phenols to diquinones.

3. inhibiting enzymatic activity

 by heating which may denature the enzymes of the browning
process;
 by adding citric acid which provides an acidic environment not
suitable for the enzyme to speed up the browning process.
Supplement to
Three major postulates of collision theory
Coursebook p.35
1. Chemical reactions in the gaseous phase result from the collisions of
reactant particles.
2. A collision results in a reaction if a certain threshold energy
(commonly known as activation energy, Ea) is exceeded. (Refer to
Chapter 54 for a more complete discussion of activation energy.)
3. A collision results in a reaction if the colliding particles are correctly
orientated to one another.
Consider the addition of hydrogen chloride, HCl, to ethene,

CH2=CH2, gives chloroethane.
CH2=CH2 + HCl → CH3CH2Cl
If enough energy is provided, the reaction can only occur when the
hydrogen end of the HCl molecule approaches the carbon-carbon double
bond. If the two molecules do not orientate properly, they simply bounce
off. In Figure S39.2, only the molecules involved in collision 1 orientate
properly to react.
Collision 1 Collision 2
Collision 3 Collision 4
Figure S39.2 Successful and unsuccessful collisions between hydrogen chloride

molecules and ethene molecules.

The mechanism of this reaction is known as electrophilic addition.

In collision 2, the double bond is electron-rich and the approaching
chlorine atom is also slightly negative because it is more electronegative
than hydrogen. Eventually, the repulsion between the double bond and
chlorine atom causes the molecules to bounce off. On the other hand, in
collision 1, the approaching hydrogen atom, which is slightly positive, is
attracted by the electron-rich double bond.
Chapter 40 Molar volume of gases at room

temperature and pressure (r.t.p.)
Supplement to
Ideal Gas Law
Coursebook p.61
The behaviour of ideal gases (or real gases at low pressures and
temperatures) can be described by the ideal gas law which can be
represented by the ideal gas equation:
PV = nRT
where P is the pressure (in N m−2 or Pascals), V is the volume (in m3), n is
the number of moles and T is the absolute temperature (in Kelvin scale, K)
of the gas; R is the universal gas constant (8.314 J K−1 mol−1). The units
used are crucial for each of the quantities. The universal gas constant is
independent of the pressure, temperature, volume and number of moles of
gas.
Example S40.1
Calculating the volume of gas by using the ideal gas equation
Calculate the volume of gas given that there is 0.015 moles of nitrogen at 350C and 100 000 N
m− 2 .
Solution
The ideal gas equation is PV = nRT
P = 100 000 N m−2
V = ? m3
n = 0.015 moles
R = 8.314 J K−1 mol−1
T = (350 + 273) K = 623 K
nRT 0.015  8.314  623
V= = m3 = 7.77  10−4 m3
P 100 000

There are some assumptions to be made when we apply the ideal gas
law:
1. The ideal gas molecules experience no intermolecular forces because
they are too far apart to attract each other.
2. The ideal gas molecules occupy no volume because the molecules are
far apart. The volume occupied by the gas molecules is negligible
compared to the total volume occupied by the gas.
(Note: In real situations, intermolecular forces do exist and ideal gas
molecules do occupy space.)
The volume occupied by one mole of an ideal gas is its molar volume.
RT
For an ideal gas, molar volume = which gives a value of 24.0 dm3
P
mol−1 at r.t.p. (room temperature and pressure).

PART X CHEMICAL EQUILIBRIUM
Chapter 42 Equilibrium constant

Supplement to
Equilibrium constants for gases
Coursebook p.94
The partial pressures of the gaseous reactants and products are proportional
to their concentrations, i.e.
PV
n RT P
c= = =
V V RT
where c is the concentration, n is the number of moles, V is the volume of
the container, P is the partial pressure of the gas, T is the temperature in
Kelvin and R is the universal gas constant. At a particular temperature, RT
is a constant, so c  P.
For reactions involving gases, the equilibrium constant expression can

therefore be written using partial pressures instead of concentrations. For
example, the equilibrium constant expression for a reaction X(g) → Y(g)
can be written as:
PY
KP =
PX
We will use the symbol, Kp, to indicate equilibrium constants derived

from partial pressures and Kc to denote equilibrium constants in terms of
molar concentrations. In general, Kc and Kp are not numerically equal. For
a reaction such as CO2(g) + OH−(aq) → HCO3−(aq) that involves both
gaseous and dissolved components, a ‘hybrid’ equilibrium constant is
commonly used:
[HCO 3− (aq)]
i.e. K =
PCO [OH − (aq)]
2
The relationship between Kp and Kc

For the general equation,
aA + bB cC + dD

PC c PD d [C]c [D]d
Kp = and K c =
PA a PBb [A]a [B]b
n
Concentration = and has the units mol dm−3. Assuming that the
V
gases are ideal, the ideal gas law is:
PV = nRT
The concentration of gas A in the mixture is:
nA PA
[ A] = =
V RT
where PA is the partial pressure of gas A. Then, PA = [A]RT. Substituting
this type of relationship into the expression for Kp, we have:
PC c PD d [C]c (R T )c [D]d (R T ) d
Kp = =
PA a PBb [A]a (R T ) a [B]b (R T )b
[C]c [D]d
Rearranging, K p = a b
(RT ) (c + d ) − ( a + b) and then:
[A] [B]
n g
K p = K c ( RT )
where ng is the change in the number of moles of gas when the reaction
changes from reactants to products.
Supplement to
Equilibrium positions and rate constants
Coursebook p.100
Consider a reaction:
xX yY
The rate of the reaction in either direction can be represented by the rate
equations (to be further discussed in detail in Book 5 Chapter 53) below:
Rate of forward reaction = kf[X]x
Rate of backward reaction = kb[Y]y
where kf and kb are the rate constants of the forward and backward
reactions respectively and the quantities in square brackets represent
concentrations; x and y are the stoichiometric coefficients in the equation.
As long as the forward reaction starts with the conversion of X to Y, the
product Y begins to build up and the backward reaction also starts. As the
reaction proceeds, the forward reaction becomes slower but the backward
reaction will be faster. Eventually, the two reactions proceed at the same
rate and the reaction is at equilibrium, i.e.

rate of forward reaction = rate of backward reaction

kf[X]x = kb[Y]y
Now, consider the following cases:

1. Forward rate constant (kf ) >> Backward rate constant (kb)
If the forward rate constant is very much greater than the backward rate
constant, it requires that [Y]y exceeds [X]x by the same ratio in order to
attain equilibrium. It means that the equilibrium position will lie strongly
on the right (product side).
very large equilibrium

very large forward
concentration of product
rate constant xX yY
Equilibrium position lies mainly to
the product side
2. Forward rate constant (kf ) << Backward rate constant (kb)

If the forward rate constant is very much smaller than the backward rate
constant, it requires that [X]x exceeds [Y]y by the same ratio in order to
attain equilibrium. We can say that the equilibrium position will lie
strongly on the left (reactant side).
very small forward little product is
rate constant formed

xX yY
Equilibrium position lies mainly to
the reactant side
3. Forward rate constant (kf )  Backward rate constant (kb)

If the values of kf and kb are comparable, there are significant
concentrations of both the reactant and product present at equilibrium.
xX yY

Chapter 43 The effect of changes in concentration

and temperature on chemical equilibria
Supplement to
Reaction quotient and equilibrium constant
Coursebook p.118
When we compare the reaction quotient, Qc, and equilibrium constant, Kc,
we can predict the shift in the equilibrium position. Consider the three
cases below:
[products]
[products] K c = Qc = [products]
Qc = [reactants] Qc =
[reactants] [reactants]
Qc > Kc Qc = Kc Qc < Kc
Net reaction to the left No net reaction Net reaction to the right
The table below shows the prediction of equilibrium position using

the reaction quotient Qc.
Qc Direction of shift of equilibrium position

Kc
>1 Reaction proceeds to the left to decrease the concentration(s) of
product(s)
=1 System is at equilibrium; no net change will occur
<1 Reaction proceeds to the right to increase the concentration(s) of
product(s)
Consider the equilibrium system of the following reaction at 298 K:

N2O4(g) 2NO2(g) Kc = 0.00590 M
[N2O4(g)]/M 0.001 0.002 0.003 0.004 0.005 0.006 0.007 0.008

[NO2(g)]/M 0.002429 0.003435 0.004207 0.004858 0.005431 0.00595 0.006427 0.00687
1
2
(Note: [NO2(g)] is calculated by rearranging the equilibrium expression: [NO2(g)] = {[N2O4(g)]Kc} )
A plot of [NO2(g)] against [N2O4(g)] is shown in the graph below

(Figure S43.1).

[NO2(g)]
Qc = 0.0490 M
Qc = Kc = 0.00590 M
Qc = 0.000167 M
[N2O4(g)]
Figure S43.1 A graph showing the concentrations of [NO2(g)] against [N2O4(g)].
In the above graph, all the points on the curve represent the
equilibrium positions that satisfy the requirement that
[ NO 2 (g)]2
K c = Qc =
[ N 2O 4 (g)]
The points such as X and Y do not fall on the curve. They correspond to
some non-equilibrium states. As chemical equilibrium is dynamic in nature,
it will adjust itself by shifting the equilibrium position to such a direction
to maintain the equilibrium constant, Kc.
For point X where Qc > Kc, we would expect a reaction that reduces
the value of Qc by converting some of the NO2 into N2O4; in other words,
the equilibrium position shifts to the left. Similarly, for point Y where Qc <
Kc, the equilibrium position shifts to the right to produce more NO2.
Supplement to
Van’t Hoff equation
Coursebook p.123
After carrying out a series of experiments, scientists have found that
equilibrium constant is related to temperature by the van’t Hoff equation,
H
lnK = constant −
RT

where K is the equilibrium constant,

H is the standard enthalpy change of the forward reaction,
R is the universal gas constant, and
T is the temperature in Kelvin.
Consider the following equilibrium system in which the forward

reaction is endothermic:
N2O4(g) 2NO2(g) H = +58.1 kJ mol−1
As H is positive, the second term on the right of van’t Hoff equation
( −H  ) is negative. When the temperature is raised, this second term
RT
becomes less negative, causing the value of lnK and hence K to increase.
[products]
Since K = , more products will be formed and the equilibrium
[reactants]
position has shifted to the product side (right). It can be concluded that an
increase in temperature favours endothermic change (the forward reaction
in the above example).
On the other hand, when the temperature is lowered, ( −H  ) becomes

RT
more negative, causing the value of lnK and hence K to decrease. Since
[products]
K= , more reactants will be formed and the equilibrium position
[reactants]
has shifted to the reactant side (left). Hence, lowering the temperature
favours exothermic change (the backward reaction in the above example).

CHEMISTRY

COURSEBOOK 4B
Contents
PART XI CHEMISTRY OF CARBON COMPOUNDS
Chapter 44 Introduction to selected homologous series
⚫ Hybridization of orbitals 1
⚫ Aromatic hydrocarbons 4
Chapter 46 Typical reactions of various functional groups
⚫ Free radical substitution 6
⚫ Electrophilic addition 7
⚫ Nucleophilic substitution 8
⚫ Nucleophilic addition 10
PART XII PATTERNS IN THE CHEMICAL WORLD
Chapter 49 Periodic variation in physical properties of the elements Li to Ar
⚫ Periodic variation in atomic radius 11
Chapter 51 General properties of transition metals
⚫ Electronic configuration of transition metals and coloured ions 12
⚫ Formation of complexes 14

PART XI CHEMISTRY OF CARBON COMPOUNDS
Chapter 44 Introduction to selected homologous

series
Supplement to
Hybridization of orbitals
Coursebook p.139
When applying the concepts of Valence Shell Electron Pair Repulsion
Theory (VSEPR Theory) to covalent molecules, it is possible for us to
predict the geometry of the atoms within the structures and the geometry of
the molecules. Based on the VSEPR Theory, structures are found to exist
in a variety of geometric patterns e.g. linear, trigonal planar, tetrahedral,
etc.
In fact, atoms use their outermost shell orbitals for sharing electrons.
Do you know
These orbitals exist with shapes that are incompatible with the predicted
As mentioned in Book 1
geometric patterns from VSEPR Theory. For instance, tetrahedral
‘Supplementary
Information’, the term
geometry consists of bonds that are arranged at angles of 109.5. However,
it is difficult to imagine the p orbitals (px, py and pz orbitals), with angles of
‘orbital’ is used to represent
a region within which there
90 between them, altering their own structures to accommodate the
required tetrahedral angles.
is a high probability of
finding an electron (usually
In order to explain this, chemists developed the hybridization theory.
90% of the time).
The theory says that atoms involved in the formation of molecules will
undergo structural changes in their valence atomic orbitals. They will
convert their atomic orbitals into a new set of orbitals called hybrid
orbitals. The hybrid orbitals can be used for bonding and will have some
characteristics of the original atomic orbitals, but differ somewhat in their
geometry.
Take methane, CH4 (the first member of straight-chained alkane), as

an example. The structural formula of methane is as follows:
Let us look at the electronic configuration of ground state (lowest energy

state) carbon:

From the ground state electronic configuration, we can see that

carbon has four valence electrons, two in the 2s subshell and two in the 2p
subshell. The 1s electrons are considered to be core electrons and are not
available for bonding. There are two unpaired electrons in the 2p subshell.
Carbon in this ground state would be able to form at most two bonds by
using the two unpaired electrons. In order to form four bonds, carbon will
form an excited state by promoting one of its 2s electrons into its empty 2p
orbital. After hybridization, all 2s and 2p orbitals have the same energy and
carbon will be able to form four bonds. The excited state configuration is
shown below (Figure S44.1).
Hybridization
Atomic orbitals Hybrid orbitals

Figure S44.1 Hybridization of the 2s and three 2p orbitals (sp3) of a carbon atom.
The four sp3 hybrid orbitals will arrange themselves in

three-dimensional spaces to get as far apart as possible (to minimize
electronic repulsion). This results in a tetrahedral geometry, where the
orbital angle is 109.5. See Figure S44.2.
sp3
2pz
2s
2py
sp3 sp3
2px
sp3
Figure S44.2 The tetrahedral geometry of sp3 hybrid orbitals.
Each hybrid orbital contains one electron. A hydrogen 1s orbital will

then come in and overlap with each of the hybrid orbitals to form a sigma
() bond (head-on overlap), as shown below (Figure S44.3).

Figure S44.3 The formation of sigma bonds between carbon and hydrogen atoms in
methane.
Now take ethene, C2H4 (the first member of straight-chained alkene),

as an example. The structural formula of ethene is shown below:
The structure shows that there are three atoms around each carbon atom.
This means that three hybrid orbitals are formed for each carbon atom. In
order to form three hybrid orbitals, three atomic orbitals are mixed. The 2s
orbital and two of the 2p orbitals for each carbon atom are mixed. Thus,
the hybridization for each carbon atom is sp2. See Figure S44.4.
Hybridization
Unhybridized p orbital
Atomic orbitals Hybrid orbitals

Figure S44.4 Hybridization of the 2s and two 2p orbitals (sp2) of a carbon atom.
The three sp2 hybrid orbitals will arrange themselves in

three-dimensional spaces to get as far apart as possible. This results in a
trigonal planar geometry, where the orbital angle is 120. The unhybridized
p orbital will be perpendicular to this trigonal plane. It is important to note
that each carbon atom is sp2 hybridized and the hybrid orbitals are
arranged in a trigonal planar geometry. See Figure S44.5.

2pz
2pz
2s sp2
sp2
2py
2px sp2
Figure S44.5 The trigonal planar geometry of sp2 hybrid orbitals.
The unhybridized p orbitals will overlap through areas of low

electron density. The head-on overlap of sp2 orbitals forms a sigma ()
bond and the lateral overlap of unhybridized p orbitals forms a pi () bond
between the carbon atoms. This accounts for the formation of
carbon-carbon double bond. See Figure S44.6. A hydrogen 1s orbital will
then come in and overlap with each of the remaining two sp2 hybrid
orbitals to form a sigma () bond (head-on overlap). Finally, each carbon
atom in ethene is trigonal planar in geometry with a bond angle of 120.
Figure S44.6 The lateral overlap of unhybridized 2p orbitals of the carbon atom in ethene.
Supplement to
Aromatic hydrocarbons
Coursebook p.168
Aromatic hydrocarbons are compounds which contain benzene ring
(Figure S44.7). Benzene is an organic chemical compound with the
molecular formula C6H6. It is a natural component of crude oil and may be
synthesized from other compounds present in petroleum. Although it is a
known carcinogen, it is quite stable and an important industrial solvent as
well as precursor in the production of drugs, plastics, synthetic rubber and
dyes.
Figure S44.7 Kekulé
structure of benzene (C6H6). In 1865, Kekulé, a German chemist, proposed the structure for
benzene as shown in Figure S44.7. The structure was thought to contain
alternate single and double bonds. However, modern techniques exclude
the above possibility. Nowadays, we can measure the bond length in
benzene ring accurately. See Table S44.1.

Bond type Bond length /nm

C−C in cyclohexane 0.154
C=C in cyclohexene 0.134
C−C in benzene 0.140
Table S44.1 The bond lengths of different bonds in cyclohexane,
cyclohexene and benzene.
It was found that all the bond lengths of C−C bonds in benzene were
the same and somewhat between that of C−C bond in an alkane and C=C
bond in an alkene. This does not fit with Kekulé’s idea of alternating single
and double bonds.
Besides, we can consider the hydrogenation of cyclohexene below.
H = −119 kJ mol−1
If three double bonds are present ― as in benzene, the comparable reaction

should liberate (3 × 119) kJ mol−1 = 357 kJ mol−1. However, the actual
value of heat released from the hydrogenation of benzene was found to be
only 207 kJ mol−1.
H = −207 kJ mol−1
It was found that benzene is (357 – 207) kJ mol−1 = 150 kJ mol−1 more
stable than expected. It was believed that benzene does not contain three
ordinary C=C bonds. See Figure S44.8.
Enthalpy /
kJ mol−1
3  −119
= −357
Benzene
−207
−119
Figure S44.8 The relative stabilities of cyclohexene, cyclohexane, 1,3,5-cyclohexatriene

and benzene.

The above phenomenon can be accounted for by the concept of

delocalization of electrons. The unhybridized 2p electron on each carbon
atom in benzene is overlapping with those on both sides of it. This
extensive sideway overlap produces a system of pi () bonds which are
spread out over the whole carbon ring. Because the electrons are no longer
held between just two carbon atoms but are spread over the whole ring, the
electrons are said to be delocalized.
In general, the more the electrons spread around, the more they are
delocalized, the more stable the molecule becomes. With the delocalized
electrons in place, benzene is about 150 kJ mol−1 more stable than
expected. This stabilization energy involved is often referred to as
delocalization energy (or resonance energy).
Although we will still come across the Kekulé structure for benzene
(Figure S44.7), for most purposes we use the structure in Figure S44.9.
The hexagon shows the ring of six carbon atoms, each of which is bonded
to one hydrogen atom. The circle represents the delocalization of electrons.
Figure S44.9 Structure of
It is essential that we include the circle. If the circle is omitted, we are
benzene reflecting the
drawing cyclohexane instead of benzene.
delocalization of electrons
inside.
Chapter 46 Typical reactions of various functional
groups
Supplement to
Free radical substitution
Coursebook p.207
The halogenation of alkanes is a free radical substitution. A substitution
is a chemical change in which an atom (or a group of atoms) of a molecule
is replaced by another atom (or group of atoms). Take the bromination of
methane as an example:
CH4 + Br2 → CH3Br + HBr
The mechanism is as follows:
1. Chain initiation
 The reaction is initiated by homolytic fission of bromine molecules,
producing highly reactive bromine radicals. After this step, a chain
reaction occurs.

uv
A half arrow, ‘ ’ denotes the movement of an electron.
2. Chain propagation
 The bromine radicals then react with methane molecules and attract H
atoms from them to form HBr molecules and methyl radicals, each
with an unpaired electron.
 The methyl radicals then react with other bromine molecules to form
bromomethane and more bromine radicals. Radicals are produced
continuously and chain propagation does not end up with stable
species.
3. Chain termination
 Chain propagation may continue with the formation of more
haloalkane molecules or be stopped when two reactive radicals
combine to form a stable neutral molecule. These are the termination
steps.
etc…
 The bromomethane may undergo more substitution reactions to give
dibromomethane, tribromomethane and tetrabromomethane.
Supplement to
Electrophilic addition
Coursebook p.211
Alkenes are more reactive than alkanes because carbon-carbon double
bonds are electron-rich. The electron-rich carbon-carbon double bonds
tend to react with the electrophiles, which are electron deficient species.

They possess an empty orbital to receive electrons. The bromination of

alkene is an electrophilic addition in which two bromine atoms are added
across a double bond. The mechanism is as follows:
1. When a bromine molecule is attracted to an alkene molecule, a
slightly positive charge is induced in the bromine atom that is facing
the double bond.
2. An unstable cyclic bromonium ion is formed as an intermediate.
3. The bromide ion attacks the cyclic bromonium ion from the other side
because of steric hindrance. As a result, the addition is named as
‘trans’ addition.
bromonium ion
‘trans’ addition
A full arrow, ‘’, denotes the movement of a pair of electrons.
Let us consider another electrophilic addition of alkene. When a

hydrogen bromide molecule is added across a carbon-carbon double bond,
hydrobromination occurs and a bromoalkane is formed. The mechanism
for the hydrobromination of alkene is shown below.
Supplement to
Nucleophilic substitution
Coursebook p.213
There are two possible reaction pathways for the substitution of halogen
atom of haloalkanes with hydroxyl group, namely SN1 and SN2. They are
both nucleophilic substitution. The hydroxide ion is regarded as a
nucleophile (an electron-rich species) as it is negatively charged and

readily attracted to a positive centre. In this reaction, the positive centre is

the slightly positive carbon atom in the C−X bond.
SN1 (Unimolecular Nucleophilic Substitution)

The following two-step mechanism of the SN1 reaction involves the
formation of an intermediate carbonium ion.
slow fast
r.d.s.
breaking of C−X bond intermediate

(a trigonal planar carbonium ion)
We should note that:

1. The rate of the overall reaction depends on the slow rate step (rate
determining step, r.d.s.). In the above reaction, r.d.s. is the formation
of the carbonium ion from alkyl halide.
2. Since the rate determining step involves only one molecular species
(the haloalkane), it is a unimolecular reaction.
SN2 (Bimolecular Nucleophilic Substitution)

The following one-step mechanism of the SN2 reaction involves the
formation of a highly unstable transition state.
slow fast
r.d.s.
side attack of OH−

transition state
1. The one-step mechanism of SN2 reaction involves a transition state

in which the entering hydroxide ion and the leaving halide ion are
both partially bonded to the same carbon atom.
2. The rate of reaction depends on the concentration of both the
hydroxide ion and the haloalkane.
3. Since the rate determining step involves two species (the haloalkane
and the hydroxide ion), it is a bimolecular reaction.

Supplement to
Nucleophilic addition
Coursebook p.222
The most typical reaction of carbonyl compounds is nucleophilic addition
to the carbon-oxygen double bond. Since the carbonyl carbon atom carries
a partial positive charge, the carbonyl group is susceptible to attack by a
nucleophile. The mechanism for the carbonyl reduction by hydride is
shown below.
1. Lithium aluminium hydride provides highly reactive hydride ions that

can attack the partial positive carbonyl carbon atoms of either
aldehydes or ketones.
2. An unstable alkoxide ion is formed as an intermediate.
3. The presence of hydrogen ions (from any typical acid) can change the
alkoxide ions into alkanols.

PART XII PATTERNS IN THE CHEMICAL WORLD
Chapter 49 Periodic variation in physical properties

of the elements Li to Ar
Supplement to
Periodic variation in atomic radius
Coursebook p.314
Within a group of elements, the size of the atoms tends to increase from
top to bottom. Down any group, the number of electrons for each element
increases, and additional electron shells are occupied by these electrons.
The additional electron shells are further away from the nucleus.
Within a period of elements, from left to right, the size of atoms tends
to decrease. Moving from left to right across a period, the number of
electrons for each element increases. Since all the electrons are occupying
the same electron shell, they are at a similar distance from the nucleus.
However, the number of protons of each element within a period increases.
The increasing positive nuclear charge enables the nucleus to draw the
electrons closer to itself, and hence, decreasing the atomic size. The trend
in atomic radius of Periods 2 and 3 main group elements is shown below
(Figure S49.1):
Atomic radius / nm
Period 2 Period 3
Atomic number
Figure S49.1 Variation in atomic radii of Periods 2 and 3 main group elements.
The atomic radius of an element affects its physical properties and

chemical properties a lot. For example, metals with larger atomic radius
are more reactive as their outermost shell electrons are further away from

the nucleus and less attracted. These metals have a higher tendency to lose
their electrons to form cations. However, non-metals with smaller atomic
radius are more reactive as their nuclei are more effective in attracting
outside electrons to form anions. Moreover, smaller non-metal atoms form
shorter covalent bonds which are stronger and usually less easily broken.
Chapter 51 General properties of transition metals

Supplement to
Electronic configuration of transition metals and coloured ions
Coursebook p.335
Electronic configurations
Since the orbital of lowest energy in the fourth shell (i.e. the 4s orbital) is
still lower in energy than the highest energy orbitals in the third shell (i.e.
the 3d orbitals), electrons fill in the more stable 4s orbital first, before 3d
orbitals are filled. This can be evident from the case of calcium (20
electrons), with electronic configuration: 1s22s22p63s23p64s2. Then the next
ten electrons of the transition metals will go into the 3d orbitals. The
electronic configurations of the transition metals are shown in Table S51.1.
Atomic number Element Inner shell 3d 4s

21 Scandium Ar  
22 Titanium Ar   
23 Vanadium Ar    
24 Chromium Ar      
25 Manganese Ar      
26 Iron Ar      
27 Cobalt Ar      
28 Nickel Ar      
29 Copper Ar      
30 Zinc Ar      
Table S51.1 Electronic configurations of the transition elements. Each of them already has a full argon core of electrons
(1s22s22p63s23p6).
The electronic configurations of chromium and copper are out of our

expectations! We expect to see [Ar]3d44s2 for chromium and [Ar]3d94s2
for copper. But they turn out to be [Ar]3d54s1 and [Ar]3d104s1 respectively.
These configurations result because the half-filled (3d5 and 4s1) and
full-filled (3d10 and 4s2) subshells gain extra stability.

Colours of transition metal ions

When the ligands form bond with the transition metal ion, there is
Do you know
repulsion between the electrons in the ligands and the electrons in the d
A ligand is either a neutral
orbitals of the metal ion. This raises the energy of the d orbitals. However,
molecule or ion, containing at
because of the way the d orbitals are arranged in space, their energies are
least one atom having a lone
not raised by the same amount. Instead, the d orbitals split into two groups
pair of electrons which can
with slightly different energy levels. See Figure S51.1.
be donated to the central
Potential energy
cation or atom to form a
dative covalent bond. Two 3d orbitals of
higher energy
All 3d orbitals have the same energy

before a ligand approaches.
Three 3d orbitals of
lower energy
Figure S51.1 Splitting of the 3d orbitals of a transition metal ion.
Take vanadium(II) ion as an example. There is an unpaired d electron

occupying one of the 3d orbitals with lower energy. When sufficient light
is absorbed, the 3d electron is promoted from the lower 3d orbital to one of
the higher 3d orbitals. This leads to d-d transition that absorbs light. The
remainder of the light reflected in the visible spectrum accounts for the
specific colour of the ion (violet).
Some common coloured transition metal complexes are listed in

Table S51.2.
Ion Colour of ion
2+
[Cu(H2O)6] Blue
[Cu(NH3)4(H2O)2]2+ Deep blue
3+
[Cr(H2O)6] Green
[Cr(NH3)6]3+ Purple
[Cr(H2O)6]2+ Blue
2+
[Co(H2O)6] Pink
[CoCl4]2− Deep blue
Table S51.2 Common transition metal complexes and their colours.

Supplement to
Formation of complexes
Coursebook p.351
The widespread occurrence of complex compounds is characteristic of
transition elements. A complex is formed by the combination of a central
atom or ion with surrounding ions or molecules, termed ligands. The
central ion usually has high charge density (small size and high electric
charge) that attracts electrons strongly. The co-ordination number of the
metal ion in a complex is the total number of lone pairs donated by the
ligands in that complex. The ligands are attached to the central ion by
dative covalent bonds.
Let us consider Fe(H2O)63+ as the first example. Iron has the

electronic configuration 1s22s22p63s23p63d64s2. When it forms an Fe3+ ion,
it loses the 4s electrons and one of the 3d electrons. Then the electronic
configuration becomes 1s22s22p63s23p63d5. Looking at this as
electrons-in-boxes:
Fe      
3d 4s
− 3 electrons
Fe3+     
3d 4s
It is important to note that the unpaired electrons in the 3d orbitals are

NOT involved in the bonding in any way. Instead, the ion uses six orbitals
from the 4s, 4p and 4d subshells to accept lone pairs from the ligands (i.e.
water molecules). Before the orbitals are used, they are re-organized
(hybridized) to produce six orbitals of equal energy.
These orbitals are hybridized into orbitals of equal energy
and used to accept lone pairs from six water molecules.
Fe3+     
3d 4s 4p 4d

The iron(III) ion will use six orbitals rather than four or eight or
whatever. This is because six is the maximum possible number of water
molecules to fit around an iron(III) ion (or most other metal ions). By
making the maximum number of bonds, it releases most energy and
becomes most stable.
Only one lone pair is shown on each water molecule in the structural
formula below. The other lone pair is pointing away from the iron(III) ion
and so is not involved in the bonding.
Fe(H2O)63+
Because the iron is forming six bonds, the co-ordination number of

the iron(III) ion is 6.
The second example is the formation of a complex CuCl42−, from

copper(II) ions and chloride ions. Copper has the electronic configuration
1s22s22p63s23p63d104s1. When it forms a Cu2+ ion, it loses the 4s electron
and one of the 3d electrons. Then the electronic configuration becomes
1s22s22p63s23p63d9.
As chloride ions are bigger than water molecules, only four chloride
ions (ligands) can fit around the central ion. In order to form bond with the
four chloride ions, the empty 4s and 4p orbitals are used (in a hybridized
form) to accept a lone pair of electrons from each chloride ion.
These orbitals are hybridized into orbitals of equal energy
and used to accept lone pairs from four chloride ions.
Cu2+     
3d 4s 4p 4d

The structural formula of the above complex ion is:
CuCl42−
The ion carries two negative charges that come from a combination of
the two positive charges on the copper(II) ion and the four negative
charges from the four chloride ions. In this case, the co-ordination number
of the copper(II) ion is, of course, 4.

CHEMISTRY

COURSEBOOK 5
Contents
PART XIII INDUSTRIAL CHEMISTRY
Chapter 52 Importance of industrial processes
⚫ Banning the development of unsafe synthetic products 1
⚫ More about MTBE (methyl tertiary-butyl ether) 2
⚫ More about production of vitamin C 2
Chapter 53 Rate equation
⚫ Integrated rate equations 4
⚫ Method of excess reactants 12
⚫ Iodine clock reaction 12
Chapter 54 Activation energy
⚫ Determining the distribution of molecular speeds 15
⚫ More about elementary reactions 17
Chapter 55 Catalysis and industrial processes
⚫ Positions of the active sites
19
⚫ More about homogeneous and heterogeneous catalyst
Chapter 56 Industrial processes
⚫ Problems associated with nitrogenous fertilizers 22
⚫ Reactions in fuel cells using different fuels 23
Chapter 57 Green chemistry for industrial processes
⚫ Maximizing atom economy 25
⚫ Producing safer chemical products 28
⚫ Designing for energy efficiency 30

PART XIII INDUSTRIAL CHEMISTRY
Chapter 52 Importance of industrial processes

Supplement to
Coursebook p.7 Banning the development of unsafe synthetic products

Phthalate esters are the dialkyl or alkyl aryl esters of phthalic acid. The
name phthalate derives from phthalic acid. They are commonly used to
soften plastics (especially PVC) or as a solvent in many different consumer
products. Phthalates are found in toys and in beauty care products such as
deodorants, nail polish, hair sprays and perfumes.
Phthalates are easily released into the environment because there is no

covalent bond between the phthalates and plastics when they are mixed.
Figure S52.1 Chemical Because phthalate plasticizers are not chemically bound to PVC, they can
structure of phthalates, where R easily leach and evaporate into food or the atmosphere. Phthalate exposure
and R’ are same or different can be through direct use or by indirect means through leaching and
alkyl/aryl groups. general environmental contamination. In general, since phthalates
evaporate into the atmosphere, their indoor concentrations are higher than
their outdoor concentrations.
Phthalates can be absorbed through the skin, inhaled as fumes or

eaten by little child. After testing with animals, it shows that phthalates
may cause birth defects, damage the kidneys, the liver, the lungs and the
reproductive system.
The use of some phthalates in children’s toys has been restricted in

the European Union since 1999. For example, diethylhexyl phthalate
(DEHP) is restricted for all toys while some phthalates such as diisononyl
phthalate (DINP) and ditridecyl phthalate (DIDP) are restricted only in
toys that can be taken into the mouth. The restriction states that the amount
of phthalates may not be greater than 0.1% by mass of the plasticized part
of the toy. These phthalates are allowed at any concentration in other
consumer products while other phthalates are not restricted.
In January 2010, the Australian Consumer Affairs Minister Craig

Emerson announced a ban on items containing more than 1% DEHP. This
is because international research linked it to reproductive difficulties.

Supplement to More about MTBE (methyl tertiary-butyl ether)

Coursebook p.8 The molecular formula of MTBE is C5H12O. It is a volatile, highly
flammable and colourless liquid which is immiscible with water. MTBE is
manufactured via the chemical reaction of methanol and isobutylene.
Methanol is derived from natural gas, and isobutylene is derived from
butane obtained from crude oil or natural gas. Thus MTBE is a substance
produced from fossil fuel.
Oxygenates are hydrocarbons that contain one or more oxygen atoms.

The oxygenates include alcohols and ethers such as ethanol and MTBE
respectively. MTBE is a fuel additive added to motor vehicles to make
petrol burn more cleanly by reducing the emission of carbon monoxide.
However, it is believed that MTBE can cause various kinds of

Figure S52.2 Structure of
illnesses. MTBE can make asthma worse for some people. It can also
MTBE (methyl tertiary-butyl
cause neurological symptoms like insomnia, anxiety, dizziness, nausea
ether).
and headache, as well as allergic symptoms like watery or itchy eyes and
skin rash.
Unlike petrol, MTBE dissolves in water easily. It would be very

difficult to remove once it gets into the underground water supply.
Moreover, MTBE has a minty odour, leading to unpleasant taste and odour
in water.
Supplement to More about production of vitamin C

Coursebook p.14 Scientists have been trying to find ways to synthesize vitamin C (chemical
name: ascorbic acid) directly by fermentation of glucose. However, one
important problem is the instability of ascorbic acid in water in the
presence of oxygen. The successful approaches nowadays involve
fermentative preparation of an intermediate, which is then converted to
ascorbic acid. Vitamin C is commonly produced by two main processes:
the Reichstein process and the two-stage fermentation process.

In both of the above processes, glucose is first reduced to sorbitol at a

high temperature. The Reichstein process transforms sorbose into DAKS
(di-acetone-ketogulonic acid) in a two-step chemical process. The first
step is the reaction with acetone which produces di-acetone sorbose, which
is then oxidized using chlorine and sodium hydroxide to produce DAKS.
Then, DAKS is dissolved in a mixture of organic solvents and its structure
is rearranged to form vitamin C, using an acid catalyst.
It should be noted that Reichstein process uses considerable

quantities of organic and inorganic solvents and reagents in the various
stages. These include acetone, sulphuric acid, chlorine and sodium
hydroxide. Although some of these compounds can be recycled, stringent
environmental control is needed. This results in significant waste disposal
costs.
The two-stage fermentation process is the newer production process.

A second fermentation step replaces the chemical reactions used to
produce DAKS in the Reichstein process. This fermentation results in a
different intermediate, KGA (2-keto-L-gulonic acid). Then, KGA is
dissolved in a mixture of organic solvents and is concerted to vitamin C
using a catalyst. Compared with the Reichstein process, the two-stage
fermentation process uses less toxic solvents and reagents. This helps to
reduce the chance of polluting the environment and the cost of processing
waste products. Generally, the conversion of glucose to vitamin C via the
two-stage fermentation process follows the following route:
ascorbic acid
glucose sorbitol sorbose KGA
(vitamin C)
fermentation fermentation

Chapter 53 Rate equation
Supplement to Integrated rate equations

Coursebook p.26-31 The rate equation tells the rate of reaction at any time and with any
concentration of reactants. We would also like to know the concentration
of a reactant after passing a certain period of time if the initial
concentration of the reactant is known.
An expression which shows how the rate depends on the

concentrations of the reactants is called a differential rate equation, or
simply called the rate equation. Let’s consider the general reaction
involving only one reactant:
A → product(s)
The rate equation is expressed as:
d [ A]
Rate = − = k [ A] n
dt
where k represents the rate constant and the power n represents the order
of reaction with respect to reactant A.
An experiment can be performed to determine the concentration of A

at various time intervals. The data obtained can be used to determine the
reaction rates at different time during the reaction. In order to obtain the
values of n and k of a rate equation, two graphs (a concentration-time
graph and a rate-concentration graph) are required to plot. Tangents are
drawn on the concentration-time graph and their slopes are calculated to
determine the rates at different concentrations. However, the reaction rates
may not be measured accurately as tangents are difficult to be drawn
accurately.
Therefore, integrated rate equation method is usually applied. The

advantage of using integrated rate equations is that they are directly related
to the concentrations and time. Thus, the process of finding the orders and
rate constants of the reactions will become simpler and more accurate.

1. Zeroth order reaction

The rate equation is:
d [ A]
Rate = − = k0
dt
The negative sign above indicates the consumption of reactant.
After integrating the rate equation, we have:

[A] = −k0t + [A]0
where [A]0 is the initial concentration of the reactant and t is the time of
the reaction.
A plot of [A] against time gives a straight line with slope −k0 and
y-intercept [A]0.
[A]
[A]0
slope = −k0
Time
Figure S53.1 A graph of [A] against time for a zeroth order reaction.
2. First order reaction

d [ A]
Rate = − = k1 [A]
dt

ln[A] = − k1t + ln[A]0
the reaction.

A plot of ln[A] against time gives a straight line with slope −k1 and
y-intercept ln[A]0.
ln[A]
ln[A]0
slope = −k1
Time
Figure S53.2 A graph of ln[A] against time for a first order reaction.
For the first order reaction, the integrated rate equation may be
rearranged as:
[A]
ln( 0 ) = k1t
[A]
Half-life of first order reaction

The time taken for the concentration of a reactant to fall to half its original
value is called half-life ( t 1 ). The half-life is the time required for the
2
1
concentration of reactant A to decrease from [A]0 to [A]0. Substituting
2
these values into the above equation:
[A]0
ln( ) = k1t 1
1
[A]0 2
2
ln 2 = k1t 1
2
ln 2 0.693
t1 = =
2
k1 k1
The half-life of a first order reaction is a constant and is independent
of the initial concentration of reactant A.

3. Second order reaction

d [ A]
Rate = − = k 2 [A] 2
dt

1 1
= k 2t +
[A] [A] 0
the reaction.
1
A plot of against time gives a straight line with slope k2 and
[A]
1
y-intercept .
[A] 0
1
[A]
1
[A] slope = k2
0
Time
1
Figure S53.3 A graph of against time for a second order reaction.
[A]
The study of chemical kinetics always involves the collection of

concentration data as a function of time. Integrated rate equation relates
concentration with time. Then, by finding a linear plot (a plot that gives a
perfect straight line), we can easily identify the order of a chemical
reaction and also the rate constant.

It should be noted that to determine the order of a reaction, always

look for a plot that gives a straight line. See Table S53.1 and Table S53.2.
Order of reaction Linear plot results
Zeroth [A] against time
First ln[A] against time
1
Second against time
[A]
Table S53.1 Linear plots for different orders of reactions.
Order of
Zeroth First Second
reaction
[A] against
time
Rate
against [A]
Graphs
plotted
from
integrated
rate
equations
Table S53.2 Types of graphs plotted for reactions involving only one reactant and of different orders.

Example S53.1
Determining the order of reaction and rate constant by plotting graphs according to
integrated rate equation method
Consider the reaction of 1-chlorobutane with water to give butan-1-ol.
C4H9Cl + H2O → C4H9OH + HCl
The following experimental data was obtained by a group of students who studied the chemical
kinetics of the reaction.
Time (s) 0 50 100 150 200 300 400 500 800
[C4H9Cl]
0.1000 0.0905 0.0820 0.0741 0.0671 0.0549 0.0448 0.0368 0.0200
(mol dm−3)
(a) Plot three graphs to determine the order of reaction with respect to C4H9Cl.
(i) [C4H9Cl] against time
(ii) ln[C4H9Cl] against time
1
(iii) against time
[C 4 H 9 Cl]
(b) Based on the graphs, how would you determine the order of the reaction?
(c) Calculate the rate constant of the reaction.
Solution
(a) (i) [C4H9Cl]
(mol dm−3)
Time (s)
Figure S53.4 A plot of [C4H9Cl] against time.

(ii)
Time (s) 0 50 100 150 200 300 400 500 800
ln[C4H9Cl] −2.30 −2.40 −2.50 −2.60 −2.70 −2.90 −3.10 −3.30 −3.90
Time(s)
ln[C4H9Cl]
Figure S53.5 A plot of ln[C4H9Cl] against time.
(iii)
Time (s) 0 50 100 150 200 300 400 500 800
1
[C 4 H 9 Cl] 10.00 11.05 12.20 13.50 14.90 18.21 20.50 27.17 50
(mol−1 dm3)
1
[C 4 H9 Cl]
(mol−1 dm3)
Time(s)
1
Figure S53.6 A plot of against time.
[C4 H9Cl]

(b)
 In Figure S53.4, the plot of [C4H9Cl] against time does not give a straight line with
negative slope, thus it is NOT a zero order reaction with respect to C4H9Cl. However,
the half-lives obtained from the curve are constant. Thus, the reaction is a first order
reaction with respect to C4H9Cl.
 In Figure S53.5, the plot of ln[C4H9Cl] against time gives a straight line with negative
slope. This also shows that it is a first order reaction with respect to C4H9Cl.
1
 In Figure S53.6, the plot of against time does not give a straight line. This
[C 4 H 9 Cl]
shows that it is NOT a second order reaction respect to C4H9Cl.
(c) Method 1
From Figure S53.4, the half-life is 345 s.
ln 2 0.693
For a first order reaction, t 1 = = .
2
k1 k1
0.693
k1 =
t1
2
0.693
k1 =
345
= 0.002 s−1
Method 2
From Figure S53.5, a straight line is obtained form the plot of ln[C4H9Cl] against time, this
shows that the reaction is first order with respect to C4H9Cl.
− 2.30 − (−2.40)
For a first order reaction, slope = = − k1.
0 − 50
− 0.002 = − k1
k1 = 0.002 s−1

Supplement to Method of excess reactants

Coursebook p.32 Rate equation can only be determined by doing experiments. Apart from
method of initial rate, there is another method for the same purpose
which is called method of excess reactants.
For reactions involving more than one reactant, the concentrations of

all reactants except one are kept in large excess. This is to make sure that
any changes in concentrations of the excess reactants do not have much
effect on the overall reaction rate. In other words, their concentrations are
taken to be constant because they do not vary much during the course of
the reaction. For example, the rate equation of a certain reaction is as
follows:
Rate = k[A]a[B]b[C]c
Experiments should be done by keeping the initial concentration of A

and B in large excess, [A] and [B] do not vary much and are taken to be
constant. Then, the rate equation can be modified as
Rate = k’ [C]c
In this case, the rate depends on the concentration of C only. Then, an

experiment can be done by measuring the initial rates of the reaction using
different initial concentrations of C. After analysing the experimental
results, the order of reaction with respect to C can be figured out. The
experiment can be repeated using the same principle to find the order of
reaction with respect to other reactants.
Supplement to Iodine clock reaction

Coursebook p.33 We can use the iodine clock experiment to determine the order of reaction
with respect to H2O2 in the following reaction:
H2O2(aq) + 2I−(aq) + 2H+(aq) → 2H2O(l) + I2(aq)
The initial rate method can be demonstrated conveniently by using

the iodine clock reaction. The method involves mixing two clear
solutions with no visible change at first. But after a short time delay, the
mixture suddenly gives a blue-black colour change. The colour change is
due to the formation of the blue-black iodine-starch complex.

A series of experiments is done using different initial concentrations

of the reactant under investigation. For each experiment, the time taken for
a definite, small amount of a product (iodine-starch complex) to form at
the start of the reaction is measured. This rate is most rapid and can be
considered as the initial rate of the reaction. The shorter the time for the
1
colour change, the higher the initial reaction rate, i.e. rate  .
time
The following worked example illustrates the use of iodine clock

experiment to determine the order of reaction with respect to H2O2.
Example S53.2
Determining the order of reaction with respect to H2O2 by using iodine clock experiment
A student mixed two solutions A and B together to start the reaction between H2O2(aq) and I−(aq)
and noted the time when the mixture changed from colourless to blue-black colour.
Solution A: 10.0 cm3 0.5 M H2SO4(aq), 10.0 cm3 0.1 M KI(aq), 1.0 cm3 0.01 M Na2S2O3(aq)
and 3 drops of freshly prepared starch indicator
Four test tubes of solution B were prepared using different volumes of 0.2 M H2O2 and distilled
water. The results of the experiment were listed in the table below:
Solution B
Time for the occurrence of the
Experiment Volume of 0.2 M Volume of distilled blue-black coloration when
H2O2(aq) added water added solutions A and B are mixed (s)
(cm3) (cm3)
1 1.0 24.0 75
2 2.0 23.0 45
3 3.0 22.0 30
4 4.0 21.0 20
(a) Explain the use of a small but fixed amount of Na2S2O3 in each reaction mixture.
(b) What is the function of adding starch indicator to the reaction mixture?
(c) Why is it necessary to add distilled water to solution B? Hence, state how is the initial
concentration of H2O2(aq) related to its volume used to make solution B.
(d) State and explain how the time measured is related to the initial rate of the chemical reaction.
(e) Determine graphically the order of reaction with respect to H2O2, the rate constant and the
overall rate equation.

Solution
(a) Sodium thiosulphate reacts immediately with a fixed amount of I2 formed at the beginning of
each experiment according to the following reaction:
2S2O32−(aq) + I2(aq) → 2I−(aq) + S4O62−(aq)
(b) When all the thiosulphate ions have consumed, the ‘excess’ iodine produced reacts with
starch forming a blue-black colour and the time for this sudden colour change is noted.
(c) Distilled water is added to prepare different initial concentrations of H2O2 for the
experiments. The initial concentration of H2O2(aq) is directly proportional to the volume of
H2O2(aq) used.
(d) Rate of reaction is inversely proportional to the time needed to reach the point of colour
change. When the colour changes sharply to blue-black, the extent of the reaction is still
small because only a small amount of Na2S2O3 is used and thus the amount of iodine
produced is also small. So this can be taken as a measure of the initial rate of the reaction.
(e) Let the rate equation of the reaction be: rate = k[H2O2]n
Taking logarithm, log (rate) = n log[H2O2] + log k.
1
Since rate  and [H2O2]  volume of H2O2 used.
t
1
A graph of log ( ) against log (volume) gives a straight line of slope n and y-intercept log k.
t
log (volume) 0 0.30 0.48 0.60
1
log −1.876 −1.654 −1.478 −1.301
t
log (volume)
1
log ( )
t
1
Figure S53.7 A plot of against log (volume).
t
From the graph, the slope of the line is 1, i.e. n = l.

It can be concluded that the reaction is first order with respect to H2O2.
The y-intercept is –1.90, i.e. log k = –1.90.
k = 0.0126 s−1
Rate equation: rate = 0.0126[H2O2(aq)]

Chapter 54 Activation energy

Supplement to
Determining the distribution of molecular speeds
Coursebook p.51
All the molecules in a sample of gas do not have the same speed. At any
particular moment, some will be almost stationary whilst others will be
moving at high speed. They will also be moving in very different
directions as a result of their random motion. During the early 1930s,
Zartmann developed a well-known experiment for determining the
distribution of molecular speeds. The apparatus is shown in Figure S54.1
below.
tin vapour
collimator
molten tin thin slit
to vacuum
disc A
disc A disc B
Figure S54.1 The apparatus used in Zartmann experiment.
Disc A and B are on a common axle and rotate rapidly at the same
speed inside an evacuated container. In front of disc A is an oven
containing molten tin at a controlled temperature. Tin vapour streams from
a small hole in the oven and strikes disc A. Tin atoms pass through disc A
in small bursts each time. The slit in disc A is in line with the opening in
the oven and the collimator (a device that narrows a beam of particles). So,
disc A acts as a starting point for repeated ‘molecular races’ between disc
A and B. No more molecules can get past disc A until the disc has
completed a full rotation and the slit is opposite the opening in the oven
again. Those molecules passing disc A travel towards the second rotating
disc B, and spread throughout its pie slices.
Disc A lets through burst after burst of tin atoms and a layer of tin
will deposit on disc B. The faster molecules hit the plate before the slower
ones, since they all started from the slit simultaneously. Figure S54.2
shows how the deposited tin spreads over the pie slices if the rotating
speed of disc A and B is carefully controlled.

Figure S54.2 The distribution of tin over the pie slices of disc B in the Zartmann
experiment.
The distribution of tin on disc B depends on the distribution of the

speeds of the tin atoms. In order to find the distribution of tin on disc B, it
is cut up into pie slices and weighed to determine the amount of solid
deposited on each slice. Figure S54.3 shows a distribution curve for the
mass of tin deposited on each pie slice.
 number of tin atoms
Mass of tin
Pie slice number

(speed of tin atoms increasing)
Figure S54.3 A distribution curve for the mass of tin deposited on the different pie slices
in the Zartmann experiment.

More about elementary reactions

An elementary reaction is a single step reaction with a single transition
state and no intermediates.
Elementary reactions add up to complex reactions; non-elementary
reactions can be described by multiple elementary reaction steps. A set of
elementary reactions comprises a reaction mechanism, which predicts the
elementary steps involved in a complex reaction. Below are two reaction
coordinates of two reactions. One describes an elementary reaction, and
the other describes a non-elementary reaction.
Types of elementary reactions

The molecularity of a reaction refers to the number of reactant particles
involved in the reaction. Because there can only be discrete
numbers of particles, the molecularity must take an integer value.
Molecularity can be described as unimolecular, bimolecular, or
termolecular. There are no known elementary reactions involving four or
more molecules.

Unimolecular reaction
A unimolecular reaction occurs when a molecule rearranges itself to
produce one or more products. An example of this is radioactive decay, in
which particles are emitted from an atom. Other examples include cis-trans
isomerization, thermal decomposition, ring opening, and racemization. The
rate at which a substance decomposes is dependent on its concentration.
Unimolecular reactions are often first-order reactions as explained by
Frederick Alexander Lindemann, which is referred to as the Lindemann
mechanism.
Bimolecular reaction
A bimolecular reaction involves the collision of two particles.
Bimolecular reactions are common in organic reactions such as
nucleophilic substitution. The rate of reaction depends on the product of
the concentrations of both species involved, which makes
bimolecular reactions second-order reactions.
Termolecular reaction
A termolecular reaction requires the collision of three particles at the
same place and time. This type of reaction is very uncommon
because all three reactants must simultaneously collide with each other,
with sufficient energy and correct orientation, to produce a
reaction. There are three ways termolecular reactions can react, and all are
third order.

Chapter 55 Catalysis and industrial processes

Supplement to
Positions of the active sites
Coursebook p.64
In the case of heterogeneous catalysis, catalysts are specific because the
reaction mechanism depends on the positions of the active sites which are
determined by the crystal structure of the catalyst, i.e. its chemical nature.
Here are some examples of catalytic reactions involving ethanol:
1. Dehydrogenation of ethanol (CH3CH2OH) to ethanal (CH3CHO)

using finely divided nickel.
2. Dehydration of ethanol to ethene (CH2=CH2) using alumina (i.e.

aluminium oxide) at higher temperature (above 300oC).
3. Formation of ethoxyethane (CH3CH2OCH2CH3) from ethanol

using alumina at lower temperature (below 300oC).

More about homogeneous and heterogeneous catalyst

Heterogeneous catalysis
In heterogeneous catalysis, the catalyst is in a different phase from the
reactants. At least one of the reactants interacts with the solid surface in a
physical process called adsorption in such a way that a chemical bond in
the reactant becomes weak and then breaks. Poisons are substances that
bind irreversibly to catalysts, preventing reactants from adsorbing and thus
reducing or destroying the catalyst’s efficiency.

Homogeneous catalysis

Chapter 56 Industrial processes
Supplement to Problems associated with nitrogenous fertilizers

Coursebook p.95 There are several types of fertilizers. The most important one is
nitrogenous fertilizers. Fertilizers are the most effective means of
increasing crop production and of improving the quality of food and
fodder. However, problems also arise from the use of fertilizers.
1. Eutrophication
Nitrates are very soluble. Rain washes or leaches them out of the soil and
into rivers. In the rivers, the nitrates promote the growth of algae, the tiny
water plants. When they die, bacteria feed on the remains. In the process,
they use up the oxygen dissolved in the water. Fish and other river life die
from oxygen starvation, and the river becomes choked and lifeless. This is
called eutrophication. Some algae are poisonous to fish and humans.
People swimming through these algae or swallowing the water may get
rashes, eye irritation, muscle pains, vomiting, and diarrhea.
2. Blue-baby syndrome
Excess nitrate in the river may get into drinking water. It increases the risk
of blue-baby syndrome. Some bacteria in a feeding bottle or a baby’s body
convert the nitrate to nitrite. This gets taken up instead of oxygen, by the
haemoglobin in blood. The baby turns blue and can die.
3. Increased pest fitness

Excessive nitrogenous fertilizer applications can lead to pest problems by
increasing the birth rate, longevity and overall fitness of certain pests.
4. Soil acidification
Many nitrogenous fertilizers acidify soil over long term because they
produce the ammonium ion which is a proton donor. This may lead to
decreases in nutrient availability.
5. Emission of greenhouse gases

During storage and application of some nitrogenous fertilizers, some
weather or soil conditions can cause release of the greenhouse gases, e.g.
dinitrogen oxide (N2O).

Supplement to
Reactions in fuel cells using different fuels
Coursebook p.108
A fuel cell can be designed for use at room temperature and pressure.
Basically, the reaction in the fuel cell can be regarded as the overall
reaction shown below:
Hydrogen + oxygen → water + energy
The fuel that provides hydrogen is oxidized at the anode, i.e.
electrons are removed. These electrons pass through the external circuit to
the cathode, where the oxygen reacts, using these electrons. The fuel
electrode (anode) is the source of electrons, thus it is the negatively
charged electrode. The air or oxygen electrode (cathode) is the positively
charged electrode.
1. Reaction at the cathode

Electrons from the external circuit flow to the cathode, reacting with
oxygen from the air and water in the electrolyte, as shown in the equation
below:
4e− + O2 + 2H2O → 4OH−
The OH− ions formed will move to the anode where they are
consumed and the alkaline concentration of the electrolyte will be
maintained.
2. Reaction at the anode

(a) Using hydrogen as fuel
This is the simplest anode reaction:
H2 + 2OH− → 2H2O + 2e−
Electrons released will flow to the cathode through the external circuit.
(b) Using ethanol as fuel

The cell works quite well, but it is not a viable fuel compared with
methanol and NaBH4 because the reaction as shown in the equation below,
releases only two electrons per molecule of fuel.
C2H5OH + 2OH− → CH3CHO + 2H2O + 2e−

(c) Using methanol as fuel

The methanol fuel reaction is a multi-stage reaction, with each reaction
releasing some electrons.
Firstly, methanol reacts to form methanal.

CH3OH + 2OH− → HCHO + 2H2O + 2e−
The next stage is the reaction of the methanal to methanoic acid.
HCHO + 2OH− → HCOOH + H2O + 2e−
The methanoic acid is finally oxidized to carbon dioxide, releasing a
further two electrons.
HCOOH + 2OH− → CO2 + 2H2O + 2e−
The half equation for the overall reaction at the anode is as follows:
CH3OH + 6OH− → 5H2O + CO2 + 6e−
Methanol gives six electrons for each molecule of fuel, which is

excellent, though not quite as good as NaBH4 that we see later. However,
carbon dioxide formed reacts with the alkaline electrolyte as shown in the
equation below:
CO2 + 2KOH → K2CO3 + H2O
The potassium carbonate formed slowly reduces the concentration of the
electrolyte and refill of it is needed to maintain the concentration of the
electrolyte.
(d) Using sodium tetrahydridoborate (NaBH4) as fuel

When NaBH4 is used as fuel, there are two possible ways of using it.
First, it is directly oxidized as shown in the equation below:

NaBH4 + 8OH− → NaBO2 + 6H2O + 8e−
This reaction is promoted by the platinum catalyst on the electrode.
Second, it reacts with water in the presence of catalyst to produce

hydrogen which further reacts at the electrode as shown in the equations
below:
NaBH4 + 2H2O → NaBO2 + 4H2
4H2 + 8OH− → 8H2O + 8e−
In both ways, eight electrons are produced per unit of NaBH4. This is
why it is such a good fuel.

Chapter 57 Green chemistry for industrial

processes
Supplement to
Maximizing atom economy
Coursebook p.133
1. The synthesis of Ibuprofen
Ibuprofen (iso-butyl-propanoic-phenolic acid) is a non-steroidal
anti-inflammatory drug. It is used for relief of symptoms of arthritis, fever,
and as an analgesic, especially when inflammation is involved. Each year,
28 to 35 million pounds of ibuprofen are produced but 37 to 46 million
pounds of waste are also produced.
Ibuprofen was developed as a new analgesic by Boots in the

mid-1960s using the rather inefficient route (6 steps) shown in Scheme A
(Figure S57.1). Although the synthesis demonstrates the ‘art’ of classic
laboratory organic chemistry, its drawback is the use of reagents rather
than catalysts to carry out transformations, leading to the formation of
large amounts of waste.
ibuprofen
Figure S57.1 The synthetic route of ibuprofen in scheme A.
In the 1980s, ibuprofen was approved for over-the-counter use and

the Boots Company patent expired. The great market of ibuprofen leads to
the development of new ways to make the drug. The BHC Company used
the new 3-step synthesis of ibuprofen to manufacture the drug as shown in
Scheme B (Figure S57.2).

ibuprofen
Figure S57.2 The synthetic route of ibuprofen in scheme B.
The atom economies of scheme A and scheme B are calculated

according to the information in Table S57.1 and Table S57.2.
Reagent Used in ibuprofen Unused in ibuprofen
Formula Mr Formula Mr Formula Mr
C10H14 134 C10H13 133 H 1
C4H6O3 102 C2H3 27 C2H3O3 75
C4H7ClO2 122.5 CH 13 C3H6ClO2 109.5
C2H5ONa 68 0 C2H5ONa 68
H3O 19 0 H3O 19
NH3O 33 0 NH3O 33
H4O2 36 HO2 33 H3 3
Total Ibuprofen Waste products
C20H42NO10ClNa 514.5 C13H18O2 206 C7H24NO8ClNa 308.5
Table S57.1 Atom economy in the Boots’ synthesis of ibuprofen.
mass of atoms in the desired product 206

Atom economy =  100% = 100% = 40%
mass of atoms in reactants 514.5
Reagent Used in ibuprofen Unused in ibuprofen

Formula Mr Formula Mr Formula Mr
C10H14 134 C10H13 133 H 1
C4H6O3 102 C2H3O 43 C2H3O2 59
H2 2 H2 2 0
CO 28 CO 28 0
Total Ibuprofen Waste products
C15H22O4 266 C13H18O2 206 C2H4O2 60
Table S57.2 Atom economy in the BHC’s synthesis of ibuprofen.

mass of atoms in the desired product 206

Atom economy =  100% = 100% = 77%
mass of atoms in reactants 266
Advantages of the BHC’s synthesis over the Boots’ synthesis:

 Great improvement of atom economy.
 Catalytic versus stoichiometric reagents.
 Recycling, reuse, recovery of by-products and reagents.
 Fewer auxiliary substances (e.g. solvents) are required because there
is a change from a 6-step process to a 3-step process.
 Greater throughput since more ibuprofen is produced in less time and
with less equipment.
 A great decrease in the waste produced so that the company will use
less money to deal with the waste generated.
2. Atom economy in elimination reactions

The base-catalyzed dehydrohalogenation of alkyl halides to make alkenes
is an elimination reaction.
Mass of atoms Mass of atoms Mass of atoms

= 137 g = 68 g = 56 g
In the above equation, 2-bromo-2-methylpropane reacts with sodium

ethoxide to give methylpropene. The atom economy is calculated as
follows:
mass of atoms in the desired product
Atom economy =  100%
mass of atoms in reactants
56 56
= 100% = 100% = 27%
137 + 68 205
The poor atom economy is not only due to the loss of the HBr. It is
because this is a base-catalyzed reaction and a base (sodium ethoxide) is
used. All of the atoms of the sodium ethoxide are found in unwanted side
products.

3. Atom economy in addition reactions

In addition reactions, all the atoms of the reactants are supposed to have
incorporated into the final desired products. Thus, this type of reaction has
a high atom economy and is environmentally more preferable to
elimination and substitution reactions.
Mass of atoms Mass of atoms Mass of atoms

= 56 g = 81 g = 137 g
In the above equation, the addition of hydrogen bromide to

methylpropene has an atom economy of 100%. The atom economy is
calculated as follows:
mass of atoms in the desired product
Atom economy =  100%
mass of atoms in reactants
137 137
= 100% = 100% = 100%
56 + 81 137
Supplement to Producing safer chemical products

Coursebook p.137 1. New insecticide
Rohm and Haas Company developed Confirm™ insecticide which
effectively and selectively control caterpillar pests in agriculture. The
insecticide has no significant risk to the applicator, the consumer, or the
ecosystem and controls caterpillars through an entirely new and safer way
than other insecticides.
Figure S57.3 The molting process of a caterpillar.

The insecticide disrupts the molting process in caterpillar pests (Figure

S57.3), causing them to stop feeding within hours of exposure and to die
soon after. This compound has no effect in most other insects and other
creatures living in the same habitat. Moreover, the insecticide does not
accumulate long in the environment.
2. Sea-Nine™ 211N marine antifouling agent

Sea-Nine™ 211N marine antifouling agent is a rapidly biodegradable
settlement inhibitor, developed by Rohm and Haas for the new generation
of environmentally acceptable marine antifouling paints for ships and
marine structures.
Fouling of ships by marine organisms is a phenomenon, which if not

prevented proves costly to the ship operators. It will increase fuel
consumption necessary to overcome the drag. Excessive use of fuel will
lead to acid rain and global warming, thus causing damage to the
environment.
Sea-Nine™ 211N works by interfering with the microorganism

settlement process, thus preventing the colonization of the painted surface.
The use of Sea-Nine™ 211N containing paints prevents the fouling of
treated surfaces and eliminates the associated costs of increased fuel usage
and more frequent repainting. Sea-NineTM 211N is highly effective against
bacterial slime, algae, barnacles, tubeworms, etc. It can work excellently
in long term and remains stable on all major types of marine coatings.
Sea-NineTM 211N has claimed the first ever Green Chemistry

Challenge Award in the category for Designing Safer Chemical Products
presented by the United States Environmental Protection Agency. It is
regarded as environmentally friendly because of several reasons. Some of
them are listed below:
 It is free from heavy metals.
 It degrades rapidly in the environment.
 It does not affect the non-target marine organisms when used at
appropriate concentrations.
 It does not lead to significant accumulation of toxic compounds in the
marine systems.

Supplement to Designing for energy efficiency

Coursebook p.139 1. Microwave induced reactions
The heating effect of microwave radiation uses the ability of some liquids
and solids to transform electromagnetic energy into heat and thereby
induce chemical reactions. This in situ mode of energy conversion has
many attractions to the chemists, because its magnitude depends on the
properties of the molecules. This may lead to reaction selectivity.
The energy of microwave radiation is insufficient for molecular

excitation of solvent, thus most of the energy is used in heating up the
reactants. The mechanism of microwave heating is different from that of
conventional heating, where heat is transferred by conduction, convection
or radiation. In microwave heating, electromagnetic energy is transformed
into heat through ionic conduction and the friction due to rapid
reorientation of the dipoles under microwave radiation. The larger the
dipole moment of a solvent molecule, the more vigorous is the oscillation
in the microwave field, consequently more heating. This type of heating is
fast and is in situ without heating the surroundings.
The use of microwave induced reactions can reduce the need for
solvents, thus it is environmental friendly. The other advantages of using
microwave radiation are higher reaction rate under controlled temperature
and pressure (especially in a closed system), higher purity products and
better yields.
2. Dry media reaction

Dry media reaction is also called solid-state reaction or solventless
reaction. It is a chemical reaction system in the absence of a solvent, when
one of the reactants is itself a solvent in the reaction.
The advantages of dry media reactions are:

 economical (save money on solvents)
 ease of purification (no solvent removal afterwards)
 high reaction rate (due to high concentration of reactants)
 environmentally friendly (solvent is not required)

The drawbacks to overcome are:

 reactants should mix in a homogeneous system
 high viscosity in reactant system
 unsuitable for solvent assisted chemical reactions

CHEMISTRY

COURSEBOOK 7
Contents
PART XV ANALYTICAL CHEMISTRY

Chapter 63 Detecting the presence of chemical species
⚫ Action of heating solid sample strongly 1
Chapter 64 Separation and purification methods

⚫ Centrifugation 2
⚫ Sublimation 2
⚫ Partition equilibrium of a solute between two immiscible solvents 3
⚫ Two-dimensional thin-layer chromatography 6
Chapter 65 Quantitative methods of analysis

⚫ Detection of end point in acid-alkali titration 8
⚫ Gravimetric Analysis 11
Chapter 66 Instrumental analytical methods

⚫ More about infrared spectroscopy 13
⚫ More about mass spectrometry 16
Chapter 67 Contribution of analytical chemistry to our society

⚫ Gas chromatography-mass spectrometry
Appendix
⚫ Sample Infrared Spectra
⚫ Characteristic Infrared Absorption Wavenumber Ranges
⚫ Standard Reduction Potentials at 298K
⚫ Common Fragment Ions

HKDSE CHEMISTRY ⎯ A Modern View (Chemistry) Supplementary Information
PART XV ANALYTICAL CHEMISTRY
Chapter 63 Detecting the presence of chemical

species
Supplement to
Coursebook p.5
Action of heating solid sample strongly
Heating the solid sample strongly is one of the preliminary tests of
substances. This can be done by heating the sample over a non-luminous
Bunsen flame in the laboratory. In case there is any gas evolved, further
tests can be done to identify the gas. See Table S63.1.
Observation Inference
Yellow sublimate Sulphur
Violet vapour and dark Iodine
grey shiny sublimate
Dark red sublimate Iron(III) chloride, FeCl3
White sublimate Ammonium halides e.g. AlCl3
Water vapour evolved Hydrated salts; hydrogencarbonates;
some hydroxides
Colour change Some hydrated salts
Rust red residue Fe2O3 formed (from decomposition of
iron compounds)
Black residue from blue CuO formed (from decomposition of
or green sample copper(II) compounds)
Yellow residue when ZnO formed (from decomposition of
hot, white when cold zinc compounds)
Orange residue when PbO formed (from decomposition of
hot, yellow when cold lead(II) compounds)
Ammonia evolved Some ammonium salts
Carbon dioxide evolved Some carbonates; hydrogencarbonates
Nitrogen dioxide Nitrates and nitrites (except those of
evolved potassium, sodium and ammonium)
Oxygen evolved Nitrates (except NH4NO3); some
oxides of metals (e.g. PbO2, HgO,
Ag2O); chlorates (e.g. KClO3)
Sulphur dioxide evolved Sulphites (except those of sodium and
potassium); some sulphates
Table S63.1 Observation and inference from the action of heating solid sample strongly.

Chapter 64 Separation and purification methods
Supplement to
Centrifugation
Coursebook p.57
Centrifugation can be used instead of filtration to separate a solid from a
liquid. It is particularly useful when there is only a small amount of
material, or when very fast separation is required.
Firstly, the mixture containing an undissolved solid and a liquid is put

into a centrifuge tube. Then the centrifuge tube, together with other tubes,
are put into the tube holders in a centrifuge (Figure S64.1). The holders
and tubes are spun around very rapidly, and are thrown outwards. The
undissolved solid and the liquid in the mixture are spun at the same time
(Figure S64.2). Finally, the denser solid is collected as a lump at the
bottom of the tube. Then the liquid can be removed by decantation.
Figure S64.1 A centrifuge.
undissolved solids
clear liquid
undissolved
solid/liquid clear liquid
mixture
undissolved solids
holders and tubes are spun
around very rapidly
Figure S64.2 Centrifugation.
Supplement to
Sublimation
Coursebook p.57
A few substances change directly from solid to vapour on heating, without
going through the liquid state. This physical change is called sublimation.
On cooling, the vapour changes back to solid directly.
Consider the following example. If a mixture of iodine and sand is

heated in a beaker, the iodine changes from solid to vapour directly (Figure
S64.3). The vapour changes back to solid directly on a cool surface. The
sand is not affected by the heat and remains in the beaker.

cold water
evaporating basin
grey-black shiny sublimate of iodine
violet iodine vapour
mixture of iodine and sand
wire gauze
tripod
heat gently
Figure S64.3 Sublimation of iodine.
Other substances which sublime include solid carbon dioxide (‘dry

ice’) (Figure S64.4), anhydrous iron(III) chloride, anhydrous aluminium
Figure S64.4 Dry ice undergoes
chloride and some ammonium salts. Since only a few solids sublime, this
sublimation.
method of separation is limited in use.
Supplement to Partition equilibrium of a solute between two immiscible

Coursebook p.66 solvents
Water and heptane are immiscible solvents. When iodine is extracted from
an aqueous solution using heptane, the heptane layer will become pink in
colour and the aqueous layer will become brown in colour. After shaking
the mixture for several times, the colours of the layers will remain
unchanged. We say that an equilibrium system has been established
(Figure S64.5).
heptane layer
iodine molecule
aqueous layer
Figure S64.5 Partition of iodine between water and heptane.

At the interface of the aqueous layer and the heptane layer, some
solute (iodine) particles move ‘up’ and some move ‘down’. The solute
particles are moving at the same rate. A dynamic equilibrium is established.
If the concentrations of solute in both layers are found, we may find that
there is a constant ratio between them no matter how much solute or
solvent is used in each layer. The ratio is a constant at a particular
temperature as stated by the partition law.
Partition law states that when a non-volatile solute is distributed between

two immiscible solvents, the ratio of concentrations of the solute in the two
solvents, at equilibrium, is a constant at a constant temperature. The
constant is known as partition coefficient.
The partition coefficient (KD) can be represented by the following

equation:
Concentration of solute in solvent 1
KD =
Concentration of solute in solvent 2
It should be noted that KD carries no unit. It is a constant dependent on
temperature only and can only apply for dilute solutions. The partition law
only applies to systems where the solute has the same molecular form in
both solvents. For example, the partition law cannot be applied to the
Figure S64.6 Dimer of ethanoic
partition of ethanoic acid between water and benzene. It is because
acid.
ethanoic acid exists as discrete molecules or ions in water but it forms
dimers in benzene. See Figure S64.6.
Another example that partition law cannot apply is the partition of

hydrogen chloride between water and chloroform (CHCl3). It is because
hydrogen chloride ionizes in water to give hydrogen ions and chloride ions
which are different from the molecular form of HCl in chloroform.
Example S64.1
Determining the mass of solute extracted by a solvent
At 298 K, the partition coefficient of an organic compound X between diethyl ether and water is
5.60.
(a) Calculate the mass of X that can be extracted by diethyl ether when 50 cm3 of an aqueous
solution containing 5.00 g of X is shaken with 50 cm3 of diethyl ether.
(b) Calculate the mass of X that can be extracted in each of two further extractions using 50 cm3

of diethyl ether each time.

(c) Calculate the mass of X extracted by three successive extractions with 50 cm3 of diethyl ether.
(d) Calculate the mass of X extracted when 150 cm3 of diethyl ether is used.
(e) Comment on the difference of results from (c) and (d).
Solution
Concentration of compound X in diethyl ether
(a) KD =
Concentration of compound X in water
Let m be the mass of compound X extracted by 50 cm3 of diethyl ether.
m
50
 KD = 5.00 − m
50
m
50
5.60 = 5.00 − m
50
 m = 4.24
Mass of compound X extracted by 50 cm3 of diethyl ether is 4.24 g.
(b) Let m2 be the mass of compound X extracted by 50 cm3 of diethyl ether in the second
extraction, the mass of X left in the aqueous layer is 5.00 g − 4.24 g = 0.76 g.
m2
50
5.60 = 0.76 − m
2
50
 m2 = 0.64
Mass of compound X extracted by 50 cm3 of diethyl ether in the second extraction is 0.64 g.
Let m3 be the mass of compound X extracted by 50 cm3 of diethyl ether in the third extraction.
The mass of X left in the aqueous layer is 0.76 g – 0.64 g = 0.12 g.
m3
50
5.60 = 0.12 − m
3
50
m3 = 0.10
Mass of compound X extracted by 50 cm3 of diethyl ether in the third extraction is 0.10 g.
Alternative method:
4.24
The fraction of X extracted in the first extraction = = 0.848
5.00

Since there is (5.00 – 4.24) g = 0.76 g of X left in water. Mass of X extracted with 50 cm3 of
diethyl ether in the second extraction = 0.76 g  0.848 = 0.64 g
After the second extraction, there is (0.76 – 0.64) g = 0.12 g of X left in water. Mass of X
extracted with 50 cm3 of diethyl ether in the third extraction = 0.12 g  0.848 = 0.10 g
(c) The mass of X extracted by three successive extractions with 50 cm3 of diethyl ether
= 4.24 g + 0.64 g + 0.10 g = 4.98 g
(d) Let n be the mass of compound X extracted by 150 cm3 of diethyl ether.
n
150
5.60 = 5.00 − n
50
 n = 4.72
Mass of compound X extracted by 150 cm3 of diethyl ether is 4.72 g.
(e) Mass of X extracted by three successive extractions with 50 cm3 of diethyl ether is 4.98 g –
4.72 g = 0.26 g more than by one extraction with 150 cm3 of diethyl ether. Thus, using three
successive extractions is more efficient than using just one extraction.
Supplement to Two-dimensional thin-layer chromatography

Coursebook p.69 Two-dimensional thin-layer chromatography uses the thin-layer
chromatographic method twice to separate spots that are unresolved by
only one solvent. After running a sample in one solvent, the thin-layer
chromatography plate is removed, dried, rotated 90, and run in another
solvent. Any of the spots from the first run that contain mixtures can now
be separated. The finished chromatogram is a two-dimensional array of
spots. See Figure S64.7.
First development
Direction of development by solvent 1
Second development
Direction of development by solvent 2
Figure S64.7 Developing a two-dimensional thin-layer chromatogram.

Example S64.2
Separating amino acids by two-dimensional thin-layer chromatography
In an experiment to analyse amino acids, thin-layer chromatography was carried out. A mixture of
three amino acids, X, Y and Z was separated by a two-dimensional thin-layer chromatography. In the
first chromatographic analysis, a mix solvent of ethanoic acid and butan-1-ol was used. While in the
second chromatographic analysis, phenol was used as the solvent. The Rf values of these three
amino acids are as follows:
Amino acid First chromatographic analysis Second chromatographic analysis
(Rf value in ethanoic acid/butan-1-ol) (Rf value in phenol)
X 0.25 0.30
Y 0.40 0.55
Z 0.65 0.60
Draw a labelled diagram to show the positions of X, Y and Z in the chromatogram.
Solution
Ethanoic acid/butan-1-ol
Solvent front
Solvent front
Phenol

Chapter 65 Quantitative methods of analysis
Supplement to
Detection of end point in acid-alkali titrations
Coursebook p.101
To detect the end point of an acid-alkali titration, several methods may be
used. These involve
 use of indicators,
 use of pH meter,
 thermometric titration, etc.
(1) Detecting the end point by use of indicators

Many acids, alkalis and their products are colourless in nature. There is no
obvious change when the reaction is completed. Thus, an indicator is
added to the reaction mixture to tell whether the reaction is completed. An
indicator is a substance, usually a weak acid or weak base, which changes
colour within a specific pH range.
The point at which the acid and the alkali have just reacted
completely during titration is called the equivalence point. During a
titration, the point at which the indicator changes colour is called the end
point. When carrying out a titration, the indicator is chosen so that the end
point appears as close as possible to the equivalence point.
The pH value of a solution is a number indicating the degree of

acidity or alkalinity of the solution. pH is equal to −log[H+], where [H+] is
the concentration of hydrogen ions in mole per dm3 (mol dm−3).
pH values usually range from 0 to 14. During an acid-alkali titration,

there will be a marked change in the pH at the end point. A suitable
indicator will give a noticeable colour change at the end point.
(2) Detecting the end point by using pH meter

A pH meter can be used to follow the course of a titration and thus
indicate the end point. Suppose 0.1 M hydrochloric acid is added slowly to
25.0 cm3 of 0.1 M sodium hydroxide solution, and the pH of the resultant
solution after each addition is found by a pH meter (Figure S65.1).

hydrochloric acid
burette
connected to computer
pH electrode
sodium hydroxide solution

plastic-coated magnet
magnetic stirrer
stand stir heat
Figure S65.1 Detecting the end point of a titration using a pH meter.
When the pH values are plotted against the volume of hydrochloric

acid added, a graph as shown in Figure S65.2 is obtained.
pH
14
12
10
8
6
4 end point
2
0
10 20 30 40
Volume of 0.1 M HCl added (cm3)
Figure S65.2 A graph of pH against volume of hydrochloric acid added.
During an acid-alkali titration, there is often a marked change in pH

at the end point, which can thus be easily located on the graph. The volume
of acid used to neutralize the alkali can then be read from the graph.

(3) Detecting the end point by thermometric titration

When an acid reacts with an alkali, heat is given out. The greatest
temperature rise occurs at the end point.
Consider 50.0 cm3 of 0.1 M sodium hydroxide solution in an

expanded polystyrene cup which is supported in a beaker as shown in
Figure S65.3. The temperature of the sodium hydroxide solution is
measured. 0.1 M hydrochloric acid is then added from a burette, 5.00 cm3
at a time, and the solution is stirred with a thermometer.
hydrochloric acid
thermometer
stirrer
lid
expanded polystyrene cup
beaker
Figure S65.3 Detecting the end point by thermometric titration.
The temperature readings after addition of each 5.00 cm3 portion are
recorded, and a graph of temperature against volume of hydrochloric acid
added is plotted (Figure S65.4).
Temperature (C)
B
A
10 20 30 40 50 60 70 80
Volume of 0.1 M HCl added (cm3)
Figure S65.4 A graph of temperature against volume of hydrochloric acid added.

Interpretation of the graph:

At A This indicates the original temperature of sodium
hydroxide solution.
A to E Temperature rises as more heat is liberated by adding
more acid. (Neutralization is an exothermic reaction
which releases heat.)
At E This is the end point. The temperature rise is
maximum when the reaction is just completed.
E to B Temperature drops as any more acid added will not
react but will absorb heat from the solution and cool it.
Gravimetric Analysis


Chapter 66 Instrumental analytical methods

Supplement to
More about infrared spectroscopy
Coursebook p.160
Electromagnetic spectrum
Electromagnetic radiation is not a ‘stranger’ in daily life. Visible light
comes from a light source in our homes; radio waves come from a radio
station. They are two examples of electromagnetic radiation. Other
examples of electromagnetic radiation are microwaves, infrared, ultraviolet
light, X-rays and gamma-rays.
Different types of radiations can be grouped together to form an

electromagnetic spectrum (Figure S66.1).
Increasing wavelength
Wavelength
Visible
(m)
light
Radio Microwaves Infrared Ultraviolet X rays Gamma rays

waves
Frequency
(Hz)
Increasing energy
Figure S66.1 An electromagnetic spectrum.
The frequency () of an electromagnetic radiation can be expressed in

terms of its wavelength () and velocity (c).
c
 =


The energy of a particular electromagnetic radiation can be expressed

according to the following equation:
E = h
where c is the speed of light (c = 3  108 m s−1) and h is Planck’s constant

(h = 6.626  10−34 J s).
Using a hydrogen atom as an example, when electromagnetic

radiation falls onto a hydrogen atom, radiation of certain frequency will be
absorbed. The electron in the hydrogen atom will be excited from the
ground state to a higher energy level. The atom is said to be in an excited
state. The electron in the higher energy level is unstable. It quickly returns
to its lower energy level, the ground state. The energy is released in the
form of light (electromagnetic radiation) which is equal to the energy
difference between the higher and lower energy levels (Figure S66.2). The
energy is quantized and can be represented as:
E = h = Eexcited state – Eground state
electron in excited state returns to its ground state
light of higher energy emitted
light of lower energy emitted
n=1
n=2 emission spectrum produced
n=3
increasing wavelength
decreasing energy
Figure S66.2 Light is emitted when an electron moves from a higher energy level to a
lower energy level.
Similarly, when electromagnetic radiation falls onto a molecule,

radiation of certain frequency will be absorbed. Electrons in the molecules
are excited to higher energy levels and quantized energies are absorbed in
a similar way as in hydrogen atom.

In addition to the excitation of electrons, the absorption of energy can

increase the extent of vibration of the bonds and the speed of rotation of
the molecule. The energy involved in the changes in vibration and rotation
is smaller than that resulting from the excitation of electrons. The
excitation of electrons fall into the energy range of ultraviolet light or
visible light region, while the vibrational change and rotational change of
molecules only require energy in the infrared region and microwaves
region respectively.
Vibration of molecules
The atoms in a molecule are not static. Instead, they vibrate about their
equilibrium positions. The covalent bonds in molecules act like springs in
continuous, high-frequency vibration (Figure S66.3).
When a molecule absorbs infrared radiation, the vibration of atoms

will increase in amplitude. The molecule is said to be in an excited
Figure S66.3 The covalent bond vibrational state (Figure S66.4). The molecule will return to its ground
in a molecule acts like a spring in state by the dissipation of heat.
continuous, high-frequency
more vigorous vibration
vibration.
infrared radiation
higher energy level
energy absorbed
lower energy level
Figure S66.4 The change in vibrational state of a molecule after the absorption of infrared
radiation.

Supplement to
More about mass spectrometry
Coursebook p.168
magnetic field
electric field
ionization chamber
connected to
vaporization chamber
ion detector
Figure S66.5 The structure of a mass spectrometer.
Formation of molecular ions

To obtain a mass spectrum, a sample is introduced into a mass
spectrometer. The sample is then vaporized to the gaseous state in the
vaporization chamber. The molecules of the gaseous sample are then
bombarded with a beam of fast-moving electrons. Some of the collisions
are energetically enough to knock one or more electrons out of the
molecule to give a positively-charged molecular ion.
molecule molecular ion
The chambers in the mass spectrometer should be kept under vacuum

so that the molecular ions produced can pass through the chambers without
hitting any air molecules.
The molecular ion is basically a radical cation with an unpaired

electron. It is not only a cation, but also a radical.
A radical cation is a free radical species that carries a positive charge.
Although it is possible that the bombardment of electrons with the

molecules can give molecular ions with +2 charges, most of the molecular
ions carry a +1 charge. This is because it is much more difficult to remove
further electrons from a positive ion. The mass-to-charge ratio (m/e) is
different if the ions carry a +2 charge. For example, if a molecular ion has
a mass of 30 and a charge of +1, the m/e would be 30. If the molecular ion
has a charge of +2, the m/e would be 15.

The molecular ions formed in the ionization chamber may undergo a

series of fragmentation reactions. The fragments generated may be
Learning tip
carbocations, radical cations, radicals or neutral molecules. Only the
Carbocation is also called
radical cations and carbocations can be deflected by the magnetic field and
carbonium ion.
detected by the detector in the mass spectrometer.
Carbocations/radical cations are then accelerated by the electric field

towards a magnetic field. Ions with different m/e are deflected to different
extents by the magnetic field. The extent of deflection depends on:
1. mass of ions: the lighter the ions, the greater is the deflection.
2. charge of ions: the higher the charge of the ions, the greater is the
deflection.
Thus, ions with a greater m/e will be deflected to a lesser extent than
Learning tip
an ion with a smaller m/e. Since only positively charged ions are deflected,
The M+1 peak
the mass spectrometer can detect the presence of radical cations and
In Figure S66.6, you may
carbocations only.
find a small peak at m/e
equal to 17. This small
Fragmentation of molecular ions
peak is called the M+1
Molecular ions undergo a series of fragmentation reactions in the mass
peak. The M+1 peak is
spectrometer to generate different positively charged fragment ions. These
caused by the presence of
fragment ions are then separated in the mass spectrometer according to
the 13C isotope in the
their m/e.
molecule. The M+1 peak at
m/e = 17 is actually due to
Figure S66.6 shows the mass spectrum of methane. The peak at m/e =
the molecular ion [13CH4]+.
16 corresponds to the molecular ion ( ). The peaks at m/e = 15, 14, 13
The intensity of the peak at
and 12 correspond to the fragment ions produced.
m/e = 17 is much smaller 100 16
Relative abundance (%)
than that of the peak at m/e

80 15
= 16 because of the low
abundance of the 13C
60
isotope in nature (13C

40
makes up about 1.11% of
all carbon atoms).
20 14
13
12 17
0
0 5 10 15 20
m/e
Figure S66.6 The mass spectrum of methane.

We can easily identify the fragmentation patterns from the mass

spectrum. The methane radical cation loses a hydrogen radical to generate
the methyl cation as shown below:
methane radical cation methyl cation hydrogen radical
m/e = 16 m/e = 15
A signal at m/e = 15 which represents the CH3+ carbocation can be

observed clearly in the mass spectrum. Further fragmentation reactions
give fragment ions with lower m/e.
m/e = 14
m/e = 13
m/e = 12
The interpretation of the mass spectrum of methane is summarized in

Table S66.1.
Fragment carbocation/radical cation m/e
16
15
14
13
12
Table S66.1 Interpretation of the mass spectrum of methane.
Fragmentation patterns
1. Straight-chain alkanes
The mass spectrum of pentane is shown in Figure S66.7. It shows the
typical characteristics of straight-chain alkanes.

100

43
80
60
40
29
20
72
0
0 10 20 30 40 50 60 70 80
m/e
Figure S66.7 The mass spectrum of pentane.
The base peak at m/e = 43 corresponds to the propyl cation resulting

from the fragmentation that also gives an ethyl radical. It should be noted
that the neutral ethyl radical is not detected because it does not have any
charge.
pentane radical cation propyl cation ethyl radical
m/e = 72 m/e = 43
Similar fragmentation gives an ethyl cation and a propyl radical. The

peak at m/e = 29 corresponds to the ethyl cation.
pentane radical cation ethyl cation propyl radical
m/e = 72 m/e = 29
Example S66.1
Interpreting the mass spectrum of a straight-chain alkane
The mass spectrum of a straight-chain alkane is shown below:

100 57
80 43
60 29
40
20
86
15
0
0 10 20 30 40 50 60 70 80 90 100
m/e
(a) Deduce, from the mass spectrum, the relative molecular mass of the alkane.
(b) What is meant by the term ‘base peak’?
(c) Locate the base peak from the mass spectrum.
(d) Name and draw the structure of the alkane.
(e) Show the fragmentation patterns that account for the peaks at m/e = 57, 43, 29 and 15.
Solution
(a) The relative molecular mass of the alkane is 86.0.
(b) The base peak is a peak at the mass spectrum that corresponds to the ion with the highest
abundance. It is assigned an abundance of 100.
(c) The base peak is at m/e = 57.
(d) Let the molecular formula of the hydrocarbon be CnH2n+2.
12.0  n + 1.0  (2n + 2) = 86.0
n=6
The alkane is hexane.
Structure:

(e)
m/e = 57
m/e = 43
m/e = 29
m/e = 15
2. Branched-chain alkanes
Figure S66.8 shows the mass spectrum of 2-methylbutane. The base peak
at m/e = 43 corresponds to the fragmentation that gives a 2-propyl cation.
An ethyl radical is also produced during fragmentation.
2-methylbutane radical cation 2-propyl cation ethyl radical
m/e = 72 m/e = 43
100 43
80
60
57
40
20
72
0
0 10 20 30 40 50 60 70 80
m/e
Figure S66.8 The mass spectrum of 2-methylbutane.

Another strong peak at m/e = 57 corresponds to the formation of a

2-butyl cation.
2-methylbutane radical cation 2-butyl cation methyl radical

m/e = 72 m/e = 57
Apart from the above fragmentations, the following fragmentation

that produces an ethyl cation and a 2-propyl radical may also happen. The
peak at m/e = 29 of the mass spectrum corresponds to the ethyl cation.
2-methylbutane radical cation ethyl cation 2-propyl radical

m/e = 72 m/e = 29
3. Haloalkanes
If the molecule contains halogen like chlorine and bromine, more than one
peak in the mass spectrum corresponds to the molecular ion. The relative
abundance of different isotopes of halogens is shown in the following
table.
Halogen Relative abundance of isotopes
35
Chlorine Cl (75.53%), 37Cl (24.47%)
79
Bromine Br (50.54%), 81Br (49.46%)
Iodine Only one stable isotope of 127I
Table S66.2 The relative abundance of different isotopes of halogens.
Figure S66.9 shows the mass spectrum of chloromethane, CH3Cl.

Chlorine consists of 75.53% 35Cl and 24.47% 37Cl. Hence, the mass
spectrum of chloromethane contains two peaks at m/e = 50 and m/e = 52 in
a ratio of approximately 3:1 corresponding to CH335Cl+ and CH337Cl+
respectively. The fragmentation pattern is as follows:
methyl radical chlorine cation

m/e = 35 and 37
chloromethane radical cation

m/e = 50 and 52
methyl cation chlorine radical
m/e = 15

100 50

80
15
60
40
52
20
35
37
0
0 10 20 30 40 50 60
m/e
Figure S66.9 The mass spectrum of chloromethane.
Figure S66.10 shows the mass spectrum of bromomethane, CH3Br.

Bromine consists of 50.54% 79Br and 49.46% 81Br. Hence, the mass
spectrum of bromomethane contains two peaks at m/e = 94 and m/e = 96 in
a ratio of approximately 1:1 corresponding to CH379Br+ and CH381Br+
respectively. The fragmentation pattern of bromomethane is as follows:
methyl radical bromine cation

m/e = 79 and 81
bromomethane radical cation

m/e = 94 and 96
methyl cation bromine radical
m/e = 15
100 94
96
80
60
15
40
20
79 81
0
0 10 20 30 40 50 60 70 80 90 100
m/e
Figure S66.10 The mass spectrum of bromomethane.

For iodomethane, as there is only one stable isotope of iodine, the

spectrum shows the molecular ion peak at m/e = 142. It corresponds to the
radical cation of iodomethane. The fragmentation of iodomethane is as
follows:
methyl radical iodine cation

m/e = 127
iodomethane radical cation

m/e = 142
methyl cation iodine radical
m/e = 15
The C−I bond of the molecular radical cation of iodomethane is

broken to give either an iodine cation (I+) together with a methyl radical or
a methyl cation (CH3+) together with an iodine radical. By comparing the
intensities of the peaks, it is clear that the molecular radical cation CH3I•+
is more stable than the other two fragment ions (Figure S66.11).
100 142
80
60
127
40
20
15
0
0 20 40 60 80 100 120 140 160
m/e
Figure S66.11 The mass spectrum of iodomethane.
Example S66.2
Interpreting the mass spectrum of a haloalkane
The following is the mass spectrum of a haloalkane which is believed to contain chlorine, bromine
or iodine.

100 156
29
80
60
127
40
20
0
0 20 40 60 80 100 120 140 160
m/e
(a) What halogen is expected to be present in the haloalkane? Explain your answer briefly.
(b) From the spectrum, what is the relative molecular mass of the haloalkane?
(c) Name and draw the structure of the haloalkane.
(d) Show the fragmentation pattern that accounts for the peaks at m/e = 127 and 29.
Solution
(a) There are no ‘twins’ molecular ion peak either in the ratio of 1:1 or 3:1. Iodine is expected to
be present in the haloalkane as there is only one stable isotope of iodine.
(b) The relative molecular mass of the haloalkane is 156.
(c) The haloalkane is iodoethane.
(d)
ethyl radical iodine cation

m/e = 127
iodoethane radical cation

m/e = 142 ethyl cation
iodine radical
m/e = 15

4. Alkenes
Figure S66.12 shows the mass spectrum of propene.
100 41

80
42
60
40 27
20
0
m/e
0 10 20 30 40 50
Figure S66.12 The mass spectrum of propene.
The molecular ion peak appears at m/e = 42. The base peaks at m/e =
41 and the peak at m/e = 27 correspond to the carbocations CH3CH=CH2+
and [CH=CH2]+. The fragmentation pattern of propene is as follows:
propene cation hydrogen radical

m/e = 41
propene radical cation

m/e = 42
ethene cation methyl radical
m/e = 27
5. Aromatic compounds
The most common fragment ion produced in the fragmentation of
alkylbenzene derivatives is the benzylic cation (C6H5CH2+). Consider
butylbenzene as an example. The radical cation is fragmented to give
benzylic cation and propyl radical. The benzylic cation rearranges to form
tropylium ion (C7H7+) which is more stable. At the same time, an acetylene
molecule is released and the fragment ion (C5H5+) is produced. The
fragmentation and rearrangement are shown below.
benzylic cation propyl radical

butylbenzene radical cation
m/e = 91
m/e = 134

rearrangement
benzylic cation tropylium ion C5H5+

m/e = 91 m/e = 91 m/e = 65
Figure S66.13 shows the mass spectrum of butylbenzene. The peak at

m/e = 134 is due to the molecular ion.
100 91
80
60
40
134
20
65
0
0 20 40 60 80 100 120 140 160
m/e
Figure S66.13 The mass spectrum of butylbenzene.
The base peak at m/e = 91 and the peak at m/e = 65 correspond to the
fragment ions C7H7+ and C5H5+ respectively.
Example S66.3
Interpreting the mass spectrum of an aromatic compound
The following shows the mass spectrum of a mono-substituted benzene.
100 91
80
60
40
106
20
0
0 20 40 60 80 100 120
m/e

(a) Deduce, from the mass spectrum, the relative molecular mass of the mono-substituted benzene.
(b) Locate the base peak from the mass spectrum.
(c) Draw the structure of the fragment ion corresponding to the base peak.
(d) Name and draw the structure of the mono-substituted benzene. Show how you obtain the
answer.
(e) Show the fragmentation pattern that accounts for the peak at m/e = 91.
Solution
(a) The relative atomic mass of the mono-substituted benzene is 106.
(b) The base peak is at m/e = 91.
(c)
or
(d) The relative molecular mass of the mono-substituted benzene is 106, while the relative
molecular mass of the benzylic cation is 91.0. The difference in relative molecular mass is
equal to 15.0 which is the relative molecular mass of a methyl group. Thus, the
mono-substituted benzene is ethylbenzene. The structure of ethylbenzene is:
6. Aldehydes and ketones

Aldehydes and ketones also undergo a series of fragmentation reactions.
Cleavage of the C−C bond on either side of the carbonyl group of
butanone gives two different cations, CH3CH2CO+ and CH3CO+. They
are formed according to the following mechanism. For example, butanone
undergoes fragmentation to give an acylium ion. Acylium ion (m/e = 43) is
formed according to the following mechanism:
butanone radical cation m/e = 43 ethyl radical

m/e = 72
butanone radical cation m/e = 43 methyl radical

m/e = 72

Figure S66.14 shows the mass spectrum of butanone. Note that the
peak of the molecular ion at m/e = 72 corresponds to butanone radical
cation. The base peak at m/e = 43 and the peak at m/e = 57 correspond to
the fragment ions, CH3CO+ and CH3CH2CO+ respectively.
100
Relative abundance (%) 43

80
60
40
20 72
57
0
0 10 20 30 40 50 60 70 80
m/e
Figure S66.14 The mass spectrum of butanone.
Example S66.4
Interpreting the mass spectrum of an unknown acyclic compound
The following shows the mass spectrum of an unknown acyclic compound X. Compound X reacts
with 2,4-dinitrophenylhydrazine to give an orange precipitate.
100 43
80
60
72
40
20
0
0 10 20 30 40 50 60 70 80
m/e
(a) Locate the base peak from the mass spectrum.

(b) From the information given by the mass spectrum, draw all possible structures for compound
X.
(c) If compound X turns acidified potassium dichromate solution from orange to green, what is the
identity of compound X?
Solution
(a) The peak at m/e = 43 is the base peak.
(b) Compound X reacts with 2,4-dinitrophenylhydrazine to give 2,4-dinitrophenylhydrazone which
is an orange precipitate. Thus, compound X may be an aldehyde or a ketone.
Let the molecular formula of compound X be CnH2nO.
From the mass spectrum, the relative molecular mass of compound X is 72.0.
(12.0 + 1.0  2)n + 16.0 = 72.0
n=4
 molecular formula of compound X is C4H8O.
There are three possible structures having the molecular formula C4H8O:
1. 2. 3.
The peak at m/e = 43 is the base peak. It is due to the CH3CO+ or (which is much
more stable than CH3CH2CH2+). It suggests that compound X may be:
or
(c) Compound X turns acidified potassium dichromate solution from orange to green. This
excludes the possibility of a ketone. Thus, compound X is 2-methylpropanal. Its structure is:
7. Carboxylic acids and esters

In the mass spectrometer, the molecular ion of carboxylic acids and
benzoic acid give stable fragment ions by losing •OH and •OR free
radicals respectively. The fragmentation of the molecular ion of carboxylic
acids produces hydroxyl radical while the fragmentation of the molecular
ion of benzoic acid produces alkoxyl radical.

The mass spectra of propanoic acid and ethyl ethanoate together with
the identities of the main fragment ions are shown from Figure S66.15 to
Figure S66.16, and Table S66.3 to Table S66.4.
100 74
80
60
57
40
20
0
0 10 20 30 40 50 60 70 80
m/e
Figure S66.15 The mass spectrum of propanoic acid.
Ion m/e
74
57
Table S66.3 Interpretation of the mass spectrum of propanoic acid.
100 43
80
60
40
20
88
0
0 10 20 30 40 50 60 70 80 90 100
m/e
Figure S66.16 The mass spectrum of ethyl ethanoate.

Ion m/e
88
CH3CO+ 43
Table S66.4 Interpretation of the mass spectrum of ethyl ethanoate.

Chapter 67 Contribution of analytical chemistry to our

society
Supplement to
Gas chromatography-mass spectrometry
Coursebook p.183
Gas chromatography-mass spectrometry (GC-MS) (Figure S67.1) is an
instrumental technique that combines the features of gas chromatography
and mass spectrometry. Figure S67.2 shows the schematic diagram of a
gas chromatography-mass spectrometry unit. When the components of a
mixture exit from a chromatographic column, they enter the mass
spectrometer. Then mass spectra are collected. They can be stored in the
computer for subsequent processing.
Figure S67.1 A gas chromatography-mass spectrometry unit.
sample injector
oven
mass
column spectrometer
gas: He, H2, N2
Figure S67.2 A schematic diagram of the gas chromatography-mass spectrometry unit.
Figures S67.3 below shows the typical output from a GC-MS unit.
Figure S67.3a is a computer-reconstructed chromatogram of a sample
mixture containing mainly ethanal and benzene. It can be seen that there
are two main peaks in the chromatogram. Figure S67.3b shows the
computer-reconstructed mass spectrum of the peak 2 on the chromatogram.
Obviously, it corresponds to benzene.

Retention time
(a)
m/e
(b)
Figure S67.3 Typical output from a gas chromatography-mass spectrometry unit. (a)
Computer-reconstructed chromatogram. (b) Computer-reconstructed mass spectrum.
Gas chromatography-mass spectrometry is one of the most powerful

tools for the analysis of organic compounds and biochemicals. It has been
used for the identification of components that are present in natural and
biological systems. Examples include characterization of the odour and
flavour components of foods and studies of drug metabolites.

Appendix
Sample Infrared Spectra
1. Hex-1-ene
(Reproduced from Modern Chemical Techniques, The Royal Society of Chemistry, Cambridge, 1992.)
Wavenumber (cm-1)
3080 C−H of C=C−H
2970 C −H
1640 C=C
2. Hex-1-yne
100
Per cent transmittance
80
60
40
20
4000 3500 3000 2500 2000 1800 1600
-1
Wavenumber (cm )
Wavenumber (cm-1)
3300 C−H * (* Absorption at 3300 cm-1
2900 to 2950 C −H is due to C−H bond in
2200 C C terminal CC triple bond.)

3. Propanal
Wavenumber (cm-1)
2980 Aliphatic C−H
2830, 2720 C−H of CHO
1730 C=O
4. 3-Methylbutan-2-one
100
80
60
40
20
4000 3500 3000 2500 2000 1800 1600
Wavenumber (cm -1 )
Wavenumber (cm-1)
2880 to 2980 C −H
1720 C=O

5. Hex-5-en-2-one
100
80
60
40
20
4000 3500 3000 2500 2000 1800 1600
-1
Wavenumber (cm )
Wavenumber (cm-1)
3080 C −H
1720 C=O
1635 C=C
6. Methanol
Wavenumber (cm-1)
3330 O− H
2940, 2820 C −H
1030 C −O

7. Phenol
Wavenumber (cm-1)
3380 O− H
3050 Aromatic C−H
1220 C −O
8. Methanoic acid
Wavenumber (cm-1)
3100 O− H

1710 C=O
9. Butyl ethanoate
100
80
60
40
20
4000 3500 3000 2500 2000 1800 1600
-1
Wavenumber (cm )
Wavenumber (cm-1)
2900 to 2950 C −H
1740 C=O
10. Butylamine
100
80
60
40
20
4000 3500 3000 2500 2000 1800 1600
-1
Wavenumber (cm )
Wavenumber (cm-1)
3300 to 3400 N− H
2850 to 2950 C −H

11. Propanenitrile
Wavenumber (cm-1)
3000 C −H
2250 C N

Correlation Table of Functional Groups and IR Absorption Wavenumbers

Characteristic Range
Bond Wavenumber (cm−1)
C=C Alkenes 1610 to 1680
C=O Aldehydes, ketones, acids, esters 1680 to 1750
C≡C Alkynes 2070 to 2250
C≡N Nitriles 2200 to 2280
O−H Acids (hydrogen-bonded) 2500 to 3300
C −H Alkanes, alkenes, arenes 2840 to 3095
O−H Alcohols, phenols 3230 to 3670
(hydrogen-bonded)
N−H Primary amine 3350 to 3500


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CHEMISTRY

HKDSE CHEMISTRY – A MODERN VIEW

PART I PLANET EARTH

© Aristo Educational Press Ltd. 2009

PART I PLANET EARTH

Chapter 1 Fundamentals of Chemistry

Supplement to The scientific method

Figure S1.1 The scientific method.

1. Look for scientific facts by the observation of nature or

It is shown by the Brownian movement experiment that particles are

air remove glass plate

and allow gas jars

and allow gas jars

random motion (a) (b)

© Aristo Educational Press Ltd. 2009 2

Applying kinetic theory to different states of matter

Figure S1.3 We can ‘see’ the

three states of matter at this

Solid Liquid Gas

© Aristo Educational Press Ltd. 2009 3

the same on every part of the

Supplement to A simple experiment to determine the percentage of oxygen in

copper + oxygen → copper(II) oxide

This reaction can be used to serve our purpose, in a set-up as shown

© Aristo Educational Press Ltd. 2009 4

air reddish brown

1. Pack a hard-glass tube with copper turnings.

© Aristo Educational Press Ltd. 2009 5

Supplement to Folding filter paper in fluted form

To fold the filter paper in fluted form, we do the following:

© Aristo Educational Press Ltd. 2009 6

(a) (b) (c)

© Aristo Educational Press Ltd. 2009 7

PART II MICROSCOPIC WORLD I

Chapter 5 Atomic structure

Supplement to Alchemy atomic symbols and Dalton’s atomic symbols

Platinum Gold Silver

Copper Iron Lead

Magnesium Mercury Phosphorus

Figure S5.1 Some of the Alchemy symbols.

© Aristo Educational Press Ltd. 2009 8

John Dalton used the above symbols to represent different elements.

However, the situation is very different in reality. For example, if we

© Aristo Educational Press Ltd. 2009 9

The atomic orbital can be represented by an electron cloud model.

John Dalton (1805) J.J. Thomson (1904)

(positive and negative charges)

Ernest Rutherford (1911)

(the nucleus) Niels Bohr (1913)

(electron cloud model)

Learning tip Classification of orbitals

© Aristo Educational Press Ltd. 2009 10

Figure S5.4 The shapes of the s orbitals.

2px 2py 2pz

Figure S5.5 The shapes and orientations of different p orbitals.

3dyz 3dxz 3dxy 3dx2−y2 3dz2

Figure S5.6 The shapes and orientations of different d orbitals.

© Aristo Educational Press Ltd. 2009 11

Energy level Orbitals present Maximum number of electrons

Electronic configuration of an element

Figure S5.7 Dalton’s model of an atom – the solid indivisible atom.

© Aristo Educational Press Ltd. 2009 12

Cathode rays can be detected by zinc sulphide screen, which emits