A’ LEVEL CHEMISTRY NOTES

COMBINED BY B.N MUPETI

1
CHAPTER 1: Atomic Structure
1.1 Inside the Atom
1.2 Isotopes

Learning outcomes:

(a) identify and describe protons, neutrons and electrons in terms of their relative charges and
relative masses.
(b) deduce the behaviour of beams of protons, neutrons and electrons in electric fields.
(c) describe the distribution of mass and charges within an atom.
(d) deduce the numbers of protons, neutrons and electrons present in both atoms and ions given
proton and nucleon numbers (and charge).
(e) (i) describe the contribution of protons and neutrons to atomic nuclei in terms of proton
number and nucleon number.
(ii) distinguish between isotopes on the basis of different numbers of neutrons present
(iii) recognise and use the symbolism where x is the nucleon number and y is the proton
number.

2
1.1 Inside the Atom
Sub-atomic particles

1) Electrons revolve around in region of space called orbitals.

2) Electrons do not move in fixed orbits.

3) The nucleus is made up of protons and neutrons which contains almost all
the mass of the atom. This is because the mass of electrons is very small
compared to others.

4) The nucleus is positively-charged because of the protons. Electrons, being

negatively-charged, surround the nucleus.

Particles Relative mass Relative Charge Charge / C

-19
Protons, p 1 +1 +1.6 x 10

Neutron, n 1 0 0
1 -19
Electron, e -1 -1.6 x 10
1836

3
Behaviour of sub-atomic particles in electric field

1) Proton will be deflected towards the negative

plate because it is positively-charged.

2) Electron will be deflected towards the positive

plate because it is negatively-charged.

3) Neutron will not be deflected and continue in their

direction of motion because it is neutral(not charged).

4) Angle of deflection of electron > Angle of deflection of proton because

the mass of electron is smaller than proton. (angle of deflection is inversely
proportional to charge/mass ratio)

5) Conclusion:
i. Protons are positively-charged
ii. Electrons are negatively-charged
iii. Neutrons are neutral
iv. Protons are much heavier than electron

Nucleon number and proton number

1) Proton number is the total number of protons in an atom.

2) Nucleon number is the total number of protons and neutrons in an atom.

3) Proton number is also known as atomic number while nucleon number is also
known as mass number.

4) In a neutral atom, the total number of protons equals to the total number of
electrons.

4
5) When an atom gains or loses electrons, a cation or anion will be formed.

6) Cation is a positively-charged ion. It is formed when an atom loses electron(s).

In cation, the number of protons is more than the number of electrons.

7) Anion is a negatively-charged ion. It is formed when an atom gains electron(s).

In anion, the number of electrons is more than the number of protons.

8) An atom or ion is said to be

i. isoelectronic if they have the same number of electrons.
ii. isotonic if they have the same number of neutrons.
iii. isotopic if they have the same number of protons.

To deduce the number of protons, neutrons and electrons in an atom/ion

5
1.2 Isotopes
Isotopes

1) Isotopes are atoms of the same element with the same number of proton but
different number of neutron.

Example:

2) Isotopes have the same:

i. number of protons and electrons
ii. electronic configuration
iii. chemical properties(because they have the same number of electrons)

3) Isotopes have different:

i. number of neutrons and nucleon number
ii. mass
iii. density
iv. molecular speed

4) Isotopes can be stable or unstable. Unstable isotopes are called radioactive

isotopes(radioisotopes).

6
CHAPTER 2: Atoms, Molecules and
Stoichiometry
2.1 Mass of Atoms and Molecules
2.2 Mass Spectrometer
2.3 Amount of Substance
2.4 Empirical Formula and Molecular Formula
2.5 Stoichiometry and Equations

Learning outcomes:

(a) define and use the terms relative atomic, isotopic, molecular and formula masses, based on the
C-12 scale.
(b) define and use the term mole in terms of the Avogadro constant.
(c) analyse mass spectra in terms of isotopic abundances [knowledge of the working of the mass
spectrometer is not required].
(d) calculate the relative atomic mass of an element given the relative abundances of its isotopes,
or its mass spectrum.
(e) define and use the terms empirical and molecular formulae.
(f) calculate empirical and molecular formulae, using combustion data or composition by mass.
(g) write and/or construct balanced equations.
(h) perform calculations, including use of the mole concept, involving:
(i) reacting masses (from formulae and equations).
(ii) volumes of gases (e.g. in the burning of hydrocarbons).
(iii) volumes and concentrations of solutions.
When performing calculations, candidates’ answers should reflect the number of significant
figures given or asked for in the question. When rounding up or down, candidates should ensure
that significant figures are neither lost unnecessarily nor used beyond what is justified.
(i) deduce stoichiometric relationships from calculations such as those in (h).

7
2.1 Mass of Atoms and Molecules
Concept of relative mass

1) Relative mass is an indication of how heavy is an atom compared to another

atom which is used as a standard model.

2) Relative mass is expressed in atomic mass unit(a.m.u).

3) C-12 was chosen to be the standard model because:

i. it is the most abundant isotope of carbon
ii. it is a solid, easy to handle and easily available

4) C-12 was assigned a mass of exactly 12 a.m.u.. This is known as C-12 scale.

5) For example, an atom which is 3.5 times heavier than a C-12 atom would have
a relative mass of (3.5 x 12) = 42 a.m.u.. That means, this atom is 42 times
heavier than the mass of (1/12 x the mass of C-12 atom).

Relative isotopic mass

1) Relative isotopic mass is the mass of an isotope measured on a scale in which a

carbon-12 atom has a mass of exactly 12 units.

Relative atomic mass, Ar

1) Relative atomic mass, Ar is the weighted average relative masses of all its isotopes
measured on a scale in which a carbon-12 atom has a mass of exactly 12 units.

Average mass of one

atom of the element
Relative atomic mass, Ar = X 12
Mass of one atom of
carbon-12

8
Example:

Ratio of Cl-35 to Cl-37 is 3:1. If you have 4 typical atoms of chlorine, total mass
is (35 x 3) + (37 x 1) = 142. So, the average mass of the isotopes is 142/4 = 35.5.

This implies that 35.5 is the relative atomic mass of chlorine while 35 is the
relative mass of Cl-35 and 37 is the relative mass of Cl-37.

Relative molecular mass, Mr

1) Relative molecular mass, Mr is the weighted average of the masses of the molecules
measured on a scale in which a carbon-12 atom has a mass of exactly 12 units.

2) It should only be applied to substances which exist as molecules.

3) It is found by adding up all the relative atomic masses of all the atoms present in
the molecule.

4) Examples:
i. Mr (H2O) = 2(1) + 16 = 18
ii. Mr (CHCl3) = 12 + 1 + 3(35.5) = 119.5

Relative formula mass, Mr

1) Relative formula mass, Mr is the weighted average of the masses of the formula
units measured on a scale in which a carbon-12 atom has a mass of exactly 12
units.

2) It works for both ionic and covalent compounds.

3) Examples:
i. Mr (NaCl) = 23 + 35.5 = 58.5
ii. Mr (CuSO4 • H2O) = 64 + 32+ 4(16) +5[2(1) + 16] = 249.5

9
2.2 Mass Spectrometer
What is mass spectrometer?

1) A mass spectrometer is used to determine:

a. relative isotopic mass
b. relative abundance of isotopes
c. relative atomic mass
d. relative molecular mass
e. structural formula of compounds

Determination of relative atomic mass using mass spectrometer

1) Five steps:
i. Vaporisation
- atoms are vaporised to form gaseous atom.

ii. Ionisation
- gaseous atoms are bombarded with high energy electrons to form positive
ions.

iii. Acceleration
- the ions are accelerated so that they have the same kinetic energy.

iv. Deflection
- ions are deflected by a magnetic field. The amount of deflection depends on:
1) the mass of the ion
2) the amount of positive charge on it
- the larger the mass, the smaller the deflection.
- the higher the charge, the larger the deflection.
- the two factors combine into mass/charge ratio (m/e or m/z).
- the smaller the value of m/e, the larger the deflection

v. Detection
- the beam of ions are detected electrically.
- the data are fed into the computer and the mass spectrum is produced.

10
 Side note

1) Ionisation chamber is vacuum

so that the ions produced can
run freely without knocking
air molecules.

Mass spectrum (How to calculate relative atomic mass, Ar from it?)

Relative abundance

c
b

m/e
m₁ m₂ m₃

(m₁ x a) + (m₂ x b) + (m₃ x c)

Ar =
a+b+c

11
Example:

The mass spectrum of boron, B is as shown, given the relative abundances:

B-10 : 23
B-11 : 100

(23 x 10) + (100 x11)

Ar =
23 + 100

= 10.8

2.3 Amount of Substance

The mole and the Avogadro's constant

1) A mole of a substance is the amount of substance that contains the same

amount of stated elementary units as there are atoms in 12 g of C-12.

2) The number of atoms is 12 g of C-12 is 6.02 x 10²³ . This number is also

known as the Avogadro's constant, L.

3) Examples:
i. 1 mol of He contains 6.02 x 10²³ He atoms.
ii. 1 mol of CO2 contains 6.02 x 10²³ CO2 molecules but 3 x (6.02 x10²³)
atoms.
iii. 1 mol of NaCl contains 6.02 x 10²³ NaCl units, Na⁺ and Cl⁻ ions.

12
Moles and mass

Mass / g
No. of mole / mol = -1
Molar mass / g mol

Moles and volumes

1) Volume occupied by a gas depends on the amount of gas, temperature and

pressure. In other words the volume of a gas is not fixed.

2) Avogadro's law states that for equal volumes of all gases, under the same
conditions, contain the same number of moles.

3) Hence, equal number of moles of any gas, under the same conditions, would
occupy the same volume. It does not depend on the nature of gas.

4) At room temperature of 20 ℃ and a pressure of 1 atm, one mole of any gas

occupies 24 dm³.

5) At standard temperature and pressure (s.t.p), which is 0 ℃ and 1 atm, one mole
of any gas occupies 22.4 dm³.

Volume of a gas / dm³

No.of mole / mol =
Molar volume / dm³ mol -1

6) i. Complete combustion of hydrocarbon produces water and carbon dioxide.

The general equation is as follow:

ii. In incomplete combustion, the possible products are carbon dioxide, carbon
monoxide, carbon soot and water.

13
Moles and concentration of solutions

1) A solution is a homogeneous mixture of two or more substance.

2) The substance presents in small quantity is called the solute while the substance
present is larger quantity is called the solvent.

3) Concentration is the amount of solute present in a fixed quantity of solution.

4) Concentration is expressed in terms of g dm⁻³. Concentration in mol dm⁻³ is

called molar concentration or molarity.

Mass of solute / g
Concentration / g dm⁻³
Volume of solution / dm³

Concentration / g dm⁻³
Molarity / mol dm⁻³
Concentration / g dm⁻³
Molar mass of solute / g mol -1
Molarity / mol dm⁻³
Molar mass of solute / g mol -1

Volume / cm³ X Molarity / mol dm⁻³

No. of moles / mol =
1000
Volume / cm³ X Molarity / mol dm⁻³
No. of moles / mol =
1000

2.4 Empirical Formula and Molecular Formula

Percentage composition by mass

Percentage composition Ar x No.of mole of that element

by mass / % = X 100%
Molar mass of compound

14
Empirical formula

1) Empirical formula is a chemical formula that shows the simplest ratio of the atoms
that combine to form a molecule.

2) Steps to find empirical formula:

i. Find the mass of each element.
ii. Find the number of mole of each element (divide by its Ar).
iii. Find the simplest ratio (divide by the smallest number).
iv. Construct the empirical formula using the simplest ratio.

[ If a decimal or fraction exists, round up or eliminate the fraction ]

[ Never assume a formula ]

3) Some facts:
i. The formula for an ionic compound is always its empirical formula.
ii. The empirical formula and molecular formula for simple inorganic molecules
are often the same.
iii. Organic molecules have different empirical and molecular formula.

Molecular formula

1) Molecular formula is a chemical formula that shows the actual number of atoms
that combine to form the compound.

2) In order to deduce the molecular formula of a compound, we need to know:

i. the relative formula mass of the compound.
ii. the empirical formula of the compound.

Principle of conservation of mass

1) Mass is neither created nor destroyed during a chemical reaction. Therefore the
total mass of the reactants is equal to the total of the products in a closed
system.

2) For example, the total mass of iodine in the reactants is equal to the total mass
of iodine in the products.
3) This can be used to solve problems in calculating the empirical formula.

15
2.5 Stoichiometry and Equations
Stoichiometry

1) Stoichiometry is the proportion of things either reacting or combining.

2) In compounds, it refers to the ratio in which the atoms are combined together.
For example, water, H2O has a stoichiometry of 2 hydrogen to 1 oxygen.

3) It also refers to the reacting proportions in a chemical equation. For example:

2H2 + O2 → 2H2O
The stoichiometry shows that 2 moles of hydrogen react with 1 mole of oxygen
to form 2 moles of water.

Ionic equations

1) Steps to construct net ionic equations:

i. Write the balanced molecular equation.
ii. Write the complete ionic equation by splitting it into ions(if possible).
iii. Cancel out the spectator ions. (Spectator ions are ions that present in the
mixture but do not participate in the reaction.)
iv. Write down the 'leftovers', that is the net ionic equation.
Chemical equation:

Complete ionic equation:

Net ionic equation:

FAQ 1: When to split compounds into FAQ 2: How to identify spectator ions?
ions?
1) The ions present on both sides of
1) Only split aqueous ionic compounds. For the equation are spectator ions.
example, NaCl(aq) and HCl(aq)
2) Do not split solid ionic compounds and
covalent compounds, as well as metals.
For example, NaCl(s), H2O(l), Mg(s)
and HCl(g)

16
CHAPTER 3: Electrons in Atoms
3.1 Sub-shells and Atomic Orbitals
3.2 Electronic Configuration
3.3 Ionisation Energy

Learning outcomes:

(a) describe the number and relative energies of the s, p and d orbitals for the principal quantum
numbers 1, 2 and 3 and also the 4s and 4p orbitals.
(b) describe the shapes of s and p orbitals.
(c) state the electronic configuration of atoms and ions given the proton number (and charge),
using the convention 1s²2s²2p⁶ etc.
(d) (i) explain and use the term ionisation energy.
(ii) explain the factors influencing the ionisation energies of elements.
(iii) explain the trends in ionisation energies across a Period and down a Group of the Periodic
Table.
(e) deduce the electronic configurations of elements from successive ionisation energy data.
(f) interpret successive ionisation energy data of an element in terms of the position of that
element within the Periodic Table.

17
3.1 Sub-shells and Atomic Orbitals
Principle quantum shell

1) Electrons are arranged outside the nucleus in energy levels or principle

quantum shell, n.

2) The principal quantum shells are numbered according how far are they from
the nucleus.

3) The lowest energy level, n = 1 is closest to the nucleus,

the energy level n = 2 is further out, and so on.

4) The electrons in energy level further away from the

nucleus have more energy and held less tightly by the
nucleus.
The circles represent
5) Electrons do not move in fixed circular paths, they energy levels
occupy a space called the atomic orbitals.

6) The total number of electrons that can occupy any principal shell is 2n², where
n is the principal quantum number.

Quantum sub-shells

1) The principal quantum shells, apart from the first, are split into sub-shells. Each
principle quantum shell contains a different number of sub-shells.

2) The first energy level contains one sub-shell, the second energy level contains
two and so on.

3) The sub-shells are distinguished by letters s, p, d, f and so on.

4) The energy of electrons in the sub-shells increases in the order s < p < d < f.

18
 Principal Maximum number of Number of Name of
quantum shell electrons sub-shells sub-shells

K, n = 1 2 1 1s

L, n = 2 8 2 2s, 2p

M, n = 3 18 3 3s, 3p, 3d

32 4 4s, 4p, 4d, 4f

N, n = 4

The impossibility of drawing orbits for electrons

1) Heisenberg Uncertainty Principle says, you cannot know with certainty where
an electron is and where it is going next.

2) This makes it impossible to draw out an orbit or pathway in which the electrons
move.

Atomic orbitals

1) An atomic orbital is a region of space around the nucleus where the probability of
finding a particular electron is maximum (>95%).

2) The sub-shells are split further into orbitals where the electrons are placed.

19
3) The number of orbital in each sub-shell depends on the sub-shells.
s - one orbital {s}
p - three orbitals {px, py, pz}
d - five orbitals {dxy, dyz, dxz, dx²-y², dz²}

4) Orbitals having the same energy are called degenerate orbitals. For example,
px, py and pz are degenerate orbitals.

5) The concept of orbitals arises from the fact that an electron has dual nature. It
behaves as a particle as well as a wave.

6) In the nth principal quantum shell, there are n sub-shells, n² orbitals and a
maximum of 2n² electrons.

The s orbital

2s

1) All the s orbitals are spherical and non-directional.

2) The shaded region represents the region in which the chance of finding the s
electron is more than 95%.

3) The size of the s orbital increases in the order 1s < 2s < 3s < 4s.

20
The p orbital

1) All the p orbitals are dumb-bell shaped and directional.

2) p orbitals are only available from the second principal

quantum shell and onwards.

3) There are 3 types of p orbitals, px, py and pz. All 3 different types of p orbitals
are perpendicular to each other along the x, y and z axes.

4) Going to a higher energy level, the 'lobes' of the p orbital become longer.

21
3.2 Electronic Configuration
Ways to represent electronic configuration

Electronic configuration describes how the electrons in an atom/ion are arranged

in their shells, sub-shells and orbitals.

1) Using 'electrons-in-boxes':

2) Using energy levels:

3) Using s, p, d and f notation:

4) Using the noble gas 'core':

22
Filling in the orbitals

1) Three general rules of filling the orbitals are:

i. Aufbau Principle states that in the ground state of an atom, the electrons must
occupy the orbitals in the order of increasing energy.

[ Note: 4s has a slightly lower energy than 3d, therefore electrons are filled in
4s orbital first before the 3d orbitals. ]

ii. Pauli's Exclusion Principle states that an orbital can only

accommodate a maximum of two electrons only. The two
electrons must have opposite spins.

iii. Hund's Rule states that in a set of degenerate orbitals, electrons

must occupy the orbital singly first before pairing. The reason is because,
two electrons occupying the same orbital will experience repulsion.

rather than

23
2) Electronic configuration of the elements (up to Z = 38)

24
3) The odd ones (K, Sc, Cr and Cu):

i. For potassium, 4s is filled before 3d because 4s has a lower energy level

than 3d.

ii. For scandium (to zinc, the d-block elements), the energy level of 3d and 4s
are reversed. 4s is at a higher energy level now. This is because once the 3d
orbital(s) is/are filled, the 3d electrons repel the 4s electrons to a higher
energy level.

iii. For chromium, the electronic configuration is [Ar]3d⁵4s¹ instead of

[Ar]3d⁴4s². This is because orbitals that are fully filled or half filled have
extra stability due to their symmetrical charge distribution.

iv. For copper, the electronic configuration is [Ar]3d¹⁰4s¹ instead of [Ar]3d⁹4s².

The reason is the same as stated in (iii).

Electronic configuration of ions

1) In the formation of cation, the electrons are removed in the order of decreasing
energy (the reverse of filling in).

2) For the d-block elements, the electrons in 4s is removed first before 3d. This is
because once the 3d orbital is filled, the 4s electrons are repelled to a higher
energy level than 3d.

3) In the formation of anion, the electrons are added in the same manner as filling
the electrons.

25
Orbitals and the Periodic Table

1) The elements in the Periodic Table can be divided into four blocks according to
their valence shell electronic configuration.

2) The s-block elements have their valence electron(s) in the s orbital.

3) The p-block elements have their valence electrons in the p orbital.

4) The d-block elements have d orbitals filling.

5) The f-block elements have f orbitals filling.

Some useful facts

1) The valence electrons always appear at the end of the electronic configuration.
(but not necessary the last one).

2) The valence electrons are large responsible for the chemical properties of an
element.

3) The number of valence electron will indicate the group number of that
element in the Periodic Table.

4) The outermost quantum shell number will indicate the period of that
element in the Periodic Table.

26
3.3 Ionisation Energy
What is ionisation energy?

1) The 1st ionisation energy, ΔHi1 is the energy needed to remove one electron from
each atom in one mole of the atoms of the element in the gaseous state to
form one mole of gaseous 1+ ions.

2) The general unit for ionisation energy is kJ mol⁻¹.

Ca(g) → Ca⁺(g) + e⁻ ; ΔHi1 = +590 kJ mol⁻¹

3) If a second electron is removed from the gaseous 1+ ions, it is the 2nd ionisation
energy, ΔHi2.

Ca⁺(g) → Ca²⁺(g) + e⁻ ; ΔHi2 = +1150 kJ mol⁻¹

4) The 2nd ionisation energy, ΔHi2 is the energy needed to remove one electron
from each gaseous 1+ ion in one mole of the ions to form one mole of gaseous
2+ ion.

5) The continuos removal of electrons until the nucleus is left only will result in
successive ionisation energies.

Factors affecting the ionisation energy

1) Charge on the nucleus (Number of proton)

- The greater the number of proton in the nucleus, the greater the amount of
positive charge.
- The greater the positive charge, the greater the attractive force between
the nucleus and outer electrons.
- More energy is needed to overcome the attractive force. So, the ionisation
energy is higher.
- The greater the nuclear charge, the higher the ionisation energy.

27
2) Distance between nucleus and outer electrons (Size of atom/ion)
- The larger the size of the atom, the greater the distance between the nucleus
and the outer electrons.
- The greater the distance between the nucleus and the outer electrons, the
weaker the attractive force between nucleus and outer electrons.
- Furthermore, the outer electrons experience greater shielding effect by the
inner electrons.
- Less energy is required to overcome the attractive force. So, the ionisation
energy is lower.
- The greater the distance between nucleus and outer electrons, the
lower the ionisation energy.

3) Shielding effect by the inner electrons

- All electrons are negatively-charged, so they repel each other. Electrons in full
inner shells will repel the outer electrons and so prevent the full nuclear
charge being felt by the outer electrons. This is called shielding or screening.
- The greater the shielding effect, the weaker the attractive force between
the nucleus and outer electrons.
- Less energy is required to overcome the attractive force. So, the ionisation
energy os lower.
- The greater the shielding effect, the lower the ionisation energy.

Pattern of ionisation down a Group

1) The first ionisation energy decreases down a Group.

2) This is because the atomic size increases and hence the

distance between the nucleus and outer electrons
increases. The outer electrons also experience a greater
shielding effect.

3) These two factors outweigh the increasing nuclear charge.

4) The above factors causes the attractive force between nucleus and outer
electrons to decrease, less energy is required to overcome the weaker attractive
force. Hence, the ionisation energy is lower.

28
Pattern of ionisation energy across a Period

1) The general trend of ionisation energy across a Period is increasing.

2) This is because, across a Period, the number of proton in the nucleus increases
by one therefore the nuclear charge increases.

3) However, the distance between the nucleus and outer electrons decreases across
a Period and the outer electrons experience the same amount of shielding.

4) The above factors causes the attractive force between nucleus and outer
electrons to increase, more energy is required to overcome the stronger
attractive force. Hence, the ionisation energy is higher.

The drop between (Be-B) and (Mg-Al)

1) There is a slight decrease in first ionisation energy between beryllium-born and

magnesium-aluminium.

2) This is because the fifth electron in boron is located in the 2p sub-shell, which is
slightly further away from the nucleus. The outer electron in boron is shielded
by the 1s² as well as 2s² electrons.

Be : 1s²2s² B : 1s²2s²2p¹

3) The decrease in first ionisation energy between magnesium and aluminium has
the same reason, except that everything is happening at the third energy level.

Mg : 1s²2s²2p⁶3s² Al : 1s²2s²2p⁶3s²3p¹

29
The drop between (N-O) and (P-S)

1) There is a slight decrease in first ionisation energy between nitrogen-oxygen and

phosphorus-sulphur.

2) This is because the electron being removed in oxygen is from the orbital which
contains a pair of electrons. The extra repulsion between the pair of electrons
results in less energy needed to remove the electron. This is called spin-pair
repulsion.

N : 1s²2s²2px¹2py¹2pz¹ O : 1s²2s²2px²2py¹2pz¹

3) The decrease in first ionisation energy between phosphorus and sulphur has
the same reason, except that everything is happening at the third energy level.

P : 1s²2s²2p⁶3s²3px¹3py¹3pz¹ S : 1s²2s²2p⁶3s²3px²3py¹3pz¹

Successive ionisation energy

1) The following data can be obtained from successive ionisation energy:

i. Total number of electrons in an atom.
- is equal to the number of separate ionisation energies possessed by the
atom.

ii. Number of principal quantum shells occupied and the number of electrons
in each.
-by looking the big difference between two successive ionisation energies.

iii. Number of sub-shells occupied and the number of electrons in each.

2) Successive ionisation energies get larger because removing an electron from a

positive ion with increasing positive charge is going to be more difficult due to
the increasing attractive force.

30
3) There is a relatively big increase in ionisation energy between the first and
second electron being removed. This suggests that the second electron being
removed is from a principal quantum shell closer to the nucleus.

4) The big jump occurs three times, so there are four principal quantum shells
occupied by this atom.

5) After the big jumps, there is a steady increase in ionisation energy, this suggests
that the electrons being removed come from the same principal quantum shell.

6) The electronic configuration for this atom can be written as 2,8,8,1.

7) Two more examples:

This element comes from Group 2 This element comes from Group 14
of the Periodic Table of the Periodic Table

31
Looking at the pattern in more detail

1) The electronic configuration of chlorine is 1s²2s²2p⁶3s²3px²3py²3pz¹.

2) Between the second and third ionisation energy, there is a slight increase in
difference in ionisation energy. This is because the first two electrons being
removed come from the orbitals which contain a paired electrons. The extra
repulsion between the electrons result in the ionisation energy being lower.

3) There is also a slight increase in difference in ionisation energy between the

fifth and sixth electron being removed. This is because the sixth electron being
removed comes from the 3s sub-shell, which is slightly closer to the nucleus.

4) The drastic increase in ionisation energy between the seventh and eighth
electrons suggests that the eighth electron comes from a principal quantum shell
closer to the nucleus.

32
CHAPTER 4: Chemical Bonding

4.1 Ionic Bonding

4.2 Covalent Bonding
4.3 Shapes of Molecules
4.4 Electronegativity, Bond Polarity, Bond Length and Bond Energy
4.5 Intermolecular Forces
4.6 Metallic Bonding
4.7 Bonding and Physical Properties of Substances

Learning outcomes:

(a) describe ionic (electrovalent) bonding, as in sodium chloride and magnesium oxide, including
the use of ‘dot-and-cross’ diagrams.
(b) describe, including the use of ‘dot-and-cross’ diagrams,
(i) covalent bonding, as in hydrogen, oxygen, chlorine, hydrogen chloride, carbon dioxide,
methane, ethene.
(ii) co-ordinate (dative covalent) bonding, as in the formation of the ammonium ion and in the
Al2Cl6 molecule.
(c) explain the shapes of, and bond angles in, molecules by using the qualitative model of
electron-pair repulsion (including lone pairs), using as simple examples: BF3 (trigonal), CO2
(linear), CH4 (tetrahedral), NH3 (pyramidal), H2O (non-linear), SF6 (octahedral), PF5
(trigonal bipyramid).
(d) describe covalent bonding in terms of orbital overlap, giving σ and π bonds, including the
concept of hybridisation to form sp, sp² and sp³ orbitals.
(e) explain the shape of, and bond angles in, ethane and ethene in terms of σ and π bonds.
(f) predict the shapes of, and bond angles in, molecules analogous to those specified in (c) and (e).
(g) describe hydrogen bonding, using ammonia and water as simple examples of molecules
containing N-H and O-H groups.
(h) understand, in simple terms, the concept of electronegativity and apply it to explain the
properties of molecules such as bond polarity and the dipole moments of molecules.
(i) explain the terms bond energy, bond length and bond polarity and use them to compare the
reactivities of covalent bonds.
(j) describe intermolecular forces (van der Waals’ forces), based on permanent and induced
dipoles, as in CHCl3(l); Br2(l) and the liquid noble gases.
(k) describe metallic bonding in terms of a lattice of positive ions surrounded by mobile electrons.

33
(l) describe, interpret and/or predict the effect of different types of bonding (ionic bonding,
covalent bonding, hydrogen bonding, other intermolecular interactions, metallic bonding) on
the physical properties of substances.
(m) deduce the type of bonding present from given information.
(n) show understanding of chemical reactions in terms of energy transfers associated with the
breaking and making of chemical bonds.

34
4.1 Ionic Bonding
Formation of ionic bond

1) Ionic bond is the electrostatic force of attraction between oppositely-charged

ions formed by the complete transfer of electrons from an atom to another
atom.

2) Ionic bond is also called electrovalent bond.

3) i. An atom(usually a metal) that loses electron(s) will form a positive ion(cation).

ii. The electron is then transferred to another atom.
iii. The atom that gains the electron(usually a non-metal) will form a negative
ion(anion).
iv. The cations and anions are then attracted by strong electrostatic force of
attraction. The force of attraction constitutes the ionic bond.

4) The force of attraction between cation and anion is very strong, therefore ionic
bond is a very strong bond.

5) Ionic bonds are non-directional, each cation will attract any neighbouring anion
and vice versa to form a huge ionic lattice.

6) The compound formed as a result of ionic bond is called ionic compound. An

example is sodium chloride, NaCl.

Dot-and-cross diagram

1) A dot-and-cross diagram shows:

i. the outer electron shell only.
ii. that the charge of the ion is spread evenly using a square bracket.
iii. the charge of each ion.

2) It is also called the Lewis diagram.

35
3) Using dot-and-cross diagram to represent the formation of ionic bond:

Strength of ionic bonds

1) The strength of ionic bond is a measure of the electrostatic force of attraction

between the ions.
(Q⁺) (Q⁻)
2) The force of attraction between the oppositely-charged E∝
ions is proportional to the charge on the ions and d²
inversely proportional to the square of distance between the ions.

3) The strength of ionic bond is manifested in the melting point of the ionic
compound.

4) i. For instance, the melting point of NaCl is higher than NaBr.

ii. This is because the size of Br⁻ ion is larger than Cl⁻ ion. Therefore the distance
between Br⁻ and Na⁺ is larger than that of between Cl⁻ and Na⁺.
iii. As a result, the electrostatic force of attraction between Na⁺ and Cl⁻ is stronger
than that of between Na⁺ and Br⁻ ion.

5) i. The melting point of NaCl is lower than MgCl2.

ii. This is because Mg²⁺ ion has a higher charge than Na⁺ ion. Besides that, the
size of Mg²⁺ ion is smaller than Na⁺ ion.
iii. The above two factors causes the electrostatic force of attraction between
Mg²⁺ and Cl⁻ to be stronger than that of between Na⁺ and Cl⁻.

36
4.2 Covalent Bonding
Formation of covalent bond

1) Covalent bond is the electrostatic force of attraction that two neighbouring nuclei
have for a localised pair of electrons shared between them.

2) Covalent bond is formed without transferring electrons, instead, the atoms

share their valence electron(s) to achieve duplet/octet electronic configuration.

3) The shared pair of electrons constitutes the covalent bond.

4) Using dot-and-cross diagram to represent the formation of covalent bond:

Formation of hydrogen Formation of oxygen gas,

gas, H₂ O₂

Single bond

1) Single bond is formed when one pair of electrons is shared between two
atoms.

2) Examples of compounds with single bonds:

37
Double bond

1) Double bond is formed when two pairs of electrons are shared between two
atoms.

2) Examples of compounds with double bonds:

Triple bond

1) Triple bond is formed when three pairs of electrons are shared between two
atoms.

2) Examples of compounds with triple bonds:

Lone pair and bond pair of electrons

1) The pair of electrons used in covalent bonding is called the bond pair while the
pair of electrons not used in covalent bonding is called the lone pair.

38
Octet-deficient and expanded octet species

1) In general, atoms tend to share their electrons to a achieve a duplet/octet

electronic configuration - the octet rule.

2) i. In octet-deficient species, the central atom has less than eight electrons.
ii. Some examples are boron trifluoride, BF3 and nitrogen monoxide, NO.

4) i. In expanded octet species, the central atom has more than eight electrons.
ii. An example is phosphorus(V) chloride, PCl5.
iii. This is possible only for Period 3 elements and beyond, this is because starting
from Period 3, the atoms have empty d orbitals in the third energy level to
accommodate more than eight electrons.

Octet deficient Expanded octet

Co-ordinate bond (dative covalent bond)

1) A co-ordinate bond is formed when one atom provides both the electrons
needed for a covalent bond.

2) Conditions of forming a co-ordinate bond:

i. one atom has a lone pair of electrons.
ii. another atom has an unfilled orbital to accept the lone pair, in other words,
an electron-deficient species.

3) Once the bond is formed, it is identical to the other covalent bonds. It does not
matter where the electrons come from.

4) In a displayed formula, a co-ordinate bond is represented by an arrow, the head

of the arrow points away from the lone pair which forms the bond.

39
5) An example is the reaction between ammonia and hydrogen chloride. In this
reaction, ammonium ion is formed by the transfer of hydrogen ion(an octet
deficient species) from hydrogen chloride to the lone pair of electrons in the
ammonia molecule.

6) Another example is aluminium chloride. At high temperature, it exists as AlCl3.

At low temperature(around 180-190°C), it exists as Al2Cl6, a dimer(two
molecules joined together). This is possible because lone pairs of electrons from
the chlorine atom form co-ordinate bonds with the aluminium atom.

Tips to draw dot-and-cross diagram for covalent molecules

1) Identify the central atom and terminal atom(s). For example, in ammonia, the
nitrogen is the central atom while the hydrogens are the terminal atoms.

2) During the sharing of electrons, the terminal atoms must attain octet
configuration(or duplet for hydrogen) but not necessarily for the central atom.

3) i. If the central atom is from Period 2 of the Periodic Table, the total number of
electrons surrounding it cannot exceed eight(but can less than eight).
ii. If the central atom is from Period 3 and beyond, the total number of electrons
surrounding it can exceed eight.

40
4) i. For polyatomic anions, the negative charge will be distributed among the
most electronegative atom(s). This is to decrease the charge density on a
particular atom and to stabilise the ion.
ii. For polyatomic cation, the positive charge will be distributed among the less
electronegative atom(s). The reason is same as above.

5) If the terminal atom already has octet configuration(for example, Cl⁻), it will
contribute two electrons to the central atom to form a co-ordinate bond.

4.3 Shapes of Molecules

Valence shell electron pair repulsion(VSEPR) theory

1) All electrons are negatively-charged, so they will repel each other when they are
close together.

2) So, a pair of electrons in the bonds surrounding the central atom in a molecule
will repel the other electron pairs. This repulsion forces the pairs of electrons
apart until the repulsive forces are minimised.

3) The amount of
repulsion is as
follow:

4) General steps to determine the shape of a molecule:

i. determine the number of valence electrons in the central atom.
ii. find the total number of electrons surrounding the central atom by adding the
number of shared electrons to it. (Dot-and-cross diagram might be necessary)
iii. find the number of electron pairs by dividing the total number of electrons by
two.
iv. determine how many pairs is/are bond pairs and lone pairs. (A double bond
or triple bond is counted as one bond pair)
v. refer to the table to obtain the shape of the molecule

41
42
Effect of lone pair on bond angle

1) For methane, ammonia and water, the electron pair

geometries are tetrahedral. However, the molecular
geometries are different.

2) In methane, all the bonds are identical, repulsion between the

bonds is the same. Thus, methane has a perfect tetrahedral
structure with bond angle 109.5°.

3) In ammonia, the repulsion between the lone pair and the bond
pairs is stronger than in methane. This forces the bond angle to
decrease slightly to 107°.

4) In water, there are two lone pairs and thus the repulsion is the greatest, the two
bond pairs are pushed closer to one another and the bond angle is reduced to
104.5°.

Effect of electronegativity on bond angle

1) Water and hydrogen sulfide have the same general

shape with the same number of bond pairs and lone
pairs. However, their bond angles are different.

2) This is because oxygen has a higher electronegativity than sulphur. The bond
pairs of electrons are closer to the oxygen atom compared to the sulfur atom.

3) This results in greater repulsion in the O-H bonds than in the S-H bonds.
Therefore, the bond angle increases from 92.5° to 104.5°.

Sigma(σ) bond and pi(π) bond

1) A sigma bond is formed by orbitals from two atoms overlapping end-to-end.

2) In a sigma bond, the electron density is concentrated between the two nuclei.

43
3) A pi bond is formed by the p orbitals from two atoms
overlapping sideways.

4) In a pi bond, there are two regions of high electron density

alongside the nuclei.

5) A pi bond is weaker than a sigma bond because the overlapping of charge

clouds is less than in a sigma bond.

6) In covalent molecules, single bonds are sigma bonds(σ), a double bond

consists of one sigma bond and one pi bond(1σ, 1π), and a triple bond
consists of one sigma bond and two pi bonds(1σ, 2π).

Hybridisation

1) Hybridisation is the mixing of atomic orbitals to produce a new set of hybrid

orbitals of equivalent energies. This is a theory used to account for the
discrepancies in explaining the shapes of covalent molecules.

2) There is a problem with simple view on methane, CH4.

Methane has two unpaired electrons only in its outer
shell to share with the hydrogen atoms, but the formula of methane is not CH2.

3) The concept of hybridisation is used to account for this discrepancy.

4) General steps in hybridisation:

i. promotion of electron.
ii. mixing of orbitals to produce a new set of hybrid orbitals of equivalent
energies(sp, sp² or sp³ hybrid orbitals)
iii. forming of a new molecular orbital.

44
sp³ hybridisation

1) An example of compound which undergoes sp³

hybridisation is methane, CH4. C:
2) The carbon atom uses some energy to promote one of
its electron from 2s to empty 2p orbital so that there
are four unpaired electrons for covalent bonding.
C* :
3) The carbon now is said to be in an excited state(C*).

4) The orbitals then 'mix' or hybridise to produce four

hybrid orbitals of equivalent energies. The new
orbitals are called sp³ hybrid orbitals because they are made from one s orbital
and three p orbitals.

5) Each hybrid orbital has one big lobe and one small lobe. They
rearrange themselves so that they are as far as possible to form a
tetrahedral geometry. The hybrid orbitals are 109.5° apart.

6) The s orbitals from the hydrogen atoms then

overlap with the four hybrid orbitals to form
four sigma bonds because the overlapping is
end-to-end. All the bonds are identical.

7) Another example is ethane, C2H6. The two

carbon atoms undergo sp³ hybridisation to form four hybrid orbitals. The two
carbon atoms are bonded by overlapping one of their hybrid orbitals. The
remaining ones then overlap with the s orbitals of the hydrogen atoms.

8) The bond angle is approximately 109.5°. This is an approximation because all

the bonds are not identical.

45
sp² hybridisation

1) An example of compound which undergoes sp² hybridisation is ethene, C2H4.

2) The same thing happens as in sp³

hybridisation, except that this time the
carbon atoms 'mix' or hybridise three of the four orbitals only because the
carbon atom is bonding with three other atoms only.

3) This produces three sp² hybrid orbitals because they

are made from one s orbital and two p orbitals. Another p
orbital remains unchanged and it is perpendicular to
the plane containing the hybrid orbitals.

4) The hybrid orbitals rearrange themselves so that they are as far as possible, that
is, a trigonal planar arrangement, the hybrid orbitals are 120° apart.

5) The hybrid orbitals then overlap with s orbitals

from the hydrogen atoms and another hybrid
orbital from the other carbon atom to form
five sigma bonds. The remaining p orbitals
overlap sideways to form a pi bond. A double
bond is formed between the two carbon atoms.

6) Another example is boron trichloride, BCl3. The boron atom undergoes sp²
hybridisation to produce three sp² hybrid orbitals. The hybrid orbitals rearrange
themselves to form a trigonal planar geometry. The p orbitals from chlorine
atoms then overlap with the hybrid orbitals to form three sigma bonds.

46
sp hybridisation

1) An example of compound which undergoes sp hybridisation is ethyne, C2H2.

2) The same thing happens as in sp³ and sp² hybridisation,

except that this time the carbon atoms 'mix' or hybridise
two of the four orbitals only because the carbon atom is bonding with two
other atoms only.

3) This produces two sp hybrid orbitals because they are

made from one s orbital and one p orbital. The other two p
orbitals remain unchanged and they are perpendicular to
each other and to the two hybrid orbitals.

4) The hybrid orbitals rearrange themselves so that they are as far as possible, that
is, a linear arrangement, the hybrid orbitals are 180° apart.

5) The hybrid orbitals overlap with the s orbitals from the hydrogen atoms and to
the hybrid orbital from the other carbon atom to form three sigma bonds.
The remaining p orbitals overlap sideways to form two pi bonds. A triple
bond is formed between the two carbon atoms.

Example of covalent molecule with multiple hybridisations

1) In carbon dioxide, CO2, the carbon atom

undergoes sp hybridisation while the
oxygen atoms undergo sp² hybridisation.
The overlapping of the hybrid and p
orbitals are shown in the diagram.

47
4.4 Electronegativity, Bond Polarity, Bond Length
and Bond Energy
Electronegativity

1) Electronegativity is the ability of an atom which is covalently bonded to the other

atom to attract the bond pair of electrons towards itself.

2) The more electronegative an atom is, the higher the tendency of that atom to
attract the bond pair of electrons towards itself.

3) The Pauling scale is commonly used to quantify the value of electronegativity

of a particular element.

4) Fluorine is the most electronegative element because of its small size, followed
by oxygen and nitrogen.

Trends of electronegativity values in the Periodic Table

1) i. The value of electronegativity increases across a

Period(from left to right).
ii. This is because the number of proton increases across
a Period. Therefore the amount of positive charge in
the nucleus also increases.
iii. The shielding effect by inner electrons remains constant.
iv. Therefore the attraction towards the bond pair of electrons increases, making
it more electronegative.

2) i. The value of electronegativity decreases

down a Group.
ii. This is because the size of the atoms
increases down a Group. Therefore the
distance between the nucleus and the bond
pair of electrons also increases.
iii. The shielding effect by inner electrons is also greater.
iv. Therefore the attraction towards the bond pair of electrons decreases, making
it less electronegative.

48
Bond Polarity

1) i. When two covalently-bonded atoms have the same

electronegativity, the electron cloud is evenly distributed between the two
atoms.
ii. The bond is described as a 'pure' covalent bond or non-polar bond.
iii. Some examples are H2, Cl2 and Br2.

2) i. However, when an atom is more electronegative than

the other, the more electronegative atom will attract the
bond pair of electrons more towards itself. The electron cloud is not evenly
distributed or distorted.
ii. The more electronegative end acquires a partial negative charge while the less
electronegative end acquires a partial positive charge.
iii. The bond is said to be polarised, or, a polar bond.
iv. Some examples of compound which contain polar bond(s) are HCl and CH4.
v. The molecule is described as 'covalent with some ionic character'.

3) i. When the electronegativity difference between the two atoms is very great, the
less electronegative atom will lose its electrons and the more electronegative
atom will gain the electrons.
ii. An ionic bond will be formed.

Polar and non-polar molecules

1) A molecule is polar, and thus, has a dipole moment(μ ≠ 0) if:

i. the bonds are polarised
ii. the dipole of the bonds do not cancel out each other(in other words, it is
asymmetrical)

2) The dipole moment, μ is the product of charges and the distance between the
centre of the charges.

49
3) Examples:

4) A liquid containing polar molecules can be

deflected by a charged rod brought near to it. This
is because there is a positive end and a negative end
in polar molecules. So, irregardless of the charge on
the rod, one end of the molecule will always be
attracted towards the charged rod.

5) When polar molecules are placed in an electric

field, the positive end of the molecule will face
towards the negative terminal while the negative
end of the molecule will face towards the positive
terminal.

6) Generally, polar molecules are more reactive than non-polar molecules because
many chemical reactions are started by a reagent attacking an electrically-
charged end of the polar molecule. An example is CO is more reactive than N2
although both of them have triple bonds because CO is polar while N2 is not.

Bond length and bond energy

1) Bond length is the distance between two nuclei of two atoms

joined by a covalent bond.

2) Bond energy is the energy needed to break one mole of covalent bonds between
two atoms in the gaseous state.
A-B(g) → A(g) + B(g) ∆H° = +x J

4) i. The shorter the bond length, the stronger is the bond.

ii. The greater the bond energy, the stronger is the bond.
iii. Hence, the shorter and bond length, the greater the bond energy.

50
4.5 Intermolecular Forces
Intermolecular and intramolecular forces

1) i. Intramolecular force is the force of

attraction that hold individual atoms
together in a molecule.
ii. Commonly referred to as covalent bonds.

2) Intermolecular force is the force of attraction between one molecule and

the neighbouring molecule.

3) There are several types of intermolecular forces:

Intermolecular forces

van der Waals' forces Hydrogen bond

- Permanent dipole-dipole forces
(Keesom forces)
- Temporary dipole-induced dipole forces
(Dispersion forces or London forces)

4) Intermolecular forces are much weaker than intramolecular forces.

5) Intermolecular forces are responsible for the melting and boiling points of
substances, as well as their physical states.

Permanent dipole-dipole forces(Keesom forces) Permanent dipole-dipole forces

1) Polar molecules have a negative end and a

positive end. The oppositely-charged ends
will attract one another. The forces of attraction is called permanent dipole-
dipole forces.

2) Only polar molecules will experience permanent dipole-dipole forces.

51
Temporary dipole-induced dipole forces(Dispersion forces or London forces)

1) Electrons are mobile, and constantly revolving around the nucleus. Even in non-
polar molecules, there is a high possibility that at any given instant, the electron
density is higher on one side than the other.

2) This will result in the formation of temporary dipole(or instantaneous dipole)

because it only lasts for just a tiny fraction of time.

3) In the next instance, the distribution of electron density will change and the
molecule has a new temporary dipole.

4) The temporary dipole set up can distort the

electron charge clouds of the neighbouring
molecules, giving rise to induced dipoles.

5) The forces of attraction between

temporary dipoles and induced dipoles
give rise to dispersion forces.

6) All molecules(polar and non-polar) will experience dispersion forces. For

polar molecules, permanent dipole-dipole forces exist in addition with
dispersion forces.

Factors affecting strength of dispersion forces

1) Number of electrons in the molecule(Size of molecule)

- As the number of electrons increases, the size of the molecule also increase.
- This causes the attraction between the nucleus and the electrons to get weaker,
the electrons become progressively easier to be distorted.
- This causes more temporary dipoles to be set up and the dispersion forces get
stronger.
- The boiling point of halogens increases going down the Group. The size of
the molecules increases and thus the van der Waals' forces become stronger.

2) Number of contact points between the molecules(Surface area)

- For two molecules of the same number of electrons, the one which has a larger
surface area has more contact points between the molecules.
- The more contact points between molecules, more temporary dipoles can be
set up and the dispersion forces become stronger.

52
 - Butane is a long chain molecule while 2-methypropane is more spherical
(more compact). This causes the number of contact point between butane
molecules to be more than in 2-methypropane.
- Therefore the van der Waals' forces of
attraction in butane is stronger than in
2-methypropane. This causes the
boiling point of butane to be higher.

Hydrogen bonding

1) Hydrogen bond is the electrostatic force of attraction between a hydrogen atom

(which is covalently bonded to a small and highly electronegative atom) and the
lone pair of electrons of another small and highly electronegative atom.

2) The 'small and highly electronegative atoms' are fluorine, oxygen and nitrogen.

3) The conditions necessary for forming hydrogen bonds:

i. a hydrogen atom bonded directly to a small and electronegative
atom, causing it to acquire a significant amount of partial positive charge.
ii. a lone pair of electrons from the small and electronegative atom.

4) The attraction between the hydrogen atom and the lone pair of electrons
constitutes the hydrogen bond.

5) The evidence of hydrogen bonding:

- H2O, HF and NH3 have
exceptionally high boiling points
compared to other compounds
with greater number of electrons.
- This suggests that there must be
an additional intermolecular force
other than van der Waals' forces
exists between them.
- This additional intermolecular force is called the hydrogen bond.

6) H2O has a higher boiling point compared to NH3 and HF. This is because a
H2O molecule can form, on average four hydrogen bonds. In NH3, the number
of hydrogen bonds is restricted by the one lone pair of electrons in the NH3
molecule. In HF, it is restricted by the number of hydrogen atoms.

53
The peculiar properties of water

1) Solid ice is less dense than liquid water

- Most solids are denser than their liquids, this is because in the solid state, the
molecules are packed closer and occupies smaller volume.
- However, solid ice is less dense than liquid water.
- This is because in the solid state, the water
molecules are bonded to each other through
hydrogen bonding to form a giant
3-dimensional tetrahedral structure. This
structure has a lot of empty spaces in between
the water molecules.
- When heat is supplied, some of the hydrogen bond breaks down and the rigid
structure collapses, filling up the spaces in between them, thus decreasing the
volume occupied and increasing its density.

2) Solubility of substances in water

- Most covalent compounds are not soluble water while ionic compounds are.
- However, some covalent compounds are soluble in water because they can
form hydrogen bonds with water, some examples are ammonia and alcohols

3) High boiling point of water

- The boiling point of water is exceptionally high compared to other Group 16
hydrides(see graph at page 21).
- This is because water molecules are capable of forming hydrogen bonds
between themselves. This additional type of intermolecular forces increases its
boiling point significantly.

4) High surface tension and viscosity

- Water has a high viscosity. This is because hydrogen bonding reduces the
ability of water to slide over each other, making it more viscous.
- Water has a high surface tension. This is because hydrogen bonds also exert a
significant downward force at the surface of liquid.

54
4.6 Metallic Bonding
Metallic bonds

1) Metallic bond is the electrostatic force of attraction between the delocalised

electrons and the positive metal ions.

2) Take sodium as an example, in the solid state,

sodium atoms are packed so closely together that the
3s orbitals(containing an electron) overlap with one
another to form a giant molecular orbital.

3) The 3s electrons is then free to move throughout the

lattice structure, it is no longer bound to any sodium
atom. The electrons are said to be delocalised. The delocalised electrons are
sometimes referred to as 'sea of delocalised electrons'.

4) The attraction between the delocalised electrons and the positive metal ions
constitutes the metallic bond.

Factors affecting the strength of metallic bonds

1) Number of electrons in the sea of delocalised electrons

- The more the number of electrons delocalised, the stronger the metallic
bond.
- For example, the melting point of magnesium is higher than sodium.
- This is because one magnesium atom can donate two electrons from its outer
shell into the sea of delocalised electrons while sodium can only donate one.
- There is twice amount of delocalised electrons in magnesium than in sodium.
So, the metallic bond in magnesium is stronger due to the stronger attraction.

2) Size of the metal

- The smaller the size of the metal, the stronger the metallic bond.
- For example, the melting point of magnesium is lower than beryllium
although both of them have two electrons delocalised per atom.
- This is because the size of magnesium is bigger, causing the attraction between
the delocalised electrons and the positive nucleus to be weaker. The shielding
effect in magnesium is also more than in beryllium.
- So, the metallic bond in magnesium is weaker than in beryllium.

55
4.7 Bonding and Physical Properties of Substances
Physical state at room temperature

1) Ionic compounds
- Ionic compounds are solids at room temperature, this is because the ionic
bond holding the oppositely-charged ions is very strong, a lot of energy is
required to overcome the strong forces of attraction.

2) Covalent compounds
- Most simple covalent molecules(like water and ammonia) are liquids or gases
at room temperature. This is because the intermolecular force between the
molecules is weak, little energy is required to overcome it.
- Some simple covalent molecules(like iodine) are solids because the
intermolecular force between them is strong enough.
- For giant covalent structures(like diamond and silicon dioxide), they are solids
at room temperature. This is because the covalent bonds holding the atoms
are very strong, a lot of energy is required to overcome it.

3) Metals
- Metals(except mercury) are solids at room temperature. This is because the
metallic bond holding the metal ions is very strong, a lot of energy is required
to overcome it.

Electrical conductivity

1) Ionic compounds
- Ionic compounds do not conduct electricity in the solid state, this is because
the ions are not free to move.
- In the molten or aqueous state, it conducts electricity because the ions are free
to move(mobile ions are present).

2) Covalent compounds
- Simple covalent molecules do not conduct electricity because the ions are not
free to move.
- Some giant covalent structures(like graphite) are able to conduct electricity
because the electrons are free to move(delocalised). (See also Chapter 5)

56
3) Metals
- Metals conduct electricity because the delocalised electrons are free to move.

Solubility

1) Ionic compounds
- Most ionic compounds are soluble in water(polar solvents) and insoluble in
non-polar solvents.
- This is because in non-polar solvents, the molecules are held together by weak
intermolecular forces. The ionic bonds in ionic compounds are much stronger
and the energy needed to break them is high. If ion-solvent bonds are formed,
the energy released is not enough to compensate the energy absorbed,
making the entire structure unstable.
[ Note: To form ion-solvent bonds, the ion-ion(ionic bond) and solvent-solvent
(van der Waal's forces) bonds must be broken first. ]
- While in polar molecules, there is an attraction between polar molecules
and the ions. So, the energy released when ion-solvent bonds are formed is
enough to compensate the energy needed to break the strong ionic bonds.

2) Covalent compounds
- This is because when a covalent molecule is dissolved in a non-polar solvent,
the molecule-solvent attraction is strong enough to compensate the energy
needed to break the weak van der Waal's forces between covalent molecules.
- While when dissolved in polar solvents, the energy needed to break the
attractions in polar solvents is too high. The energy released when molecule-
solvent attraction set up is not enough to compensate it. This makes the
structure to gain energy overall, making it less stable.
- Some covalent compounds react with water rather than dissolving in it. For
example, hydrogen chloride reacts with water to form hydrogen ions and
chloride ions, and the ions are soluble.

3) Metals
- Metals do not dissolve in polar and non-polar solvents.
- However, some metals like sodium and calcium can react with water.

57
CHAPTER 6: Chemical Energetics
6.1 Enthalpy Changes
6.2 Standard Enthalpy Changes
6.3 Hess' Law
6.4 Bond Energy

Learning outcomes:

(a) explain that some chemical reactions are accompanied by energy changes, principally in the
form of heat energy; the energy changes can be exothermic (∆H, negative) or endothermic.
(b) explain and use the terms:
(i) enthalpy change of reaction and standard conditions, with particular reference to:
formation, combustion, hydration, solution, neutralisation, atomisation.
(ii) bond energy (∆H positive, i.e. bond breaking).
(c) calculate enthalpy changes from appropriate experimental results, including the use of the
relationship enthalpy change, ∆H = –mc∆T.
(d) apply Hess’ Law to construct simple energy cycles, and carry out calculations involving such
cycles and relevant energy terms, with particular reference to:
(i) determining enthalpy changes that cannot be found by direct experiment, e.g. an enthalpy
change of formation from enthalpy changes of combustion.
(ii) average bond energies.
(e) construct and interpret a reaction pathway diagram, in terms of the enthalpy change of the
reaction and of the activation energy.

58
6.1 Enthalpy Changes
Exothermic and endothermic reactions

1) Most chemical reactions are accompanied by energy changes. Some absorbs

energy while some releases it.

2) An exothermic reaction is a reaction that releases energy to the surroundings.

Therefore the product contain less energy with respect to the reactants. The
energy is released as heat energy, so the surroundings warm up.

3) An endothermic reaction is a reaction that absorbs energy from the surroundings.

Therefore the products contain more energy with respect to the reactants. The
energy is absorbed as heat energy, so the surroundings cool down.

4) An energy level diagram shows the relative energies of the products and
reactants. The higher its energy, the higher its position.

An exothermic reaction An endothermic reaction

5) i. Examples of exothermic reactions are neutralisation, combustion, dissolving

anhydrous salts and the reaction between acids and metal carbonates.
ii. Examples of endothermic reactions are atomisation, photosynthesis,
dissolving crystalline salts and thermal decomposition.

Enthalpy changes

1) Enthalpy, H is an indication of the total energy of a substance and it cannot be

measured directly. However, enthalpy change, ∆H is measurable.

59
2) Enthalpy change of a reaction, ∆H is the heat change(heat is absorbed or evolved)
when a chemical reaction takes place.

3) i. In exothermic reactions, the enthalpy change is always negative.(∆H < 0)

ii. In endothermic reactions, the enthalpy change is always positive.(∆H > 0)

Energetic stability of a system

1) Exothermic reactions are more energetically favourable than endothermic ones

because a system with lower energy content is more stable.

2) Thus, the more negative the ∆H value, the more stable the system is.

3) For example, oxygen,O2 is energetically more

stable than ozone, O3. Their relative positions on
the energy level diagram are as follow:

4) But ozone does not convert to oxygen

immediately in atmosphere, this is because ozone
is kinetically stable although it is energetically
unstable with respect to the products. The
activation energy is not sufficient for the reaction to take place.

Measuring enthalpy changes

1) Enthalpy changes can be measured experimentally by measuring the

temperature change as a reaction proceeds. Two common examples are
measuring the enthalpy change of neutralisation and combustion.

2) The formulae:

where m = mass of substance(or solution)/g

Heat energy absorbed c = specific heat capacity of solution/J g⁻¹ °C⁻¹
= mc∆T where m = mass of solution/g
(c is normally assumed to be 4.18 J g⁻¹ °C⁻¹)
or released c = specific heat capacity
∆T = change in temperature/°C
of solution
(c is normally taken
as 4.13 J g⁻¹ K⁻¹ )
heat energy absorbed or released ∆T = change in temperature
∆H = Unit = kJ mol⁻¹
no. of moles of the limiting reagent

60
3) Assumptions made in this calculation:
- The density of all aqueous solution is 1 g cm⁻³. Thus, numerically, 1 cm³ = 1 g.
- The solution has the same specific heat capacity as water(4.18 J g⁻¹ °C⁻¹).

4) An example - to calculate the enthalpy change of the reaction between sodium

hydroxide, NaOH(aq) and hydrochloric acid, HCl(aq).
NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l)

i. Pour 25 cm³ of NaOH into 25 cm³ of HCl

in a polystyrene cup(polystyrene cup is used
because it is a good heat insulator). Both solutions
have concentrations of 1.0 mol dm⁻³.
ii. Measure the initial and maximum temperature
reached.
iii. For example, the mean initial temperature of both
solutions is 18.1 °C and the maximum temperature
reached is 24.8 °C. Then, ΔT = 6.7 °C.
iv. Mass of both solutions is (25+25) x 1 = 50 g since density = mass/volume.
v. Therefore heat released = 50 x 4.18 x 6.7 = 1400 J = 1.4 kJ
vi. Number of moles of water = 0.025 mol
vii. Therefore ΔH = -(1.4/0.025) = -56 kJ mol⁻¹

5) Another example - to calculate the enthalpy change of the reaction of

combustion of ethanol, C2H5OH.
C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(g)

i. In this experiment, a spirit burner is used to

combust the flammable liquid ethanol. The heat
evolved is used to heat up the water, the maximum
temperature reached is then measured.
ii. Mass of water = 250 g
Initial temperature of water = 19.5 °C
Maximum temperature of water = 23.7 °C
Initial mass of ethanol = 41.36 g
Final mass of ethanol = 41.18 g
iii. Therefore, ΔT = 4.2 °C and m = 250 g.
iv. Heat released = 250 x 4.18 x 4.2 = 4389 J = 4.389 kJ
v. Number of moles of ethanol burned = 0.18/46 = 0.0039 mol
vi. Therefore ΔH = -(4.389/0.0039) = -1100 kJ mol⁻¹ (2 s.f)

61
6.2 Standard Enthalpy Changes
The standard condition

1) To make comparison of enthalpy changes a fair comparison, same conditions

must be used. These are called the standard conditions:
- A pressure of 100 kPa(approximately atmospheric pressure).
- A temperature of 298 K or 25 °C.
- Where solutions are involved, a concentration of 1.0 mol dm⁻³.
- Every substance involved must be in its normal physical state at 100 kPa
and 298 K. For example, water is in liquid, not ice or steam.
- If allotropes are involved, the allotrope which is more energetically stable is
used. For example, for carbon, graphite is chosen over diamond because
graphite is energetically more stable than diamond.

2) Standard enthalpy changes can be represented by the symbol ΔH°. This

refers that the reaction is carried out under standard conditions. For example:

CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ; ΔH° = -890.3 kJ mol⁻¹

Various enthalpy changes

1) Enthalpy changes are described according to the type of reaction. Examples:

- standard enthalpy change of reaction, ΔH°r (in general)
- standard enthalpy change of formation, ΔH°f
- standard enthalpy change of combustion, ΔH°c
- standard enthalpy change of neutralisation, ΔH°n
- standard enthalpy change of atomisation, ΔH°at
- standard enthalpy change of solution, ΔH°sol
- standard enthalpy change of hydration, ΔH°hyd

Standard enthalpy change of reaction, ΔH°r

1) Standard enthalpy change of reaction, ΔH°r is the enthalpy change when the amount
of reactants shown in the equation react to give products under standard
condition. The reactants and products must be in their standard states.

2H2(g) + O2(g) → 2H2O(l) ; ΔH°r = -576 kJ mol⁻¹

62
2) The equation shows that 576 kJ of energy is released when two moles of
hydrogen react with one mole of oxygen to give two moles of water.

3) This is a theoretical reaction, it does not happen in practice. The enthalpy

change can be found by applying Hess' law.

Standard enthalpy change of formation, ΔH°f

1) Standard enthalpy change of formation, ΔH°f is the enthalpy change when one mole
of a compound is formed from its elements under standard condition.
The reactants and products must be in their standard states.

2Fe(s) + 1½O2(g) → Fe2O3(s) ; ΔH°f [ Fe2O3(s) ] = -824.5 kJ mol⁻¹

2) By definition, the standard enthalpy change of formation of an element is zero.

3) The standard enthalpy change of formation can be exothermic or endothermic.

Standard enthalpy change of combustion, ΔH°c

1) Standard enthalpy change of combustion, ΔH°c is the enthalpy change when one mole
of a substance is burnt in excess oxygen under standard conditions. The
reactants and products must be in their standard states.

CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ; ΔH°c [ CH4(g) ] = -890.3 kJ mol⁻¹

2) The standard enthalpy change of combustion is always exothermic.

Standard enthalpy change of neutralisation, ΔH°n

1) Standard enthalpy change of neutralisation, ΔH°n is the enthalpy change when one
mole of water is formed by the reaction of an acid with an alkali under
standard conditions.

HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l) ; ΔH°n = -57.1 kJ mol⁻¹

2) For any acid-alkali reaction, the ionic equation is:

H⁺(aq) + OH⁻(aq) → H2O(l)

63
3) The enthalpy change of neutralisation between strong acids and strong
bases is a constant(-57.1 kJ mol⁻¹). This is because all strong acids and strong
bases dissociate completely in water to form aqueous ions.

4) So, neutralisation between strong acids and strong bases involves the same
reaction, that is, H⁺ reacts with OH⁻ to form H2O. The other ions present are
just simply spectator ions. They do not take part in the reaction. Hence, the
heat released is the same.

5) However, the enthalpy change of neutralisation between sulfuric acid and

sodium hydroxide is more exothermic(-66.8 kJ mol⁻¹) than expected. This is
because the enthalpy change of dilution of sufuric acid is significant. When
sulfuric acid is added to sodium hydroxide, the acid is diluted in the process and
heat is released.

6) The enthalpy change of neutralisation involving weak acids or weak bases

is less than 57.1 kJ mol⁻¹. For example:
CH3COOH(aq) + NaOH(aq) → CH3COONa(aq) + H2O(l) ;
ΔH°n = -56.1 kJ mol⁻¹
NaOH(aq) + HCN(aq) → NaCN(aq) + H2O(l) ; ΔH°n = -11.7 kJ mol⁻¹

7) This is because weak acids and weak bases only partially dissociated in water.
For example:
CH3COOH(aq) ⇌ CH3COO⁻(aq) + H⁺(aq) ; ΔH° = positive
8) On addition of strong base such as NaOH, the OH⁻ ions react with H⁺ from the
dissociation of CH3COOH. The removal of H⁺ ions causes the position of
equilibrium to shift to the right and more CH3COOH molecules dissociate.
However the dissociation of CH3COOH is an endothermic process, hence,
some energy is absorbed and the enthalpy change overall is less negative.

9) The standard enthalpy change of neutralisation is always exothermic.

Standard enthalpy change of atomisation, ΔH°at

1) Standard enthalpy change of atomisation, ΔH°at is the enthalpy change when one mole
of gases atoms is formed from its element under standard conditions.

½H2(g) → H(g) ; ΔH°at [ ½H2 ] = +218 kJ mol⁻¹

Na(s) → Na(g) ; ΔH°at [ Na ] = +107 kJ mol⁻¹

64
2) By definition, the standard enthalpy change of atomisation of the noble gases is
zero because all of them exist as monoatomic gases at standard conditions.

3) The standard enthalpy change of atomisation of diatomic gases(example: O2,

Cl2, N2 and F2) is equal to half the value of their bond energies.

4) The standard enthalpy change of atomisation is always endothermic.

Standard enthalpy change of solution, ΔH°sol

1) Standard enthalpy change of solution, ΔH°sol is the enthalpy change when one mole
of solute is dissolved in a solvent to form an infinitely dilute solution under
standard conditions.

NaCl(s) + aq → NaCl(aq) ; ΔH°sol = +6.0 kJ mol⁻¹

NaOH(s) + aq → NaOH(aq) ; ΔH°sol = -44.5 kJ mol⁻¹

2) An infinitely dilute solution is one which does not produce any further enthalpy
change when more solvent is added.

3) The standard enthalpy change of solution can be exothermic or endothermic.

Standard enthalpy change of hydration, ΔH°hyd

1) Standard enthalpy change of hydration, ΔH°hyd is the enthalpy change when one mole
of gases ions dissolves in water to form hydrated ions of infinite dilution under
standard conditions.

Ca²⁺(g) + aq → Ca²⁺(aq) ; ΔH°hyd = -1650 kJ mol⁻¹

2) Water is a polar molecule, this means that it has a negative end and a positive
end. The negative end of the water molecule will be attracted to the cations
while the positive end of the water molecule will be attracted to the anions.

3) The attraction set up is called the ion-dipole forces.

4) The standard enthalpy change of hydration is always exothermic.

65
6.3 Hess' Law
Hess' law and Hess' cycle

1) Hess' law states that the total enthalpy change in a chemical reaction is
independent of the route which the reaction takes place as long as the initial
and final conditions are the same.

2) For example, the enthalpy change of reaction from A to C is the same whether
the reaction takes place in one stage(A to C) or two stages(A to B then to C).

3) This is because the enthalpy change of a chemical reaction depends only on the
difference between enthalpy of the products and the reactants. It does not
depend on how the reaction took place.

4) Hess' law is useful to calculate enthalpy changes that cannot be measured

directly from experiments(theoretical reactions that will not occur under
standard conditions).

5) Steps to construct a Hess' cycle:

i. Write down the equation for the enthalpy change that you are asked to find
and write ΔH on top of the arrow.
ii. Use the information that you have been given to complete a cycle.
iii. Find the direct route and indirect route. The routes should not go against any
arrows. (Equations may be reversed when necessary, but do not forget to
reverse the sign as well.)
iv. Apply Hess' law and form an equation to solve for ΔH.

66
6) Examples:

6.4 Bond Energy

Bond breaking and bond forming

1) i. Breaking bonds needs energy, energy is absorbed from the surroundings.

Therefore, bond breaking is an endothermic process.
ii. Forming bonds releases energy to the surroundings. Therefore, bond forming
is an exothermic process.

2) i. If the energy needed to break bonds is less than the energy released when
new bonds are formed, then the reaction will be exothermic
ii. If the energy needed to break bonds is more than the energy released when
new bonds are formed, then the reaction will be endothermic.

3) In most chemical reactions, bonds have to be broken first and then reformed
into a new compound.

67
 An endothermic reaction An exothermic reaction

Bond energy

1) Bond energy, E is the energy needed to break one mole of covalent bonds between
two atoms in the gaseous state.

Br-Br(g) → 2Br(g) ; E(Br-Br) = +193 kJ mol⁻¹

2) Bond energy is often called bond enthalpy or bond dissociation energy.

Average bond energy

1) Bond energy is often affected by the presence of other atoms in the molecule.
For example, the O-H bond in water has a different bond energy value than the
O-H bond in ethanol. Even in the same molecule, for example, CH4, the energy
needed to break all the C-H bonds are not identical.

2) Therefore, bond energies are taken from a number of bonds of the same type
from different environment and average out to get the average bond energy.
The values are not always accurate.

68
Hess' law involving average bond energy

1) Average bond energies can also be used to estimate enthalpy changes of

reactions involving covalent molecules

2) Example:

3) If the given reactants or products are not in the gaseous state, enthalpy
change of vaporisation or enthalpy change of fusion must be considered
because the non-gaseous compounds needed to be converted to the gaseous
state. Changing from other states to the gaseous state needs to absorb extra
energy.

69
CHAPTER 7: Redox Reactions and Electrolysis
7.1 Oxidation and Reduction
7.2 Electrolysis

Learning outcomes:

(a) (i) calculate oxidation numbers of elements in compounds and ions.

(ii) describe and explain redox processes in terms of electron transfer and/or changes in
oxidation number (oxidation state).
(iii) use changes in oxidation numbers to help balance chemical equations.
(b) explain, including the electrode reactions, the industrial processes of:
(i) the electrolysis of brine, using a diaphragm cell.
(ii) the extraction of aluminium from molten aluminium oxide/cryolite.
(iii) the electrolytic purification of copper.

70
7.1 Oxidation and Reduction
Redox reactions

1) Oxidation is:
i. gain of oxygen
ii. loss of hydrogen
iii. loss of electrons
iv. increase in oxidation number

2) Reduction is:
i. gain of hydrogen
ii. loss of oxygen
iii. gain of electrons
iv. decrease in oxidation number

3) Oxidation and reduction always occur simultaneously in a chemical reaction.

Such reaction is called a redox reaction. In a redox reaction, one substance
must be oxidised and another must be reduced.

4) i. An oxidising agent is a substance which oxidises another substance and itself is

reduced.
ii. A reducing agent is a substance which reduces another substance and itself is
oxidised.

5) In short, an oxidising agent undergoes reduction while a reducing agent

undergoes oxidation.

6) Disproportionation is a redox reaction in which both oxidation and

reduction occurs on the same atom. The atom is simultaneously oxidised and
reduced.

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Oxidation state (oxidation number) of a substance

1) Oxidation state shows that total number of electrons which have been removed
from or added to an element to get to its present state.

2) i. When electrons have been removed, the oxidation number increases.(positive)

ii. When electrons have been added, the oxidation number decreases.(negative)

3) i. Since removing electrons is an oxidation process, therefore oxidation is the

increase in oxidation number
ii. Since adding electrons is a reduction process, therefore reduction is the
decrease in oxidation number.

3) For example, from V to V²⁺, two electrons have been removed, therefore the
oxidation state of is +2. From V to V³⁺, three electrons have been removed,
therefore the oxidation state is +3. Removing another electron gives:
V³⁺ + H2O → VO²⁺ + 2H⁺ + e⁻

Four electrons have been removed starting from V, therefore the oxidation state
is +4. In all cases, V has been oxidised.

4) Another example, from S to S²⁻, two electrons have been added, therefore the
oxidation state is -2. S is said to have been reduced.

Rules to determine oxidation numbers of a substance

1) All atoms in an atom, molecule or ion can be given an oxidation number.

2) The rules to determine the oxidation number of a substance:

i. All free atoms in elements have an oxidation number of zero.
e.g.

ii. For simple ions, the oxidation number is the same as the charge on the ion.
e.g.

iii. For polyatomic ion, the sum of all the oxidation numbers of the atoms in
the ion is equal to the charge of the ion.

72
 e.g.

iv. For a neutral covalent molecule, the sum of all the oxidation numbers of
the atoms in the molecule is equal to zero.
e.g.

Also, the more electronegative atom is always given a negative oxidation

number while the less electronegative atom is given a positive one.

v. For Group I and Group II elements, their oxidation number are always +1
and +2 respectively. For aluminium, it is always +3.

vi. For hydrogen, its oxidation number is always +1 except in metal hydrides.
For example, NaH, where its oxidation number is -1.

vii. For oxygen, its oxidation number is always -2 except in peroxides and
fluorine compounds. For example, BaO2, where its oxidation number is -1.

viii. For fluorine, its oxidation number is always -1, with no exceptions.

3) A summary:

4) To work out the oxidation number of a particular atom in a molecule/ ion, find
the sum of all the oxidation number of the atoms present and equate it to zero/
charge of the ion. An example:

73
Balancing redox equations

1) There are two methods to balance complicated redox equations:

i. Using electron half-equations.
ii. Using changes in oxidation number.

2) Using electron half-equations:

i. In this method, the redox equation is divided into two half-equations. One for
oxidation and another for reduction.
ii. Steps(in acidic condition):
- Divide the equation or information given into two half-equations.
- Balance all other elements other than oxygen and hydrogen.
- Balance the oxygen by adding H2O to the appropriate side of the equation.
- Balance the hydrogen by adding H⁺ to the appropriate side of the equation.
- Balance the charge by adding electrons to the appropriate side of the
equation.
- Combine two half-equations such that the electrons cancel out each other.
iii. An example:
Q: Balance and complete this equation:
Cr2O7²⁻ + Fe²⁺ → Cr³⁺ + Fe³⁺
A: 1) Divide into two equations:
Cr2O7²⁻ → Cr³⁺..........reduction
Fe²⁺ → Fe³⁺................oxidation

2) Balance the atoms:

Cr2O7²⁻ → 2Cr³⁺
Fe²⁺ → Fe³⁺

3) Balance the oxygen:

Cr2O7²⁻ → 2Cr³⁺ + 7H2O
Fe²⁺ → Fe³⁺

4) Balance the hydrogen:

Cr2O7²⁻ +14H⁺ → 2Cr³⁺ + 7H2O
Fe²⁺ → Fe³⁺

5) Balance the charge:

Cr2O7²⁻ +14H⁺ + 6e⁻ → 2Cr³⁺ + 7H2O
Fe²⁺ → Fe³⁺ + e⁻

74
 6) Cancel the electrons and combine the equations:
[ Cr2O7²⁻ +14H⁺ + 6e⁻ → 2Cr³⁺ + 7H2O ] x 1
[ Fe²⁺ → Fe³⁺ + e⁻ ] x 6
the combine....
Cr2O7²⁻ +14H⁺ + 6e⁻ → 2Cr³⁺ + 7H2O
+ 6Fe²⁺ → 6Fe³⁺ + 6e⁻
-----------------------------------------------------------
Cr2O7²⁻ +14H⁺ + 6e⁻ + 6Fe²⁺ → 2Cr³⁺ + 7H2O + 6Fe³⁺ + 6e⁻
same number of electrons on both sides, cancel it....
Cr2O7²⁻ +14H⁺ + 6Fe²⁺ → 2Cr³⁺ + 7H2O + 6Fe³⁺
is the final answer.

iv. Steps(in alkaline condition):

- Balance the equation as if it happens in an acidic condition first.
- Add OH⁻ to both sides of the equation to react with all the H⁺ to form H2O.
- Cancel the excess H2O on either side of the equation.
Note: If it is obvious enough that OH⁻ must be added in order to
balance the equation, then add OH⁻ instead.

3) Using changes in oxidation number:

i. This method utilises the fact that an increase in certain amount of oxidation
number in a substance must be accompanied by a decrease in same amount
of oxidation number in another substance.
ii. An example:
Q: Balance and complete this equation:
Cr2O7²⁻ + Fe²⁺ → Cr³⁺ + Fe³⁺
A: 1) Calculate the changes in oxidation number:
For Cr: +6 to +3, change is -3
For Fe: +2 to +3, change is +1
2) Balance the changes:
For Cr: -3(1) = -3
For Fe: +1(3) = +3
1Cr2O7²⁻ + 3Fe²⁺ → 1Cr³⁺ + 3Fe³⁺
3) Multiply everything by 2 except Cr2O7²⁻ because there are already two
atoms of chromium inside it.
Cr2O7²⁻ + 6Fe²⁺ → 2Cr³⁺ + 6Fe³⁺
4) Balance the oxygen and hydrogen:
Cr2O7²⁻ + 6Fe²⁺ +14H⁺ → 2Cr³⁺ + 6Fe³⁺ + 7H2O
Cr2O7²⁻ +14H⁺ + 6Fe²⁺ → 2Cr³⁺ + 7H2O + 6Fe³⁺ is the final answer.

75
7.2 Electrolysis
Electrolytic cells

1) Electrolysis is the decomposition of a compound into its elements by an electric

current.

2) Uses of electrolysis:
- to extract useful metals from their ores.
- to produce useful by-products such as chlorine gas.
- to purify metals.

3) Electrolysis is carried out in an electrolytic cell. An electrolytic cell consists of:

i. the electrolyte which is the compound being decomposed. It is either a molten
ionic compound or a concentrated aqueous solution of ions. Solid ionic
compounds and covalent compounds cannot be used because they do not
conduct electricity.
ii. the electrodes which are rods made from graphite or a metal which conducts
electricity to and from the electrolyte.
- anode is the positive electrode.
- cathode is the negative electrode.
iii. external power supply of direct current and a complete d.c. circuit.

Redox reactions in electrolysis

1) During electrolysis, the cations are attracted to the cathode while the
anions are attracted to the anode.

76
2) i. At the cathode, cations gain electrons and are reduced. Reduction occurs
at the cathode.
ii. At the anode, anions lose electrons and are oxidised. Oxidation occurs at
the anode.

3) A simple example is the electrolysis of molten sodium chloride:

i. At the cathode: Na⁺ + e⁻ → Na...........gain electrons, reduction.
ii. At the anode: 2Cl⁻ → Cl2 + 2e⁻...........lose electrons, oxidation.
iii. Sodium metal and chlorine gas are produced.

4) For electrolysis of aqueous sodium chloride:

i. In an aqueous solution of sodium chloride, four types of ions are present
(Na⁺, Cl⁻, H⁺ and OH⁻).
ii. However, only one type of ion can be discharged at each electrode.

5) Factors that determine the selective discharge of ions in an electrolytic cell:

i. Position of the ion in the electrochemical series
- the lower it is in the electrochemical series, the higher the possibility for it to
be discharged.
ii. Concentration of the ions
- the higher the concentration of the ion, the higher the possibility for it to be
discharged.

6) For electrolysis of aqueous sodium chloride:

i. At the cathode: 2H⁺ + 2e⁻ → H2............because H⁺ is lower in the
electrochemical series.
ii. At the anode: 4OH⁻ → O2 + 2H2O + 4e⁻.............because OH⁻ is lower in the
electrochemical series.

77
Extraction of aluminium from bauxite ore

1) Bauxite is impure aluminium oxide, Al2O3. The impurities are iron oxides,
silicon dioxide and titanium dioxide. Bauxite is the major aluminium ore.

2) The first step is to purify the bauxite to get pure aluminium oxide, Al2O3.

3) Molten aluminium oxide is electrolysed in a solution of cryolite, Na3AlF6 to give

out the required aluminium metal.

4) The function of dissolving aluminium oxide in large amount of cryolite is to:

i. lower the melting point of the electrolyte from about 2140 °C to 970 °C.
ii. improve the electrical conductivity of the electrolyte.

5) Electrolysis of aluminium oxide is carried out in long narrow cells using carbon
(graphite) electrodes.

6) At the cathode: Al³⁺ + 3e⁻ → Al...........reduction

At the anode: 2O²⁻ → O2 + 4e⁻............oxidation
Overall equation: 4Al³⁺ + 6O²⁻ → 4Al + 3O2 or 2Al2O3 → 4Al + 3O2

7) Aluminium is denser than the electrolyte. It drops to the bottom of the

electrolytic cell and is removed using a suction tube or through a tap hole.

8) The oxygen gas released will oxidise the hot carbon electrodes to carbon dioxide
and carbon monoxide. So the electrodes have to be replaced from time to time.

9) Some environmental issues related:

i. The carbon monoxide gas produced is poisonous.
ii. Large amount of energy is needed because the current needed to electrolyse
the electrolyte is very high.

78
Electrolysis of brine

1) Brine is concentrated aqueous solution of sodium chloride. It is

obtained from sea water or by dissolving rock salt in water.

2) Electrolysis of brine is used to produce chlorine, hydrogen and sodium

hydroxide. A diaphragm cell is used to carry out this reaction.

3) The electrolyte level in the anode compartment is kept higher than in the
cathode compartment. This ensures the flow of the solution is always towards
the cathode compartment. This reduces the possibility of sodium hydroxide
solution formed moving back as they are to be collected.

4) The ions present in the aqueous solution of sodium chloride are Na⁺, Cl⁻, H⁺
and OH⁻. H⁺ and OH⁻ comes from the slight ionisation of water.
H2O ⇌ H⁺ + OH⁻
5) At the cathode: 2H⁺ + 2e⁻ → H2.........because H⁺ is lower in the electrochemical
series.
At the anode: 2Cl⁻ → Cl2 + 2e⁻...........because Cl⁻ is in a far more greater
concentration than OH⁻.
Overall: 2NaCl + 2H2O → 2NaOH + H2 + Cl2

6) As more and more H⁺ are removed, more are formed from the ionisation of
water because the position of equilibrium shifts to the right. The H⁺ formed are
being removed again until none is left.

7) At the same time, more and more OH⁻ are being produced. When all the H⁺ are
removed, only OH⁻ and Na⁺ are left in the electrolyte and NaOH is formed.

79
Electrolytic purification of copper

1) Copper is purified to be used for electrical wiring because 99.99% of purity is

required for efficient transmission of electrical energy. Even small amounts of
impurity reduces its conductivity greatly.

2) Electrolytic purification of copper is carried out in cells using:

i. an electrolyte of copper(II) sulfate solution acidified with sulfuric acid.
ii. an anode of impure copper.
iii. a cathode of pure copper.

3) At the anode: Cu → Cu²⁺ + 2e⁻

At the cathode: Cu²⁺ + 2e⁻ → Cu

4) The result is the transfer of copper from the anode to the cathode. As a result,
the cathode gets thicker and the anode get thinner. The impurities in the
anode settle down as anode 'sludge'.

5) The concentration of copper(II) sulfate solution does not change because the
number of moles of Cu²⁺ ions formed at the anode is exactly the same as the
number of moles of Cu²⁺ ions discharged at the cathode.

80
CHAPTER 8: Chemical Equilibria
8.1 Dynamic Equilibria
8.2 Factors Affecting Chemical Equilibria
8.3 Equilibrium Constant
8.4 Theory of Acids and Bases

Learning outcomes:

(a) explain, in terms of rates of the forward and reverse reactions, what is meant by a reversible
reaction and dynamic equilibrium.
(b) state Le Chatelier’s Principle and apply it to deduce qualitatively (from appropriate
information) the effects of changes in temperature, concentration or pressure, on a system at
equilibrium.
(c) state whether changes in concentration, pressure or temperature or the presence of a catalyst
affect the value of the equilibrium constant for a reaction.
(d) deduce expressions for equilibrium constants in terms of concentrations, Kc, and partial
pressures, Kp. [treatment of the relationship between Kp and Kc is not required]
(e) calculate the values of equilibrium constants in terms of concentrations or partial pressures
from appropriate data.
(f) calculate the quantities present at equilibrium, given appropriate data (such calculations will
not require the solving of quadratic equations).
(g) describe and explain the conditions used in the Haber process and the Contact process, as
examples of the importance of an understanding of chemical equilibrium in the chemical
industry.
(h) show understanding of, and use, the Brønsted-Lowry theory of acids and bases, including the
use of the acid-I, base-II concept.
(i) explain qualitatively the differences in behaviour between strong and weak acids and bases and
the pH values of their aqueous solutions in terms of the extent of dissociation.

81
8.1 Dynamic Equilibria
Reversible reactions

1) A reversible reaction is one which can proceed in both directions, as indicated

by the "⇌" sign. For example:
H2 + I2 ⇌ 2HI 2SO2 + O2 ⇌ 2SO3
2) In a reversible reaction, the reactants react to form the products. The products
in turn also react to re-form the reactants. A mixture of reactants and products
is present, an equilibrium is established between them.

3) Whether a reaction is reversible or not depends on

its activation energy. If the activation energy of the
backward reaction is very high, the reaction is not
reversible.

Characteristics of equilibrium

1) An equilibrium have four particular features under constant conditions:

i. It is dynamic
- Dynamic equilibrium is a situation where the rate of forward reaction
becomes equal to the rate of reverse reaction and the amount of
substance present to do not vary with time as long as the conditions remain
the same.
- In the microscopic scale, the reactants and products are continuously
reacting but in the macroscopic scale, there seem to be no change at all.

ii. The concentrations of the reactants and products remain constant

- This is because at equilibrium, the rate of forward reaction equals to the rate
of backward reaction.
- For example, H2 + I2 ⇌ 2HI
At equilibrium, for every one mole of the reactants get
converted to two moles of products, two moles of the
products are re-forming the reactants.

82
 iii. It requires a closed system
- A closed system is one which none of the substances can be added or
removed, but energy can move in and out freely.
- In an open system, the products formed will escape, this will not allow
them to react and re-form the reactants, an equilibrium will never be
reached.

8.2 Factors Affecting Chemical Equilibria

Position of equilirbium

1) The position of equilibrium refers to the relative amount of products and

reactants present in an equilibrium mixture.

Le Chatelier's principle

1) Le Chatelier's principle states that if a change is made to a system in equilibrium,

the system reacts in such a way so as to oppose the change and a new
equilibrium is established.

2) In other words, "whatever done to the system, the system does the opposite".

Effect of change in concentration

A+ B⇌ C + D
1) When something is added or removed, the system will does the opposite so as to
remove or replace it.

2) When the concentration of A or B increases, by Le Chatelier's principle, the

position of equilibrium shifts to the right to decrease the concentration
back. More C and D are being formed.

3) When the concentration of A or B decreases, by Le Chatelier's principle, the

position of equilibrium shifts to the left to increase the concentration back.
More A and B are being formed.

83
Effect of change in pressure

2A(g) + B(g) ⇌ C(g) + D(g)

1) Changes in pressure will only affect reactions between gases.

2) When the pressure of a system is altered, the system will respond to

neutralise the change.

3) When the pressure is increased, by Le Chatelier's principle, the position of

equilibrium shifts to the right to reduce the total number of molecules
and to decrease the pressure.

4) When the pressure is decreased, by Le Chatelier's principle, the position of

equilibrium shifts to the left to increase the total number of molecules
and to increase the pressure.

5) i. Increased pressure favours the reaction which produces fewer molecules.

ii. Decreased pressure favours the reaction which produces more molecules.

6) If there are equal number of molecules on each side of the equation, changes
in pressure will not affect the position of equilibrium. However, it will still
affect the rate of reaction.

Effect of change in temperature

A+ B⇌ C + D ΔH° = enthalpy change of forward reaction

1) If heat is introduced to the system, the system will respond to neutralise the
change, either by absorbing or releasing heat.

2) If ΔH° > 0 (endothermic reaction):

i. When temperature is increased, by Le Chatelier's principle, the position of
equilibrium shifts to the right to remove the extra heat (the endothermic
reaction is favoured).
ii. When temperature is reduced, by Le Chatelier's principle, the position of
equilibrium shifts to left to release heat (the forward reaction, an
exothermic reaction is favoured).

3) i. Increased temperature favours endothermic reaction.

ii. Decreased temperature favours exothermic reaction.

84
Effect of catalyst

1) Catalysts will not affect the position of equilibrium. This is because a catalyst
increases both the rate of forward and reverse reaction.

2) However, catalysts can speed up the time taken to reach equilibrium.

8.3 Equilibrium Constants

Equilibrium constants, Kc and Kp

1) Equilibrium constant is the value of the reaction quotient when the reaction
has reached equilibrium. Alternatively, it can also be defined as the measure of
the extent in which reactants are converted into products.

2) At any given temperature, every reaction has a specific value of equilibrium

constant which is independent of changes in concentration, pressure, use of
catalyst or the amount of reactants you start with.

3) Equilibrium constant expressed in concentration is called Kc while expressed in

partial pressure is called Kp.

4) For any reaction: aA + bB ⇌ cC + dD

85
5) For reaction involving gases, equilibrium constant can be expressed in terms of
partial pressures.
aA(g) + bB(g) ⇌ cC(g) + dD(g) ..............(1)

Mole fraction and partial pressures

1) From equation (1), the mole fraction of A is given by:

2) The partial pressure of a gas A in a mixture of gases is the pressure that gas
A will exert, if gas A alone was to occupy the same volume at the same
temperature. It is given by:

More about Kc and Kp

1) Note:
i. Concentration of liquids and solids are omitted in the expression of Kp and Kc.
ii. State symbols are not essential in writing the expressions.

2) The magnitude of Kp and Kc gives the measure of the extent of equilibrium, it

does not give any information about the rate of reaction.

86
3) Examples on writing an expression for Kp and Kc.

Factors affecting the value of Kp and Kc

1) In short, the equilibrium constants are constants at constant temperature. Only

temperature can affect the value of Kc and Kp.

2) i. For endothermic reaction, the value of Kc or Kp increases with increasing

temperature.
ii. For exothermic reaction, the value of Kc or Kp decreases with increasing
temperature.

[ Note: Statement (g) is omitted in this section and is discussed in Chapter 13 ]

8.4 Theory of Acids and Bases

The Arrhenius theory

1) According to Arrhenius theory:

i. An acid is a substance which ionises in water to give hydrogen ions, H⁺.
ii. A base is a substance which ionises in water to give hydroxide ions, OH⁻.

2) Limitations of this theory:

i. When ammonia gas reacts with hydrogen chloride gas, ammonium chloride is
produced. Although this really is an acid-base reaction but it contradicts with
the Arrhenius theory because no H⁺ or OH⁻ is produced.

87
The Brønsted-Lowry theory

1) According to the Brønsted-Lowry theory:

i. An acid is a proton donor.
ii. A base is a proton acceptor.

2) A proton is a hydrogen ion, H⁺.

3) For example, when hydrogen chloride dissolves in water to form hydrochloric

acid, the following reaction occurs:
HCl(g) + H2O(l) → H3O⁺(aq) + Cl⁻(aq)............(2)
HCl is acting as an acid because it has donated a proton. H2O is acting as a
base because it has accepted a proton.

4) When the acidic solution reacts with a base, what is actually functioning as an
acid is the hydroxonium ion, H3O⁺.
H3O⁺ + OH⁻ → 2H2O

H3O⁺ is acting as an acid because it has donated a proton. OH⁻ Is acting as a

base because it has accepted a proton.

5) Brønsted-Lowry acids and bases do not nave to involve aqueous solutions.

Conjugate pairs

1) When ammonia gas dissolves in water, the reaction that occurs is reversible:
NH3(aq) + H2O(l) ⇌ NH4⁺(aq) + OH⁻(aq)..............(3)
In the forward reaction, H2O is acting as an acid because it has donated a
proton and NH3 is acting as a base because it has accepted a proton.
In the backward reaction, OH⁻ is acting as a base because it has accepted a
proton and NH4⁺ is acting as an acid because it has donated a proton.

2) Therefore OH⁻ is the conjugate base of the acid H2O while NH4⁺ is the
conjugate acid of the base NH3.

88
3) In general:
i. Every acid has a conjugate base, this is the particle left when the acid has
given away its proton.
ii. Every base has a conjugate acid, this is the particle left when the base has
accepted a proton.

4) Alternatively, the acid-I, base-II terminology can also be used:

i. HA is acid-I and A⁻ is base-I, they are one conjugate pair.
ii. H2O is base-II and H3O⁺ is acid-II, they are another conjugate pair.

5) Substances which can behave as an acid as well as base are described as

amphoteric. One example is water:
i. In reaction (2), water is behaving as a base.
ii. In reaction (3), water is behaving as an acid.

Strength of acids and bases

1) i. A strong acid is one which dissociates completely in a solution.

HCl(g) + H2O(l) → H3O⁺(aq) + Cl⁻(aq)
ii. This produces high concentration of hydroxonium ions. Therefore the pH of
the solution is very low, pH ≈ 1.
iii. Examples of strong acids are HCl, H2SO4 and HNO3.

2) i. A strong base is one which dissociates completely in a solution.

NaOH(s) + aq → NaOH(aq)
ii. This produces high concentration of hydroxide ions. Therefore the pH of the
solution is very high, pH ≈ 14.
iii. Examples are Group I metal hydroxides.

3) i. A weak acid is one which dissociates partially in a solution.

CH3COOH(l) + H2O(l) ⇌ CH3COO⁻(aq) + H3O⁺(aq)
ii. This produces very low concentration of hydroxonium ions, the position of
equilibrium is far over the left. Therefore the pH of the solution is higher,
pH ≈ 3.
iii. Examples are organic acids.

89
4) i. A weak base is one which dissociates partially in a solution.
NH3(aq) + H2O(l) ⇌ NH4⁺(aq) + OH⁻(aq)
ii. This produces very low concentration of hydroxide ions, the position of
equilibrium is far over the left. Therefore the pH of the solution is lower,
pH ≈ 12.
iii. Examples are ammonia, amines and some hydroxides of transition metals.

5) Note:
i. Strength of acids and bases is defined in terms of degree of dissociation
while concentration is defined as the number of moles per unit volume.
ii. Therefore a weak acid in high concentration is still classified as a weak acid.
iii. Also, a strong acid in low concentration is still classified as a strong acid.

90
CHAPTER 9: Rate of Reaction
9.1 Rate of Reaction
9.2 Factors Affecting Rate of Reaction
9.3 Catalysis

Learning outcomes:

(a) explain and use the terms: rate of reaction, activation energy and catalysis.
(b) explain qualitatively, in terms of collisions, the effect of concentration changes on the rate of
a reaction.
(c) show understanding, including reference to the Boltzmann distribution, of what is meant by
the term activation energy.
(d) explain qualitatively, in terms both of the Boltzmann distribution and of collision frequency,
the effect of temperature change on the rate of a reaction
(e) (i) explain that, in the presence of a catalyst, a reaction has a different mechanism, i.e. one of
lower activation energy.
(ii) interpret this catalytic effect in terms of the Boltzmann distribution.
(f) describe enzymes as biological catalysts (proteins) which may have specific activity.

91
9.1 Rate of Reaction

What is the rate of reaction?

1) Rate of reaction is the change in concentration of reactants or products per unit

time. It refers to the rate of product formed or the rate of reactant used up.

2) A balanced chemical equation gives no information about the rate of reaction.

It has to be measured experimentally.

3) The rate of reaction can also be obtained by calculating the gradient of a

concentration-time graph.

4) The higher the gradient(the steeper the graph), the higher the rate of reaction.

5) The gradient of the graph decreases with time, this shows that the rate of
reaction is inversely proportional to time. Which means, the rate of
reaction decreases as the reaction proceeds.

Collision theory

1) The collision theory states that, for the particles to react with each other, they must
collide in the correct orientation with energy greater than or equal to
the activation energy.

2) The activation energy is the minimum energy that that the reacting particles must
possess for a successful collision to take place.

3) Every reaction has a specific activation energy.

4) If the collision results in the reactants changing into products, it is said to be an

effective(or successful) collision.

92


9.2 Factors Affecting the Rate of Reaction

How to increase the rate of reaction?

1) According to the collision theory, the rate of reaction will increase if:
i. the frequency of collision and effective collision increases.
ii. the proportion of particles with energy greater than activation energy
increases.

Effect of surface area

1) The larger the surface area of the reactant particles, the higher the rate of
reaction.

2) This is because the surface area exposed for collision is larger, frequency of
collision between the reactant particles increases and hence the frequency
of effective collision also increases. More products are formed per unit
time and hence the rate of reaction increases.

93
3) For example, the reaction between hydrochloric acid and marble chips(calcium
carbonate) is as follow:
HCl(aq) + CaCO3(s) → CaCl2(aq) + CO2(g) + H2O(l)

The rate of reaction can be found by measuring the volume of CO2 gas given
out per unit time. The volume of CO2 is determined at regular intervals. The
set up of apparatus is as follow:

It is found that powdered marble chips react faster than big lumps of marble
chips

4) This is because powdered marble chips are smaller in size and hence have a
larger total surface area.

Effect of concentration

1) The higher the concentration of the reactant particles, the higher the rate of
reaction.

2) This is because in a more concentrated solution, there are more reactant

particles per unit volume. The frequency of collision between the
reactant particles increases and hence the frequency of effective collision
also increases. More products are formed per unit time and hence the rate of
reaction is higher.

3) For example, the reaction between magnesium ribbon and hydrochloric acid is
as follow:
Zn(s) + HCl(aq) → ZnCl2(aq) + H2(g)
The rate of reaction can be found by measuring the time
taken for the magnesium ribbon to disappear from sight.

It is found that when HCl has a higher concentration, the time taken for the
magnesium ribbon to disappear is shorter.

4) Since rate of reaction is inversely proportional to time, the shorter the time, the
higher the rate of reaction.

94
5) There are also times where increasing the concentration does not help in
increasing the rate of reaction:
i. Reactions involving only a single reactant particle splitting
- The rate of reaction is not governed by the rate of collision between them.
- The rate is governed by the amount of energy possessed by the reactant
particles.
- If a large proportion of the particles have energy greater than activation
energy, more particles will split up per unit time and hence the rate of
reaction is higher.
ii. Where a catalyst is working as fast as it can
- If a high enough concentration of reactant particles is mixed with a
small amount of catalyst, the reaction proceeds.
- The rate of reaction will not increase if the concentration of the reactant
particles is increased because the catalyst is saturated.
- The rate of reaction can be increased by adding more catalysts.

Effect of pressure

1) The higher the pressure of the system, the higher the rate of reaction.

2) The explanation is the same as the one in the effect of concentration. However,
increasing the pressure will only increase the rate of a reaction involving
gases. Changing the pressure of a reaction which involves only solid or liquid
has no effect on it.

Effect of temperature

1) The higher the temperature of the reacting system, the higher the rate of
reaction.

2) This is because at higher temperature, the average kinetic energy of the

particles increases, so:
i. more reacting particles have energy equal to or greater than the activation
energy. (This is the major reason)
ii. the reacting particles travel at higher speed, the frequency of collision
between the reacting particles increases. (This is the minor reason)
This causes the frequency of effective collision to increase. More products are
formed per unit time and hence, the rate of reaction is higher.

3) In fact, the rate of reaction doubles for every increase in 10 °C.

95
4) The effect of temperature on rate of reaction can be shown in a Maxwell-
Boltzmann distribution curve. A typical curve looks like this:

5) The area under the curve represents the total number of molecules, it is
constant if no additional molecules are added.

6) An increase in temperature increases the number of particles with higher

energy, the curve shifts to the right. So that there are more particles with energy
greater than the activation energy, as illustrated below:

There are more particles with energy greater than the activation energy
at T2

7) When drawing the curve at a higher temperature, the height of the curve
should reduce so that the area under the curve remains constant.
Number of
molecules

Energy

96
9.3 Catalysis
What is a catalyst?

1) A catalyst is a substance that increases the rate of reaction but is chemically

unchanged at the end of the reaction.

2) Catalysis is the increase in the rate of chemical reaction by a catalyst.

3) Characteristics of catalysts:
i. Catalysts are needed in small amounts only. This is because a catalyst is not
used up at the end of a reaction, the same catalyst can be used to catalyse a
large number of reactions.
ii. Catalysts do not initiate the reaction, they accelerate it.
iii. Catalysts do not alter the enthalpy change of a reaction.
iv. Catalysts can be poisoned by impurities, thus losing its catalytic abilities.
v. Most catalysts are transition metals or compounds of them.
vi. Catalysts are usually specific, a reaction can only be catalysed by a specific
catalyst.

4) Examples of catalysts used in industries:

The role of catalyst

1) A catalyst works by providing an alternative route for the reaction to occur.

This alternative route has a lower activation energy. This increases the
proportion of reacting particles with energy greater than the activation energy.
As a result, the frequency of effective collision increases. More products are
formed on per unit time and the rate of reaction is higher.

97
2) A catalyst neither alters the energies of reacting particles nor lower the original
activation energy. It provides an alternative route with lower activation
energy.

3) An example is the decomposition of hydrogen peroxide into water and oxygen.

2H2O2(aq) → 2H2O(l) + O2(g)
The reaction proceeds very slowly at room temperature and there are no
observable changes. However, when a little manganese(VI) oxide, MnO2 is
added, effervescence is seen immediately. This suggests that oxygen gas is
released.

Autocatalysis

1) For most reactions, the rate of reaction decreases with time because the
concentration of reactants decreases.

2) However in some reactions, one of the products can act as a catalyst for
that reaction. In these reactions, the rate is low at the beginning because there is
no catalyst but increases as soon as the product(catalyst) is being formed. After
that, the rate decreases again because the concentration of reactant decreases.

98
Enzymes as catalysts

1) Enzymes are proteins which have catalytic function and can act as biological
catalysts that catalyses biological reactions in living organisms.

2) i. Enzymes are highly specific, catalysing only one type of reaction.

ii. Enzymes are also very sensitive to changes in pH and temperature. Most
enzymes can only function in a small range of temperature(usually 37 °C, the
body temperature) and pH.

iii. Enzymes are super-efficient catalysts, they are much more efficient compared
to inorganic catalysts.

3) Enzymes function via the lock-and-key mechanism. According to this

model, the substrate(reactant) molecule and the active site of the enzyme have
complementary shapes so that the substrate fits in precisely.

4) The substrate binds to the active site of the enzyme just like a key binds to a
lock. Bond-breaking and bond-forming processes then take place, transforming
the substrate into products.

99
CHAPTER 10: Chemical Periodicity
10.1 Periodicity in Physical Properties
10.2 Periodicity in Chemical Properties
10.3 Period 3 Oxides
10.4 Period 3 Chlorides

Learning outcomes:

(a) describe qualitatively (and indicate the periodicity in) the variations in atomic radius, ionic
radius, melting point and electrical conductivity of the elements (see the Data Booklet).
(b) explain qualitatively the variation in atomic radius and ionic radius.
(c) interpret the variation in melting point and in electrical conductivity in terms of the presence
of simple molecular, giant molecular or metallic bonding in the elements.
(d) explain the variation in first ionisation energy.
(e) describe the reactions, if any, of the elements with oxygen (to give Na2O, MgO, Al2O3,
P4O10, SO2, SO3), chlorine (to give NaCl , MgCl2, Al2Cl6, SiCl4, PCl5) and water
(Na and Mg only).
(f) state and explain the variation in oxidation number of the oxides and chlorides in terms of
their valence shell electrons.
(g) describe the reactions of the oxides with water.
[treatment of peroxides and superoxides is not required]
(h) describe and explain the acid/base behaviour of oxides and hydroxides including, where
relevant, amphoteric behaviour in reaction with sodium hydroxide (only) and acids.
(i) describe and explain the reactions of the chlorides with water.
(j) interpret the variations and trends in (f), (g), (h), and (i) in terms of bonding and
electronegativity.
(k) suggest the types of chemical bonding present in chlorides and oxides from observations of
their chemical and physical properties.
(l) predict the characteristic properties of an element in a given group by using knowledge of
chemical periodicity
(m) deduce the nature, possible position in the Periodic Table, and identity of unknown elements
from given information about physical and chemical properties.

100
10.1 Periodicity in Physical Properties
What is periodicity?

1) Periodicity is the recurrence of similar properties at regular intervals when the

elements are arranged in increasing atomic number.

Variation in size of atoms

1) Covalent radius is half the internuclear distance between two like atoms
bonded by a single covalent bond.

2) Van der Waal's radius is half the average distance

between two adjacent non-bonded atoms.

3) For example, the covalent radius of Cl2 is 0.099 nm

while the van der Waal's radius of Cl2 is 0.180 nm.
Note: van der Waal's radius is always larger than covalent radius.

4) Metallic radius is half the distance between two like metal atoms bonded by
metallic bond.

5) All these measurable quantities can be given a general name called 'atomic
radii'.

101
6) Across Period 3, the atomic radius decreases gradually. This is because the
nuclear charge increases while the shielding effect remains constant.
The outer electrons are more attracted towards the nucleus, making the atoms
smaller.

7) For comparison, metallic radii are used for Na, Mg and Al, covalent radii are
used for Si, P, S and Cl. For argon, van der Waal's radius is used(argon do not
form any bonds)
Note: This trend excludes argon because comparing van der Waal's radius with
covalent and metallic radius is not fair.

Variation in ionic radius

1) Cations are formed when an atom loses

electron(s). In Period 3, Na, Mg, Al and Si form
cations by losing electron(s) to achieve stable
octet electronic configuration. The ions formed
are Na⁺, Mg²⁺, Al³⁺ and Si⁴⁺ respectively.

2) Cations are smaller than their respective atoms

because a whole layer of electrons are lost. The
remaining electrons are attracted more strongly
towards the centre by the same nuclear charge.

3) Anions are formed when an atom gains electron(s). In Period 3, P, S and Cl

form anions by gaining electron(s) to achieve stable octet electronic
configuration. The ions formed are P³⁻, S²⁻ and Cl⁻ respectively.

4) Anions are bigger than their respective atoms because they have more
electrons than protons. The electrons are held less strongly by the nucleus.
Besides, a repulsion is created between the electrons when a new electron is
introduced and this causes the ion to expand.

5) Anions are bigger than cations because anions have one more shell of
electrons compared to cations.

6) In the isoelectronic series(from Na⁺ to Si⁴⁺ and P³⁻ to Cl⁻), the ionic radius
decreases gradually. This is because the same number of electrons are
attracted more strongly by the increasing nuclear charge.

102
Variation in melting and boiling points

1) Across a Period,
i. melting point increases from Na to Al because
the strength of the metallic bond increases.
ii. melting point of Si is highest because Si has a
giant covalent structure, a lot of energy is
required to overcome the strong covalent bonds.
iii. melting points of P, S, Cl and Ar are lower because these have simple
molecular structures, only weak van der Waal's forces of attraction exist
between them.

2) Melting point of S > P > Cl > Ar because these elements exist as S8, P4, Cl2 and
Ar respectively. S8 contains the most number of electrons, followed by P4,
Cl2 and Ar. Van der Waal's forces get stronger with increasing number of
electrons.

Variation in electrical conductivity

1) Across the Period, the elements change from

metals(Na to Al) to semi-metal(Si) and then to
non-metals(P to Ar).

2) Electrical conductivity is highest is metals, lower in semi-metals and lowest in

non-metals(Most non-metals do not conduct electricity at all).

3) The electrical conductivity of Period 3 elements:

i. increases from Na to Al because the number of electrons contributed by
per atom to the sea of delocalised electrons increases from one in Na, two in
Mg and three in Al. There are more electrons to conduct electricity.
ii. decreases from Al onwards. Si is a semi-metal therefore it is a semi-
conductor. The remaining elements do not conduct electricity because there
are no mobile electrons.

Variation is first ionisation energy

(Refer Chapter 3)

103
10.2 Periodicity in Chemical Properties
Reaction with oxygen gas, O2

1) Sodium burns on heating with an orange-yellow flame to

form white sodium oxide.
4Na(s) + O2(g) → 2Na2O(s)

2) Magnesium burns on heating with a brilliant white

flame to form white magnesium oxide.
2Mg(s) + O2(g) → 2MgO(s)

3) An oxide layer will form on the aluminium when it is exposed to air, this oxide
layer prevents aluminium from reacting. However, if powdered aluminium is
used, it burns on heating with white flames to form white aluminium oxide.
4Al(s) + 3O2(g) → 2Al2O3(s)

4) Silicon burns slowly at red heat to form silicon(Vl) oxide or silicon dioxide.
Si(s) + O2(g) → SiO2(s)

5) Phosphorus burns on heating with a white flame to form clouds of white

covalent oxides, phosphorus(III) oxide and phosphorus(V) chloride.
P4(s) + 3O2(g) → P4O6(s) ; if oxygen gas is limited
P4(s) + 5O2(g) → P4O10(s) ; if oxygen gas is in excess

6) Sulfur burns on heating with a blue flame to form sulfur dioxide gas.
S(s) + O2(g) → SO2(g)
Under suitable conditions, sulfur dioxide can be converted to
sulfur trioxide.(See also the Contact process)
2SO2(g) + O2(g) ⇌ 2SO3(g)

7) Chlorine forms several oxides(Cl2O and Cl2O7), but it will not

react directly with oxygen.

8) Argon does not react with oxygen to form any oxides.

9) Going across Period 3, the reactivity towards oxygen decreases because

the reducing power(tendency to be oxidised) of the elements decreases.

104
Reaction with chlorine gas, Cl2

1) Sodium burns on heating in chlorine gas with an orange-yellow flame to

form white sodium chloride.
2Na(s) + Cl2(g) → 2NaCl(s)

2) Magnesium burns on heating in chlorine gas with a brilliant white flame

to form white magnesium chloride.
Mg(s) + Cl2(g) → MgCl2(s)

3) Aluminium burns on heating to form ionic aluminium chloride.

2Al(s) + 3Cl2(g) → 2AlCl3(s)
At temperature about 180 °C, aluminium chloride converts to a molecular
form, Al2Cl6, a dimer of covalent AlCl3. At even higher temperature, Al2Cl6
breaks into simple AlCl3 molecules.
2Al(s) + 3Cl2(g) → Al2Cl6(g)

4) Silicon burns slowly in chlorine gas at red heat to form covalent silicon(IV)
chloride or silicon tetrachloride, a colourless liquid which vaporises.
Si(s) + Cl2(g) → SiCl4(l)

5) Phosphorus burns in chlorine gas to produce a mixture of two chlorides,

phosphorus(III) chloride, PCl3 and phosphorus(V) chloride, PCl5. In excess
chlorine gas, PCl5 is the major product.
P4(s) + 6Cl2(g) → 4PCl3(l) ; if chlorine gas is limited
P4(s) + 10Cl2(g) → 4PCl5(s) ; if chlorine gas is in excess
PCl3 is a fuming liquid while PCl5 is an off-white solid.

6) Sulfur burns in chlorine gas to produce disulfur dichloride, an orange, evil-

smelling liquid.
2S(s) + Cl2(g) → S2Cl2(l)

7) Chlorine obviously does not react with chlorine gas.

8) Argon does not react with chlorine gas to form any chlorides.

105
Reaction with water, H2O

1) Sodium catches fire in cold water and a violently exothermic reaction occurs to
form sodium hydroxide and hydrogen gas.
2Na(s) + 2H2O(l) → 2NaOH(aq) + H2(g)

2) Magnesium reacts very slowly with cold water, taking several days to collect a
test tube of hydrogen gas and a weakly alkaline magnesium hydroxide solution.
Mg(s) + 2H2O(l) → Mg(OH)2(aq) + H2(g) ; very slow
However, it reacts rapidly with steam to produce magnesium hydroxide and
hydrogen gas.
Mg(s) + H2O(g) → MgO(s) + H2(g) ; very fast

Variation in oxidation number of Period 3 oxides and chlorides

1) Oxidation number of a Period 3 oxide or chloride corresponds to the number

of electrons used for bonding. It is always positive because oxygen is more
electronegative than any of the element.

2) The maximum oxidation number is the same as Group number. This

corresponds to the total number of valence electrons.

3) i. In the oxides, the maximum oxidation number

increases from +1 in Na to +6 in S.
ii. In the chlorides, the maximum oxidation
number increases from +1 in Na to +5 in P.

4) Phosphorus and sulfur show several oxidation

numbers because they can expand their octet
through the excitation of electrons to the empty
3d orbitals.

5) For example:
i. In SO2, S has oxidation number +4 because only four electrons are used for
bonding.
ii. In SO3, S has oxidation number +6 because all six electrons are used for
bonding.

106
10.3 Period 3 Oxides
Summary of the properties of Period 3 oxides.

Reaction with water, H2O

1) Sodium oxide reacts exothermically with cold water to form sodium

hydroxide. A strongly alkaline solution of sodium hydroxide is produced.
Na2O(s) + H2O(l) → 2NaOH(aq) ; pH = 13

2) Magnesium oxide reacts slightly with water to the extent that it is almost
insoluble. A weakly alkaline solution of magnesium hydroxide is produced.
MgO(s) + H2O(l) → Mg(OH)2(aq) ; pH = 9

3) Aluminium oxide does not react or dissolve in water due to its high lattice
energy.

4) Silicon dioxide does not react or dissolve in water due to the strong
covalent bonds.

5) Phosphorus oxides react with water to form acidic solutions(pH = 2).

Phosphorus(III) oxide reacts with water to form phosphorous acid.
P4O6(s) + 6H2O(l) → 4H3PO3(aq)
Phosphorus(V) oxide reacts with water to form phosphoric(V) acid.
P4O10(s) + 6H2O(l) → 4H3PO4(aq)

6) Sulfur oxides react with water to form acidic solutions(pH = 2).

Sulfur dioxide reacts with water to give sulfurous acid or sulfuric(IV) acid.
SO2(g) + H2O(l) → H2SO3(aq)
Sulfur trioxide reacts violently with water to form a mist of sulfuric acid.
SO3(g) + H2O(l) → H2SO4(aq)

107
Acid-base behaviour of Period 3 oxides

1) Going across Period 3, the nature of the oxide changes from basic(Na2O,
MgO) to amphoteric(Al2O3) then to acidic(SiO2, P4O6/P4O10, SO2/SO3).
The acidity of the oxides increases across the Period.

2) Sodium and magnesium oxides are basic oxides, they react with acid to
give the corresponding salts and water.
Na2O(s) + 2HCl(aq) → 2NaCl(aq) + H2O(l)
MgO(s) + 2HCl(aq) → MgCl2(aq) + H2O(l)

3) Aluminium oxide is amphoteric, it can react with both acid and base.
Aluminium oxide reacts with hot and concentrated acids to give salt and water
Al2O3(s) + 6HCl(aq) → 2AlCl3(aq) + 3H2O(l)
Aluminium oxide reacts with hot and concentrated sodium hydroxide to give
sodium aluminate.
Al2O3(s) + 2NaOH(aq) + 3H2O(l) → 2NaAl(OH)4(aq)
sodium aluminate
4) Silicon dioxide is an acidic oxide, it reacts with hot and concentrated
sodium hydroxide to give a colourless solution of sodium silicate.
SiO2(s) + 2NaOH(aq) → Na2SiO3(aq) + H2O(l)
sodium silicate
5) Phosphorus oxides are acidic oxides, they react with alkalis to form salts and
water.
Phosphorus(III) oxide reacts with sodium hydroxide to form sodium
phosphate(III) and water.
P4O6(s) + 12NaOH(aq) → 4Na3PO3(aq) + 6H2O(l)
Phosphorus(V) oxide reacts with sodium hydroxide to form sodium
phosphate(V) and water.
P4O10(s) + 12NaOH(aq) → 4Na3PO4(aq) + 6H2O(l)

6) Sulfur oxides are acidic oxides, they react with alkalis to form salt and water.
Sulfur dioxide reacts with sodium hydroxide to form sodium sulfate(IV) and
water.
SO2(g) + 2NaOH(aq) → Na2SO3(aq) + H2O(l)
Sulfur trioxide reacts with sodium hydroxide to form sodium sulfate(VI) and
water.
SO3(g) + 2NaOH(aq) → Na2SO4(aq) + H2O(l)

108
10.4 Period 3 Chlorides
Summary of the properties of Period 3 chlorides

Reaction with water, H2O

1) Sodium chloride dissolves in water to form a neutral solution of sodium

chloride.
NaCl(s) + aq → Na⁺(aq) + Cl⁻(aq) ; pH = 7

2) Magnesium chloride dissolves in water with slight hydrolysis to form a

solution of magnesium chloride.
MgCl2(s) + 6H2O → [Mg(H2O)6]²⁺(aq) + 2Cl⁻(aq)
hexaaquamagnesium ions
[Mg(H2O)6]²⁺(aq) +H2O(l) ⇌ [Mg(H2O)5(OH)]⁺(aq) + H3O⁺(aq) ; pH = 6.5

3) Aluminium chloride, AlCl3 hydrolyses in water to give an acidic solution,

white fumes of hydrogen chloride gas are formed.
AlCl3(s) + 6H2O(l) → [Al(H2O)6]³⁺(aq) + 3Cl⁻(aq)
[Al(H2O)6]³⁺(aq) +H2O(l) ⇌ [Al(H2O)5(OH)]²⁺(aq) + H3O⁺(aq) ; pH = 3

4) Silicon tetrachloride undergoes complete hydrolysis in water to form a

strongly acidic solution, white fumes of hydrogen chloride gas are formed.
SiCl4(l) + 2H2O(l) → SiO2(s) + 4HCl(g) ; pH = 2

5) Phosphorus(III) chloride reacts violently with water in a hydrolysis reaction

to give a strongly acidic solution and fumes of hydrogen chloride gas.
PCl3(l) + 3H2O(l) → H3PO3(aq) + 3HCl(g) ; pH = 2

109
 Phosphorus(V) chloride is an off-white ionic solid at room temperature and
sublimes at 163 °C to give phosphorus(III) chloride and chlorine gas.
PCl5(s) ⇌ PCl3(l) + Cl2(g)
It reacts violently with water in a hydrolysis reaction to give a strongly acidic
solution and fumes of hydrogen chloride gas.
PCl5(s) + 4H2O(l) → H3PO4(aq) + 5HCl(g) ; pH = 2

6) The acidity of the chlorides increases across the Period as the nature of
the chlorides changes from ionic to covalent.

110
CHAPTER 11: Group II
11.1 Physical Properties of Group II Elements
11.2 Reactions of Group II Elements
11.3 Group II Oxides, Hydroxides and Carbonates
11.4 Thermal Decomposition
11.5 Uses of Group II Compounds

Learning outcomes:

(a) describe the reactions of the elements with oxygen, water and dilute acids.
(b) describe the behaviour of the oxides, hydroxides and carbonates with water and with dilute
acids.
(c) describe the thermal decomposition of the nitrates and carbonates.
(d) interpret, and make predictions from, the trends in physical and chemical properties of the
elements and their compounds.
(e) explain the use of magnesium oxide as a refractory lining material
(f) describe and explain the use of lime in agriculture.

111
11.1 Physical Properties of Group II Elements
Introduction to Group II elements

1) Group II elements(also called the 'alkaline earth metals') are s-block elements
with a characteristic outer shell configuration ns².

2) Group II elements are very reactive metals. They have low electronegativity and
are readily oxidised, they always exhibit an oxidation state of +2 in their
compounds. This is because the two outer s electrons are readily lost during a
reaction to achieve a noble gas configuration.
M → M²⁺ + 2e⁻ ; where M = A Group II element

Variation in atomic radius

1) The atomic radius increases going down the Group.

This is because going down the Group, each
succeeding element has one more shell of
electrons. The distance between nucleus and outer
electrons are progressively further.

Variation in first ionisation energy

1) The first ionisation energy decreases down the

Group. This is because the distance between nucleus
and outer electrons increases, and the outer electrons
are more shielded.

2) These two factors outweigh the increasing nuclear charge. So, the attractive
force between nucleus and outer electrons decreases and less energy is
required to remove the electron.

112
Variation in electronegativity

1) Electronegativity decreases down the Group. This is

because the distance between the nucleus and the
bonded pair of electrons increases down the Group.
Therefore the electrons are held less strongly by the
nucleus.

2) In other words, the reducing power(and reactivity) increases down the Group.

11.2 Reactions of Group II Elements

Reaction with oxygen gas, O2

1) All Group II elements(except beryllium) burn in oxygen with a bright flame to

form monoxides.
2M(s) + O2(g) → 2MO(s) ; where M = A Group II element

2) i. 2Mg(s) + O2(g) → 2MgO(s) ; burns with brilliant white flame

ii. 2Ca(s) + O2(g) → 2CaO(s) ; burns with brick red flame
iii. 2Sr(s) + O2(g) → 2SrO(s) ; burns with crimson red flame
iv. 2Ba(s) + O2(g) → 2BaO(s) ; burns with apple green flame

Magnesium burning Calcium burning Strontium burning Barium burning

113
Reaction with water, H2O

1) All Group II elements(except beryllium) reacts with water to form hydroxides

and hydrogen gas.
M(s) + 2H2O(l) → M(OH)2(aq) + H2(g) ; where M = A Group II element

2) i. Beryllium has no reaction with cold water or steam even at red heat due to
the formation of protective oxide layer on its surface.
ii. Magnesium reacts very slowly with cold water, taking several days to collect
a test tube of hydrogen gas and a weakly alkaline magnesium hydroxide
solution.
Mg(s) + 2H2O(l) → Mg(OH)2(aq) + H2(g) ; very slow, pH = 9
However, it reacts rapidly with steam to produce magnesium oxide and
hydrogen gas. This is because the hydroxide formed thermally decompose
into an oxide.
Mg(s) + H2O(g) → MgO(s) + H2(g) ; very fast

iii. Calcium, strontium and barium reacts vigorously with cold water to give
hydroxides.
Ca(s) + 2H2O(l) → Ca(OH)2(s) + H2(g)
Sr(s) + 2H2O(l) → Sr(OH)2(aq) + H2(g)
Ba(s) + 2H2O(l) → Ba(OH)2(aq) + H2(g)
Note:
i. Ca(OH)2 appears as white precipitate. It is sparingly soluble therefore a
weakly alkaline solution will also be formed.

3) The reactivity of the elements with water increases down the Group. In other
words, they become more soluble going down the Group.

Reaction with acids

1) All Group II elements react with acid to give hydrogen gas and the
corresponding salt.
M(s) + H⁺(aq) → M²⁺(aq or s) + H2(g) ; where M = A Group II element

2) i. Beryllium reacts slowly with acids and has no reaction at room temperature.
ii. The rest of Group II metals react with increasing vigorous going down the
Group.

114
11.3 Group II Oxides, Hydroxides and Carbonates
Group II oxides

1) All Group II oxides(except beryllium oxide) reacts with water, at least to some
extent to give the corresponding hydroxides.

2) i. Beryllium oxide is insoluble because Be²⁺ ion is a very small and highly
charged ion, thus making the lattice energy of BeO exceptionally high.
ii. Magnesium oxide is only slightly soluble in water, producing a weakly alkaline
solution.
iii. Addition of calcium oxide with water is a very vigorous and exothermic
reaction.

3) All Group II oxides(except beryllium oxide) are basic. They react with acids to
give the corresponding salt and water.

4) Beryllium oxide, on the other hand, is amphoteric. It reacts with both acid and
base.

Group II hydroxides

1) Group II hydroxides are not very soluble, and they do not react with water.
However, the solubility increases down the Group.

2) i. Magnesium hydroxide is only slightly soluble in water, with a pH of about 9.

ii. Calcium hydroxide(slaked lime) is moderately soluble to give a solution called
"lime water".

115
3) Group II hydroxides behave as a base and react with acids to give the
corresponding salt and water.

Group II carbonates

1) Group II carbonates are mainly insoluble, and they do not react with water. The
solubility decreases down the Group.

2) Group II carbonates react with acid to form salt, carbon dioxide and water.
MCO3(s) + H⁺ → M²⁺(aq or s) + CO2(g) + H2O(l) ; where M = A Group II
element

11.4 Thermal Decomposition

Thermal decomposition of Group II salts

1) In general, compounds with high charge density cation and large anion
size tend to decompose more easily(less stable on heat) due to the greater
polarisation of anion by the cation.

2) Thermal decomposition of Group II salts decreases down the Group. In other

words, the thermal stability of Group II salts increases down the Group.

3) This is because going down the Group, the cation size increases while the anion
size remains unchanged. Therefore the charge density and polarising power of
cation decreases and the anion cloud is less polarised. The compound is more
stable on heating.

4) Group II salts are less stable compared to Group I salts due to the higher
charge density of M²⁺ ion.

Thermal decomposition of Group II nitrates

1) All Group II nitrates decompose on heating to give the corresponding metal

oxide, brown nitrogen monoxide gas and oxygen gas.
2M(NO3)2(s) → 2MO(s) + 4NO2(g) + O2(g) ; where M = A Group II element

116
2) Thermal stability of Group II nitrates increases down the Group. This is
because the cation size increases down the Group, this reduces the charge
density and polarising power of cation. The nitrate ion is less polarised and the
compound is more stable.

Thermal decomposition of Group II carbonates

1) All Group II carbonates decompose on heating to give the corresponding metal

oxide and carbon dioxide gas.
MCO3(s) → MO(s) + CO2(g) ; where M = A Group II element

2) Thermal stability of Group II carbonates increases down the Group. This is

because the cation size increases down the Group, this reduces the charge
density and polarising power of cation. The carbonate ion is less polarised and
the compound is more stable.

11.5 Uses of Group II Compounds

1) Some ceramics contain magnesium oxide, MgO and they can be used as:
i. electrical insulators in industrial electrical cables.
ii. a refractory in furnace linings because it has a high melting point.(However, it
cannot be used in furnaces where acid is present due to its basic nature)
iii. in fire-resistant wall boards.

2) Calcium compounds have many uses, this includes:

i. calcium carbonate(limestone) to make cement.
- It is roasted in a lime kiln so that it decomposes into calcium oxide, CaO
(quicklime). The cement made is mixed with rocks to make concrete.
ii. using calcium hydroxide/oxide/carbonate to treat acidic soil as they react
with acids.

117
CHAPTER 12: Group VII
12.1 Physical Properties of Group VII Elements
12.2 Reactions of Group VII Elements
12.3 Reactions of Halide Ions
12.4 Uses of Halogens

Learning outcomes:

(a) describe the colours of, and the trend in volatility of chlorine, bromine and iodine.
(b) interpret the volatility of the elements in terms of van der Waals’ forces.
(c) describe the relative reactivity of the elements as oxidising agents.
(d) describe and explain the reactions of the elements with hydrogen.
(e) (i) describe and explain the relative thermal stabilities of the hydrides.
(ii) interpret these relative stabilities in terms of bond energies.
(f) describe and explain the reactions of halide ions with
(i) aqueous silver ions followed by aqueous ammonia.
(ii) concentrated sulfuric acid.
(g) outline a method for the manufacture of chlorine from brine by a diaphragm cell.
(h) describe and interpret in terms of changes of oxidation number the reaction of chlorine with
cold, and with hot, aqueous sodium hydroxide.
(i) explain the use of chlorine in water purification.
(j) state the industrial importance and environmental significance of the halogens and their
compounds (e.g. for bleaches, PVC, halogenated hydrocarbons as solvents, refrigerants and in
aerosols).

118
12.1 Physical Properties of Group VII Elements
Introduction to Group VII elements

1) Group VII elements(also called the 'halogens') are p-block elements with a
characteristic outer shell configuration of ns²np⁵.

2) Some common physical properties of the halogens are as follow:

Note:
i. Bromine is a dark red liquid but forms reddish-brown gas.
ii. Iodine is a black solid but forms a purple vapour on gentle heating.
iii. The trend is the halogens get darker going down the Group.
iv. Iodine is insoluble in water but it dissolves in potassium iodide, KI solution
due to the formation of I3⁻ ion.
v. In organic solvents, halogens exist as free molecules, X2.

Variation in atomic radius

1) The atomic radius of halogens increases

going down the Group. This is because going
down the Group, each succeeding element has
one more shell of electrons. The distance
between nucleus and outer electrons are
progressively further.

119
Variation in electronegativity

1) The electronegativity of halogens decreases down

the Group. This is because going down the Group,
the distance between the nucleus and bonding
electrons increases. Therefore the electrons are
attracted less strongly by the nucleus.

2) Fluorine is the most electronegative element, and is assigned an

electronegativity of 4.0 on the Pauling scale.

3) In other words, the oxidising power(and reactivity) decreases down the Group.

Variation in volatility

1) The volatility of halogens decreases

down the Group. This is because going
down the Group, the number of
electrons in the halogen molecules
increases. More temporary dipoles can
be set up and the strength of van der
Waal's forces increases.

2) Hence the boiling point increases and the halogens become less volatile.

Variation in bond enthalpy

1) Excluding fluorine, the bond enthalpy of halogens

decreases down the Group. This is because going
down the Group, the distance between the
nucleus and bonding pair of electrons
increases. The bonding electrons are less attracted
and as a result, the covalent bond gets weaker. Less
energy is required to break the bond.

2) The bond enthalpy is exceptionally low because F2 is

a very small molecule with six lone pairs of
electrons. The repulsion created between these
electrons reduces the energy needed to break the
covalent bond.

120
12.2 Reactions of Group VII Elements
Halogens as oxidising agent

1) Halogens are powerful oxidising agents. However, the oxidising ability

decreases down the Group. Therefore, F2 is the most powerful oxidising agent
while I2 is the weakest.

2) This is reflected in their ability to oxidise other halide ions, as follow:

Note:
i. A halogen can oxidise the halide ion below it on the Periodic Table,
fluorine is excluded in this argument because it is too powerful as an
oxidising agent and will oxidise water into oxygen.
ii. If chlorine is able to displace bromide ion from its aqueous solution, this
indicates that chlorine has a higher tendency to be reduced and to accept
electrons to form ions.

Reaction with hydrogen gas, H2

1) All halogens react with hydrogen gas to form hydrides, HX.

H2 + X2 → 2HX ; where X = A halogen

2) i. H2(g) + F2(g) → 2HF(g) ; explosive reaction under all temperature

ii. H2(g) + Cl2(g) → 2HCl(g) ; explosive reaction under sunlight
iii. H2(g) + Br2(g) → 2HBr(g) ; slow reaction on heating
iv. H2(g) + I2(g) ⇌ 2HI(g) ; an equilibrium mixture is obtained

3) The reactivity of halogens towards hydrogen gas decreases down the Group due
to the decrease in oxidising ability of the halogens.

121
Thermal stability of hydrogen halides, HX

1) The thermal stability of the hydrogen halides, HX

decreases down the Group. This is because the
size of the atom increases and so the strength of
the H-X bond decreases. In other words, the
hydrogen halides become less stable on heating
going down the Group.

2) i. Hydrogen iodide decomposes easily on heating, thick purple fumes of I2 are

observed.
ii. Hydrogen bromide decomposes slightly, little orange-brown of Br2 is
observed.
iii. Hydrogen chloride and fluoride are stable on heating.

3) When hydrogen halides decompose, X⁻ ions are oxidised. The ease of oxidation
down the Group indicates the increase in reducing ability of X⁻ ion. Hence, I⁻ is
the strongest reducing agent while F⁻ is the weakest.

Reaction with aqueous sodium thiosulfate, Na2S2O3

1) Chlorine and bromine can oxidise sodium thiosulfate, Na2S2O3 to sodium

sulfate, Na2SO4. The oxidation number of sulfur changes from +2 to +6.
4Cl2 + S2O3²⁻ + 5H2O → 2SO4²⁻ + 10H⁺ + 8Cl⁻
4Br2 + S2O3²⁻ + 5H2O → 2SO4²⁻ + 10H⁺ + 8Cl⁻

2) However, iodine can only oxidise sodium thiosulfate to sodium tetrathionate,

Na2S4O6. The oxidation number of sulfur changes from +2 to +2.5.
I2 + 2S2O3²⁻ → S4O6²⁻ + 2I⁻

Reaction with aqueous iron(II) ions, Fe²⁺

1) Chlorine and bromine would oxidise Fe²⁺ to Fe³⁺ but not iodine.
Cl2 + 2Fe²⁺ → 2Cl⁻ + 2Fe³⁺
Br2 + 2Fe²⁺ → 2Br⁻ + 2Fe³⁺

122
Reaction with iron, Fe

1) i. When chlorine gas is passed over hot iron, iron(III) chloride is formed. The
oxidation number of iron changes from 0 to +3.
Cl2 + Fe → FeCl3 ; rapid and vigorous reaction
ii. When bromine vapour is passed over hot iron, iron(III) chloride is formed.
The oxidation number of iron changes from 0 to +3.
Br2 + Fe → FeBr3 ; less rapid and vigorous reaction
iii. When iodine vapour is passed over hot iron, iron(II) chloride is formed. The
oxidation number of iron changes from 0 to only +2.
I2 + Fe → FeI2 ; even less vigorous

Reaction with hot and cold alkali

1) Chlorine undergoes disproportionation when it reacts with alkali. In this

reaction, chlorine is simultaneously oxidised and reduced.

2) In cold alkali(15 ºC), the reaction is as follow:

Cl2(aq) + 2NaOH(aq) → NaCl(aq) + NaClO(aq) + H2O(l)
The ionic equation is:
Cl2(aq) + 2OH⁻(aq) → Cl⁻(aq) + ClO⁻(aq) + H2O(l)

3) In cold alkali, the oxidation number of chlorine changes from 0 in Cl2 to -1 in

Cl⁻(reduction) and +1 in ClO⁻(oxidation).

4) In hot alkali(70 ºC), the reaction is as follow:

3Cl2(aq) + 6NaOH(aq) → 5NaCl(aq) + NaClO3(aq) + 3H2O(l)
The ionic equation is:
3Cl2(aq) + 6OH⁻(aq) → 5Cl⁻(aq) + ClO3⁻(aq) + 3H2O(l)

5) In hot alkali, the oxidation number of chlorine changes from 0 in Cl2 to -1 in

Cl⁻(reduction) and +5 in ClO3⁻(oxidation).

6) This reaction is the result of disproportionation of chlorate(I) ions in the

presence of heat.
3ClO⁻(aq) → 2Cl⁻(aq) + ClO3⁻

7) Bromine and iodine react in a similar manner. However, the bromate(I) and
iodate(I) ions formed disproportionate readily at all temperatures.

123
12.3 Reactions of Halide Ions
Introduction to halide ions, X⁻

1) The halogens are typical non-metals, they:

i. form singly charge negative ions, X⁻.
ii. form ionic compounds with metals and covalent compounds with non-metals.

Preparation of halogens in the laboratory

1) Halogens can be prepared in the laboratory by the oxidation of X⁻ ions using

manganese(IV) oxide, MnO2 in the presence of concentrated sulfuric acid.
2X⁻ + MnO2 + 4H⁺ → X2 + Mn²⁺ + 2H2O ; where X = A halogen

2) The apparatus needed is shown below:

Note:
i. In each case, hydrogen
halide is also formed
from the reaction of X⁻
with H2SO4 and must be
removed in order to
obtain pure halogen.

124
Test for halide ions(reaction with silver ion, Ag⁺)

1) Halide ions are colourless in their aqueous solutions and a test is needed to
identify their presence.

2) Silver ions, Ag⁺ can be used to test halide ions because the silver halide is
formed as precipitate.
Ag⁺(aq) + X⁻(aq) → AgX(aq or s) ; where X = A halogen
The silver halides formed can be differentiated by:
i. their colour.
ii. their reaction with dilute aqueous ammonia, NH3.

3) The test is summarised below: (Fluoride does not form precipitates)

4) NH3 is used as a confirmatory test as cream and white precipitate may be hard
to distinguish.

5) Alternatively, concentrated sulfuric acid can be used to test halide ions:

Note:
i. F⁻ and Cl⁻ can be
differentiated using the silver
ion test.
ii. The chemistry of this test is
explained next.

125
Reaction with concentrated sulfuric acid, H2SO4

1) When halides(NaX) are reacted with concentrated sulfuric acid, the following
happens:

2) The ease of oxidation of halide ions increases from Cl⁻ to I⁻ because the
tendency to be oxidised(the reducing power) increases. The HBr and HI
produced are oxidised to Br2 and I2 respectively while the HCl produced is not.
(HI is oxidised readily while HBr is not)

3) To prepare HI or HBr, phosphoric acid, H3PO4 is used instead because all

halides react to give the corresponding hydrides.
2NaX + H3PO4 → 2HX + Na2HPO4 ; where X = A halogen

12.4 Uses of Halogens

1) Chlorine is used in the chlorination of water to kill bacteria. The chlorine
undergoes disproportionation.
Cl2(aq) + H2O(l) → HCl(aq) + HClO(aq)
Chloric(I) acid, HClO produced decomposes slowly to produce reactive oxygen
atoms that kill bacteria in water.
HClO → HCl + O

2) Bleach is an equal mixture of sodium chloride, NaCl and sodium chlorate(I),

NaClO. Sodium chlorate(I) is a powerful oxidising agent and bleaches dye and
other coloured molecules by oxidising them.

126
3) i. Halogens are also used in chlorofluorocarbons(CFCs). CFCs are widely
used as refrigerants, propellants and aerosols. They are also used as solvents
for dry cleaning and generating foamed plastics like expanded polystyrene or
polyurethane foam.
ii. Unfortunately, CFCs are largely responsible for destroying the ozone layer. In
the high atmosphere, the carbon-chlorine bonds break to give chlorine free
radicals and these radicals destroy the ozone. CFCs are now being replaced by
less environmentally harmful compounds.

4) i. Plastic PVC(poly(chloroethene) or polyvinyl chloride) are made from

halogen compounds.
ii. Poly(chloroethene) is made through polymerisation of organic molecules, the
organic molecule is chloroethene, CH2CHCl. These organic molecules join
together repeatedly to form the polymer.

iii. Poly(chloroethene) is used to make a wide range of things including

guttering, plastic windows, electrical cable insulation, sheet materials for
flooring and other uses, footwear, clothing, and so on.

5) Bromine and iodine are often used in the manufacture of dyes and drugs.

127
CHAPTER 13: Nitrogen and Sulfur
13.1 Nitrogen Compounds
13.2 Environmental Consequences of Using Nitrogen Compounds
13.3 Sulfur Compounds

Learning outcomes:

(a) explain the lack of reactivity of nitrogen.

(b) describe and explain:
(i) the basicity of ammonia.
(ii) the structure of the ammonium ion and its formation by an acid-base reaction.
(iii) the displacement of ammonia from its salts.
(c) describe the Haber process for the manufacture of ammonia from its elements, giving essential
operating conditions, and interpret these conditions (qualitatively) in terms of the principles of
kinetics and equilibria.
(d) state the industrial importance of ammonia and nitrogen compounds derived from ammonia.
(e) state and explain the environmental consequences of the uncontrolled use of nitrate fertilisers.
(f) state and explain the natural and man-made occurrences of oxides of nitrogen and their
catalytic removal from the exhaust gases of internal combustion engines.
(g) explain why atmospheric oxides of nitrogen are pollutants, including their catalytic role in the
oxidation of atmospheric sulfur dioxide.
(h) describe the formation of atmospheric sulfur dioxide from the combustion of sulfur
contaminated carbonaceous fuels.
(i) state the role of sulfur dioxide in the formation of acid rain and describe the main
environmental consequences of acid rain.
(j) state the main details of the Contact process for sulfuric acid production.
(k) describe the use of sulfur dioxide in food preservation.

128
13.1 Nitrogen Compounds
The lack of reactivity of nitrogen

1) Nitrogen, N2 exists as a diatomic molecule, two nitrogen atoms

are bonded by a triple bond.

2) Nitrogen is very unreactive because the bond energy is very high

(about +944 kJ mol⁻¹) and reactions involving nitrogen tend to break the entire
bond.

3) However, nitrogen still undergoes the following reactions:

i. When nitrogen and oxygen are struck by lightning in the atmosphere,
nitrogen monoxide, NO is produced. In this case, the lightning provides the
activation energy required to start the reaction.
N2(g) + O2(g) → 2NO(g) ; ΔH = +181 kJ mol⁻¹
ii. Magnesium nitride, Mg3N2 is formed when magnesium is heated in nitrogen.
The reaction is exothermic because the ionic bond formed is much stronger
than the original bonds and a net energy is released.
3Mg(s) + N2(g) → Mg3N2(s) ; ΔH = -461 kJ mol⁻¹

4) Carbon monoxide, CO with a triple bond and similarly high bond energy is
more reactive because:
i. it has a dipole moment hence the molecule is polar. They are more
attractive to nucleophiles or electrophiles and this initiates a reaction to occur.
ii. the reaction involving carbon monoxide will normally not break the
entire triple bond. Instead, the bond is partially broken to produce a
double-bonded carbon dioxide, CO2.

Ammonia, NH3 and its reactions

1) Ammonia, NH3 is a trigonal pyramidal molecule with a net

dipole moment, hence the molecule is polar.

2) Ammonia is a weak base, it is also a Brønsted-Lowry base,

hence it is capable of accepting a hydrogen ion to form ammonium ion, NH4⁺.

129
3) i. Ammonia reacts with acids to form ammonium salts. For example, the
reaction between ammonia and hydrogen chloride, HCl gas:
NH3(g) + HCl(g) → NH4⁺Cl⁻
ii. Ammonium salts react with bases to liberate ammonia gas, salt and
water is also formed. This is because ammonia is a weak base, the proton
accepted is easily removed again. For example, the reaction between
ammonium sulfate, (NH4)2SO4 and calcium oxide, CaO:
2NH4Cl(s) + Ca(OH)2(s) → CaCl(s) + 2NH3(g) + 2H2O(l)
The ionic equation is:
NH4⁺(aq or s) + OH⁻(aq) → NH3(g) + H2O(l)

This is also a common test for ammonium ions in a compound. When a

suspected compound is warmed with sodium hydroxide, NaOH solution,
ammonia gas will be released if it contains ammonium ions. The ammonia
gas can be confirmed by using a red litmus paper.
iii. This reaction can also be used to prepare ammonia in school laboratories,
the setup is as follow:

Note:
i. This reaction is also known as the displacement of ammonia.
ii. Calcium oxide, CaO is used as a drying agent. Other drying agents like
calcium chloride, CaCl2 and sulfuric acid, H2SO4 are not used because they
react with ammonia.

130
Manufacture of ammonia - the Haber process

1) The Haber process is used to manufacture ammonia on a large scale. A

brief summary of the Haber process:
3H2(g) + N2(g) ⇌ 2NH3(g) ; ΔH = -92 kJ mol⁻¹

2) i. Hydrogen gas is obtained by reacting methane, CH4(natural gas) with steam at

around 700 ºC and the presence of nickel as catalyst.
CH4(g) + H2O(g) → CO(g) + 3H2(g)
ii. Nitrogen gas is obtained by the purification of air. Air which contains mostly a
mixture of nitrogen and oxygen gas is reacted with hydrogen gas at high
temperature. Oxygen from the air will react with hydrogen to form water.
2H2(g) + O2(g) → 2H2O(g)
Oxygen gas is removed, leaving only nitrogen gas behind.

131
3) The required conditions for optimum yield are:
i. (400 - 450) ºC.
ii. 200 atm (equivalent to 20000 kPa).
iii. Presence of fine iron as catalyst.

4) Nitrogen and oxygen gas are fed into the reactor in a ratio of 1:3, which is the
one demanded by the equation. Excess of reactants are not used because it
wastes the space in the reactor and decrease the efficiency of the catalyst, since
the excess reactants will have nothing to react with.

5) i. The production of ammonia is an exothermic reaction in equilibrium.

According to Le Chatelier's principle, in order to shift the position of
equilibrium to the right as much as possible(to increase the yield), a low
temperature should be used. However, (400 - 450) ºC is not a low
temperature.
ii. A low temperature will decrease the rate of reaction albeit having a high
yield. The reaction will take a long time to complete and it is not
economically plausible.
iii. Hence, (400 - 450) ºC is the compromise temperature that produces a
good enough yield in a short time.

6) i. According to Le Chatelier's principle, the position of equilibrium will shift to

the right if the pressure is increased because there are less molecules on
the right of the equation. Besides, a high pressure can also increase the rate
of reaction. Hence, a high pressure, 200 atm is used.
ii. Higher pressures are not used because:
- it is expensive to build and maintain the pipes and generators to withstand
the pressure, this increases the production cost.
- there is a risk of the pipes exploding.
iii. Hence, 200 atm is the compromise pressure chosen on economic grounds.

7) A catalyst of fine iron is used to increase the rate of reaction. Although it

has no effect on the position of equilibrium, it is essential because without it, the
reaction will too long to complete.

8) Under these conditions, about 15% of nitrogen and hydrogen converts to

ammonia. Unreacted molecules are recycled again so that the overall
percentage conversion is about 98%.

132
Industrial use of ammonia and nitrogen compounds derived from ammonia

1) i. Ammonia can be used to make fertilisers. Common fertilisers include

ammonium sulfate, ammonium nitrate, ammonium phosphate and urea,
CO(NH2)2.
ii. This is because they contain the element nitrogen. Nitrogen is essential for
plants to grow healthy.

2) Ammonia is also a precursor for most nitrogen-containing compounds.

One famous example is the manufacture of nitric acid, HNO3 by the oxidation
of ammonia in the Ostwald process.

3) Nitric acid has several uses:

i. To make fertilisers such as ammonium nitrate(the main use).
ii. To make explosives such as TNT.
iii. To be used in the manufacture of dyes, polymers and drugs.

13.2 Environmental Consequence of Using

Nitrogen Compounds
Excessive use of nitrate fertilisers

1) When excessive nitrate or ammonium fertilisers are used, the unabsorbed ones
will dissolve in rain water and it leaches into lakes and rivers.

2) An excess of these chemicals in the waters can promote the growth of

algae, eventually causing an algae bloom. The algae grow exponentially across
the surface of water, blocking sunlight from the reach of aquatic plants and
causes the plants to die.

3) The algae grow faster than being consumed, eventually a large number of algae
die without being consumed. When their remains decompose, the process
takes up a lot of oxygen from the water. The oxygen level in the water will
eventually reach a level where no life can sustain.

4) This process of excess growth leading to the destruction of life in the water is
known as eutrophication.

133
5) Since nitrates are soluble in water, removing them from drinking water is very
expensive. High levels of nitrates in drinking water can cause a disease in young
babies called 'blue baby syndrome'. Nitrates in water can also potentially
cause stomach cancer.

Oxides of nitrogen as pollutants

1) i. Nitrogen monoxide, NO is formed when electric spark is passed through a

medium of nitrogen and oxygen.
ii. This happens in the atmosphere during lightning storms. In petrol engines, it
is formed when sparks are used to ignite the petrol.
N2(g) + O2(g) → 2NO(g)
iii. It can be removed in petrol engines using a catalytic converter. A catalytic
converter uses expensive metals like platinum as a catalyst to convert harmful
pollutants into non-harmful substances. In this case, it converts the harmful
nitrogen monoxide and carbon monoxide into non-harmful nitrogen and
carbon dioxide gases.
2NO(g) + 2CO(g) → N2(g) + CO2(g)

134
2) i. Nitrogen monoxide is converted to nitrogen dioxide, NO2 in the atmosphere.
2NO(g) + O2(g) → 2NO2(g)
ii. Nitrogen dioxide acts as a catalyst in the conversion of sulfur dioxide, SO2
into sulfur trioxide, SO3.
SO2(g) + NO2(g) → SO3(g) + NO(g)
iii. Sulfur dioxide and sulfur trioxide are the main causes of acid rain. Sulfur
dioxide oxidises into sulfur trioxide and sulfur trioxide reacts with water in the
atmosphere to form sulfuric acid.
SO3(g) + H2O(l) → H2SO4(aq)
iv. The sulfuric acid then fall on earth as acid rain.
v. The nitrogen monoxide reacts with water in the atmosphere to re-form
nitrogen dioxide and the cycle repeats.
2NO(g) + O2(g) → 2NO2(g)

13.3 Sulfur Compounds

Uses and formation of sulfur dioxide, SO2 and its consequences

1) Atmospheric sulfur dioxide is formed during the burning of fossil fuels.

Fossil fuels like coal and oil all contain sulfur compounds, and when the coal or
the oil product are burned, sulfur dioxide is produced.

2) As discussed above, sulfur dioxide in the atmosphere can cause acid rain. The
consequences of acid rain include:
i. the corrosion of limestone buildings as the calcium carbonate reacts
with the acid.
ii. the corrosion of ironwork as the iron reacts with the acid.
iii. the acidification of lakes and rivers leading to the death of aquatic life.
This is complicated by the fact that a fall in pH dissolves aluminium ions from
the soil. Aluminium ions are toxic to fish.
iv. damage to trees. This again is partly the result of aluminium ions being
toxic to plants.

3) On the other hand, sulfur dioxide can be used as food preservative in, for
example, wine and dried fruit and vegetable. It has two functions:
i. It slows oxidation of the food by oxygen in the air.
ii. It also kills bacteria.

135
Manufacture of sulfuric acid - the Contact process

1) The Contact process:

i. makes sulfur dioxide.
ii. converts the sulfur dioxide into sulfur trioxide.
iii. converts the sulfur trioxide into concentrated sulfuric acid.

2) The sulfur dioxide, SO2 can be made by using two methods:

i. Burning sulfur in an excess of air.
S(s) + O2(g) → SO2(g)
ii. Heating sulfide ores like pyrite in an excess of air.
4FeS2(s) + 11O2(g) → 2Fe2O3(s) + 8SO2(g)

3) The sulfur dioxide made is then converted into sulfur

trioxide. This is the key process in the Contact process.
2SO2(g) + O2(g) ⇌ 2SO3(g) ; ΔH = -196 kJ mol⁻¹

4) The required conditions to achieve this are:

i. (400 - 450) ºC.
ii. (1 - 2) atm (equivalent to about 101 kPa).
iii. Presence of vanadium(V) oxide, V2O5 as catalyst.

4) i. Sulfur dioxide and oxygen gas are fed into the reactor in a
ratio of 1:1. An excess of oxygen is used to shift the
position of equilibrium to the right.
ii. Higher proportions of oxygen are not used because it
wastes the space in the reactor and decrease the efficiency
of the catalyst, since the excess oxygen will have nothing
to react with.

5) i. The production of sulfur trioxide is an exothermic reaction in equilibrium.

According to Le Chatelier's principle, in order to shift the position of
equilibrium to the right as much as possible(to increase the yield), a low
temperature should be used. However, (400 - 450) ºC is not a low
temperature.
ii. A low temperature will decrease the rate of reaction albeit having a high
yield. The reaction will take a long time to complete and it is not
economically plausible.

136
 iii. Hence, (400 - 450) ºC is the compromise temperature that produces a
good enough yield in a short time.

6) i. According to Le Chatelier's principle, the position of equilibrium will shift to

the right if the pressure is increased because there are less molecules on
the right of the equation. Besides, a high pressure can also increase the rate
of reaction.
ii. However, the reaction is done almost at atmospheric pressure. This is because
even at this relatively low pressure, the conversion rate is already about
99.5 %. Increasing the pressure will only result in minor improvements.
ii. Higher pressures are not used because:
- it is expensive to build and maintain the pipes and generators to withstand
the pressure, this increases the production cost.
- there is a risk of the pipes exploding.

7) A catalyst of vanadium(V) oxide, V2O5 is used to increase the rate of

reaction. Although it has no effect on the position of equilibrium, it is essential
because without it, the reaction will too long to complete.

8) i. Then, sulfur trioxide is first converted into oleum or fuming sulfuric acid.
This is done by dissolving sulfur trioxide in concentrated sulfuric acid.
H2SO4(l) + SO3(g) → H2S2O7(l)
ii. It is then reacted with water to produce sulfuric acid.
H2S2O7(l) + H2O(l) → 2H2SO4(l)

9) In the last step, water cannot just react with sulfur trioxide. This is because a
mist of poisonous and uncontrollable sulfuric acid will be formed.
Dissolving it in concentrated sulfuric acid is a more gentle and safe way.

137
CHAPTER 14: An Introduction to Organic
Chemistry

14.1 Organic Compounds

14.2 Organic Reactions
14.3 Isomerism

Learning outcomes:

(a) interpret, and use the general, structural, displayed and skeletal formulae of the following
classes of compound:
(i) alkanes and alkenes.
(ii) halogenoalkanes.
(iii) alcohols (including primary, secondary and tertiary).
(iv) aldehydes and ketones.
(v) carboxylic acids and esters.
[Candidates will be expected to recognise the shape of the benzene ring when it is present in
organic compounds. Knowledge of benzene or its compounds is not required for AS.]
(b) interpret, and use the following terminology associated with organic reactions:
(i) functional group.
(ii) homolytic and heterolytic fission.
(iii) free radical, initiation, propagation, termination.
(iv) nucleophile, electrophile.
(v) addition, substitution, elimination, hydrolysis.
(vi) oxidation and reduction.
[in equations for organic redox reactions, the symbols [O] and [H] are acceptable]
(c) (i) describe the shapes of the ethane and ethene molecules.
(ii) predict the shapes of other related molecules.
(d) explain the shapes of the ethane and ethene molecules in terms of σ and π carbon-carbon
bonds.
(e) describe structural isomerism, and its division into chain, positional and functional group
isomerism.
(f) describe stereoisomerism, and its division into geometrical (cis-trans) and optical isomerism.

138
(g) describe cis-trans isomerism in alkenes, and explain its origin in terms of restricted rotation
due to the presence of π bonds.
(h) explain what is meant by a chiral centre and that such a centre gives rise to optical isomerism
(i) identify chiral centres and/or cis-trans isomerism in a molecule of given structural formula.
(j) deduce the possible isomers for an organic molecule of known molecular formula.
(k) deduce the molecular formula of a compound, given its structural, displayed or skeletal
formula.

139
14.1 Organic Compounds
What is organic chemistry?

1) Organic chemistry is the study of carbon compounds (excluding simple

compounds like CO, CO2, CO3²⁻, HCO3⁻).

Formulae of organic compounds

1) There are five ways in which organic compounds/molecules can be presented:

i. Empirical formula
ii. Molecular formula
iii. Structural formula
iv. Displayed formula
v. Skeletal formula

2) i. Empirical formula gives the simplest ratio of the number of atoms of

each element present in the compound.
ii. Molecular formula gives the actual number of atoms of each element
present in the compound.
iii. These two formulae are least useful and rarely used in organic chemistry
because they do not reveal much information about the compounds.

3) Structural formula shows the order of the atoms joined together in an

organic compound. These formulae are usually written in one line.
Examples: Ethane - CH3CH3
Ethene - CH2=CH2 (only double and triple bonds are shown)
Ethanoic acid - CH3COOH
2-methylpentane - CH3CH(CH3)CH2CH3

4) Displayed formula shows the order of the atoms joined together, as well as
the orientation of the atoms and bond angles.
Examples:

Ethane Ethene Ethanoic acid 2-methylbutane

140
5) Skeletal formula shows only the functional groups. The carbon and hydrogen
atoms are simplified and hidden. In a skeletal formula:
i. there is a carbon atom at each junction and at the end of the bond, there
is no carbon atom at a place occupied by another functional group.
ii. there is enough hydrogen atoms bonded to each carbon so that each
carbon has four bonds only.

2-methylpentane 3-methylbutanoic
acid Propene Benzene

Cyclohexane 2-methylbutanol

6) It is essential to learn to convert between different formulae of the same

compound.

Names of organic compounds

1) Organic compounds are named systematically according to the IUPAC

(International Union of Pure and Applied Chemistry) nomenclature.

2) For details, refer to the attached document at the end of the notes.

3) Some examples to fill the

page:

141
Functional groups

1) A functional group is a group of atoms in an organic compound that

determines the chemistry of that particular compound.

2) A homologous series is a series of compounds with the same functional group,

and the adjacent members differ in the number of carbon atoms.

[ Note: You do not need to memorise the table above at this moment. ]

142
Bonding in organic molecules

1) Carbon atoms which are sp³ hybridised(typically forming 4 bonds) have the
atoms bonded to it arranged in tetrahedral shape with a bond angle of
109.5°.

2) One such example is ethane. In an ethane molecule, the

two carbon atoms undergo sp³ hybridisation. All other
atoms are bonded to the carbon atoms via σ bonds. All
bond angles are 109.5°.

3) If the carbon chain is longer, all the bond angles are still 109.5°, the molecule
has a zig-zag shape.

Butane Octane
4) Carbon atoms which are sp² hybridised(typically forming 3
bonds) have the atoms bonded to it arranged in a trigonal
planar shape with bond angle 120°.

5) One such example is ethene. In an ethene molecule, the two carbon atoms
undergo sp² hybridisation. The two carbon atoms are connected via σ and π
bonds, a double bond is formed between the two carbon atoms. The bond
angle is 120°.

6) If the carbon chain is longer, depending on the number of double bonds, a

mixture of trigonal planar and tetrahedral shape is possible. However, each
carbon atoms can only have either one.

7) Observe the but-1,2-ene molecule beside. Carbon 1 3 4

and 2 are sp² hybridised, so the atoms around it
have a trigonal planar arrangement. Carbon 3 and 2

4 are sp³ hybridised, so the atoms around it have a 1

tetrahedral arrangement.

[ Note : For greater detail on hybridisation and bonding, refer Chapter 4 ]

143
14.2 Organic Reactions
Reactions that organic compounds undergo

1) Organic reactions are classified using two ways:

i. By the type of reagent used:
- Nucleophilic
- Electrophilic
ii. By what happens during the reaction:
- Addition
- Substitution
- Elimination

2) Some common reactions:

- Free-radical substitution
- Electrophilic addition
- Electrophilic substitution
- Nucleophilic addition
- Nucleophilic substitution
- Redox (oxidation and reduction)
- Hydrolysis
[ Note : You do not need to be familiar with these names at this moment. ]

Homolytic and heterolytic bond fission

1) Organic reactions involve the breaking of covalent bonds. There are two ways
in which a covalent bond can be broken, by homolytic or heterolytic fission.

2) Homolytic fission is the breaking of a covalent bond in

such a way that one electron goes to each atom,
forming free-radicals.

3) A free-radical is an atom or a group of atoms with an unpaired electrons

formed from the homolytic fission of a covalent bond and is very reactive.

4) Heterolytic fission is the breaking of a covalent

bond in such a way that both electrons go to
the same atom, forming cation and anion.

144
Curly arrows

1) Curly arrows are used in organic chemistry to represent the movement of

electron(s). It is often used in the presentation of an organic mechanism.

2) The tail of the arrow shows where the electron(s) originates from
while the head shows the place where electron(s) is/are moved to.
The electrons can either originate from a lone pair or from a
bond.

3) Half arrows show the movement of one electron while a full arrow shows the
movement of two electrons. In the diagram above, the first is a half arrow
while the second is a full arrow.

4) Curly arrows can only be used to represent the movement of electron(s), they
may not be used for other purposes to avoid ambiguity.

Nucleophiles and electrophiles

1) A nucleophile is a species which contains a lone pair of electrons and is

attracted to regions of positive charge or electron-deficient sites. They are often
negatively-charged or carry a partial negative charge.

2) Some examples of nucleophiles are NH3, CN⁻, OH⁻, Cl⁻, Br⁻ and H2O.

3) An electrophile is an electron-deficient species which can accept electrons and is

attracted to regions of negative charge or electron-rich sites. They are often
positively-charged or carry a partial positive charge.

4) Some examples of electrophiles are H⁺, Br⁺, Cl⁺ and NO2⁺.

[ Note : A benzene ring is an electron-rich region ]

145
14.3 Isomerism
What are isomers?

1) Isomers are two or more compounds with the same molecular formula but a
different arrangement of atoms in space. Organic molecules which exhibit this
property show isomerism.

2) This excludes any different arrangements which are simply due to

the molecule rotating as a whole, or rotating about particular bonds. For
example, both of the following are the same molecule. They are not isomers,
both are butane.

3) Isomers must have different names. A good way to identify isomers is by

naming the molecules, molecules with the same name are not isomers.

4) There are two types of isomerism

i. Structural isomerism
ii. Stereoisomerism

146
Structural isomerism

1) Chain isomerism arises due to the different arrangement of carbon

atoms in a chain. The carbon atoms may be arranged in a straight chain or
branched chain.

Isomers of butane, C₄H₁₀ Isomers of pentane, C₅H₁₂

2) Positional isomerism arises due to different positions of functional

group in the carbon chain.

Isomers of C3H7Br
Isomers of butanol, C₄H₉OH

3) Functional isomerism arises due to different functional groups.

Some isomers of C₃H₆O

[ Note : Propanal is an aldehyde while propanone is a ketone, they belong to

different homologous series ]

147
4) More examples:

Stereoisomerism - Geometrical (cis-trans or E-Z) isomerism

1) Geometrical isomerism arises due to the rotation about a bond is

restricted. It is common in compounds containing carbon-carbon double
bond(C=C bond) and certain ring systems.

2) i. A C=C bond cannot be rotated due to the presence of π bond. A π bond

will break if a rotation occurs. Conversely, a carbon-carbon single bond is
rotatable.

≡ ≠

ii. In ring systems, rotation about a bond is restricted due to the linkage of the
ring because the C-C bond is now part of the ring system.

148
3) Geometrical isomers occur in pairs, differing from each other in the
positioning of the two groups across the double bond.
i. A cis-isomer has the two groups on the same side of the double bond.
ii. A trans-isomer has the two groups on the opposite sides of the double bond.

4) To identify geometrical(cis-trans) isomers, it is essential to draw the groups

around the double bond showing the correct bond angles(120°).

5) Geometrical(cis-trans) isomerism cannot exist if either carbon carries

identical groups. In short, to have geometrical isomers, it is essential to have
two different groups on the left and two different groups on the right.

6) More examples:

149
7) Geometrical isomers have similar(not identical) chemical properties but different
physical properties.

8) cis-isomer generally has a higher boiling point than trans-isomer. This is

because dipoles in a cis-isomer do not cancel out each other, causing the entire
molecule to have a net dipole moment and it is polar. Permanent dipole-
dipole forces exist and more energy is required to overcome it.

9) trans-isomer generally has a higher melting point than cis-isomer. This is

because in the solid state, trans-isomers pack more efficiently in the crystalline
lattice due to its shape.

Stereoisomerism - Optical isomerism

1) Optical isomerism arises due to the ability of compounds to rotate the

plane of polarisation of a plane-polarised light.

2) A compound is said to be optically-active(optical isomerism exists) if it rotates

the plane of polarised light. If it does not, it is said to be optically-inactive.

3) For a compound to be optically active:

i. It needs to have an asymmetrical carbon with
four different groups attached to it so that
there is no plane of symmetry. The carbon atoms
with four different groups attached to it is called
the chiral carbon or chiral centre.
ii. The isomers must be mirror-images of each other
and are non-superimposable. That is, no matter
how the molecules are rotated, they never fully
resemble each other.
A and B are optical isomers

150
4) An example:

5) To identify optical isomers:

i. In chain systems, check which carbon has four different groups attached to it.
ii. In ring systems, check also which carbon has four different groups attached to
it. A different group here can be identified by tracking around that ring
from a particular carbon atom in either clockwise or anti-clockwise direction.
If the pattern along the way is the same, that carbon atom is not chiral, and
the converse is also true.
iii. An example:

Only carbon 9 is not a chiral carbon in this

cholesterol molecule

151
Attachment
NOMENCLATURE OF ORGANIC COMPOUNDS
©2010, 2003, 1980, by David A. Katz. All rights reserved.

Organic chemistry is the chemistry of carbon compounds. Carbon has the ability to bond with itself to
form long chains and, as a result, millions of compounds from simple hydrocarbons to large
biomolecules such as proteins, lipids, carbohydrates, and nucleic acids. Originally it was believed that
these compounds had to come from a living organism, now they are synthesized in the laboratory.

The simplest organic compounds are composed of carbon and hydrogen and are known as hydrocarbons.
There are four types, or classes, of hydrocarbons:
Alkanes: contain all C-C single bonds. These are known as saturated hydrocarbons.
Alkenes: contain at least one C=C double bond.
Alkynes: contain at least one C≡C triple bond. Both alkenes and alkynes are known as
unsaturated hydrocarbons
Aromatic hydrocarbons: contain a benzene structure

Lewis structures of alkanes look like this:

These are also called structural formulas. Since these take up a lot of space, condensed structural
formulas are used.

Even simpler than condensed structures are skeletal or line structures:

There are a range of structures used to represent organic compounds:

Before we start naming organic compounds, it is important to understand how carbon atoms are bonded.
Every carbon atom will try to form 4 bonds.
H
A carbon atom on the end of a chain of single bonded carbon atoms will be bonded to
one carbon atom and three hydrogen atoms:
C C H

1 152
 H
A carbon atom in the middle of a chain of single bonded carbon atoms will be H
bonded to two carbon atoms and two hydrogen atoms. C C C
C C C
H

H
A carbon atom bonded to 3 other single bonded carbon atoms will be bonded to one
hydrogen. C C C

H
A carbon atom on the end of a chain that is double bonded to another carbon atom be
bonded to two hydrogen atoms. C C
\
H

H H
A carbon atom in the middle of a chain of that is double bonded to another carbon
atom will be bonded to one carbon atom and one hydrogen atom. C C C C

A carbon atom on the end of a chain that is triple bonded to another carbon atom
will be bonded to one hydrogen atom. The second carbon atom in that chain is only C C C H
bonded to another carbon atom, but no hydrogen atoms.

I. Naming Saturated Hydrocarbons - The Alkanes

The names of the alkanes are derived from the Greek prefix for the particular number of carbon atoms
in the compound with an -ane ending. The names of the first ten alkanes are given in the following
table.

2 153
 Not all the alkanes are straight chained compounds, as shown in the previous table, they can have side chains or
branches. These variations of compounds which have the same number of carbon and hydrogen atoms, but a
different arrangement are known as isomers. Some isomers are shown in the diagram below.

Rules for Naming of Branched Hydrocarbons.

There are four parts to the name of a branched hydrocarbon
1. The parent chain: Tells how many carbons are in the longest continuous chain.
meth = 1 eth = 2 prop = 3 but = 4 pent = 5
2. The suffix: Tells what type of compound it is.
ane = an alkane ene = an alkene yne = an alkyne
3. The prefix: Tells what groups, or branches are attached to the parent chain.
methyl = CH3 ethyl = CH2 CH3 propyl = CH2 CH2 CH3
4. The location: Tells where groups, or branches, are attached to the parent chain.
nd rd th
2 = 2 carbon atom 3 = 3 carbon atom 4 = 4 carbon atom
st
Note: alkyl groups, or branches cannot be located on the 1 or last carbon

3 154
 Example 1:
CH3-CH-CH2-CH-CH3

CH3 CH3
1. Select as the parent chain the LONGEST CONTINUOUS CHAIN of carbon atoms. The
compound is considered to have been derived from the parent structure by the replacement of
hydrogens by various alkyl groups.

CH3-CH-CH2-CH-CH3

CH3 CH3

The longest continuous chain of carbon atoms in this example contains five carbon atoms.
Since the carbon atoms in this compound all contain The alkane that contains five carbon
atoms is pentane.

2. Identify the branches, or side chains, attached to the parent chain.

CH3-CH-CH2-CH-CH3

CH3 CH3

Both branches consist of single carbon atoms, there are called methyl groups

3. Starting from either end of the longest carbon chain, number the carbon atoms in the parent
chain consecutively so that the alkyl groups (or branches) are attached to the carbon atoms
with the lowest possible numbers.

1 2 3 4 5
CH3-CH-CH2-CH-CH3

CH3 CH3

For this compound, it makes no difference which end you start the numbering. In both
cases the alkyl groups, or branches are attached to the second and fourth carbon atoms in
the parent chain.

4. Name the compound in order of: number of carbon atom-alkyl group attached(number of
carbon atom-alkyl group attached- etc...) name of parent compound. If there are several
different alkyl groups attached to the parent chain, name them in order of increasing size or
in alphabetical order.

The name for this compound looks like it would be called would be called 2-methyl-4-
methylpentane, however, all branches with the same name are grouped together. The
number of these branches have a prefix:

di = 2 tri = 3 tetra = 4 penta = 5

But, each branch needs a specified location, so, the correct name is 2,4-dimethylpentane

4 155
Example 2
CH3 CH3

CH3- CH-CH2-CH-CH-CH2-CH3

CH2-CH2-CH3

In this compound, the longest continuous chain is 8 carbon atoms long. Note that the
longest continuous chain does not have to be straight. This longest chain is oct- (for 8
carbons)

All the bonds are single bonds, so this is an alkane. The suffix is -ane

This parent chain is octane

CH3 CH3

CH3- CH-CH2-CH-CH-CH2-CH3

CH2-CH2-CH3

There are three branches attached to the parent chain. Two of these are methyl groups
and one is an ethyl group.

Number the carbon atoms, so that the groups are attached to the carbon atoms with the
lowest possible numbers.

CH3 CH3

CH3- CH-CH2-CH-CH-CH2-CH3
1 2 3 4 5
CH2-CH2-CH3
6 7 8

The two methyl groups in this compound are attached on the 2nd and 4th carbon atoms and
the ethyl group is attached to the 5th carbon atom.

This compound is named 5-ethyl-2,4-dimethyloctane. Note that the branches are named
in alphabetical order.

II. Naming Unsaturated Hydrocarbons – Alkenes and Alkynes

Rules for Naming Alkenes and Alkynes

Alkenes contain at least one carbon to carbon double bond. The suffix used is –ene.

Alkynes contain at least one carbon to carbon triple bond. The suffix used is –yne.

5 156
Naming is the same as used for alkanes, except that the parent structure is the longest continuous
chain of carbon atoms that contains the carbon-carbon double bond or triple bond. The name is
derived by changing the suffix of the corresponding alkane name to –ene for an alkene and –yne for
an alkyne and a number is added to denote the location of the multiple bond.

Example:
CH3 CH CH CH3

The longest continuous chain in this compound contains four carbon atoms. The parent
structure would be named but + ene (to denote the double bond)

Number the carbon atoms in' the longest chain in such a way that the carbon atoms
containing the double bond have the lowest possible numbers.

1 2 3 4
CH3 CH CH CH3

For this compound, the numbering should start on the left side so the double bond will be
located between carbon atom no. 2 and carbon atom no. 3. Although the double bond involves
two carbon atoms, its position is designated by the number of the first doubly-bonded carbon
atom when numbering from the end of the parent chain nearest the double bond. So, this
compound would be named 2-butene.

Example:
CH3 CH2 CH=CH2

In this compound the double bond is located between the 1st and 2nd carbon atoms.
The compound is named 1-butene.

Example:
CH3 CH CH CH=CH2

The longest continuous chain in this compound contains five carbon atoms. The parent
structure would be named pent- however, the compound contains two carbon-carbon double
bonds. The number of double bonds, if greater than 1, is denoted by a prefix added to the
suffix.
di = 2 tri = 3 tetra = 4

The p[aren’t chain is named pentadiene Note that an “a” is added to the name to make it easier
to pronounce.

Number the carbon atoms in' the longest chain in such a way that the carbon atoms containing
the double bond have the lowest possible numbers.

5 4 3 2 1
CH3 CH CH CH=CH2

For this compound, the numbering should start on the right side so the double bonds will be
located between carbon atom no. 1 and carbon atom no. 2 and carbon atom no. 3 and carbon
atom no. 4. The name of the compound is 1,3-pentadiene

6 157
 Example
CH3 CH2 C CH

The longest continuous chain in this compound contains four carbon atoms. The parent
structure would be named but + yne (to denote the triple bond)

Number the carbon atoms in' the longest chain in such a way that the carbon atoms containing
the triple bond have the lowest possible numbers.

4 3 2 1
CH3 CH2 C CH

For this compound, the numbering should start on the right side so the triple bond will be
located between carbon atom no. 1 and carbon atom no. 2. This compound would be named 1-
butyne.

If the compound is branched, the name is determined similar to that used for the alkanes.

Example. CH 3-CH-CH=CH-CH3

CH3

This compound is named 4-methyl-2-pentene. Note that the double bond takes precedence in
naming.

III. Naming Aromatic Compounds

Aromatic Compounds are cyclic hydrocarbons containing a benzene structure.

Benzene can be represented by the resonance structures:

The actual structure of benzene, however, is a resonance hybrid of these two structure
usually written as:

7 158
 Benzene rings can be fused together. These compounds have common names.

Naphthalene Anthracene

An aromatic compound which is formed by having an alkyl group attached to a benzene ring
is named by prefixing the alkyl group name to the word benzene. An example of this is
named methylbenzene or toluene

If there are only two groups attached to the benzene ring, their relative positions can be
designated by numbers or by the terms ortho, meta. or para, abbreviated o-, m-, or p-.

1,2-dinitrobenzene 1,3-dinitrobenzene 1,4-dinitrobenzene

ortho-dinitrobenzene meta-dinitrobenzene para-dinitrobenzene

Ortho = the 1 and 2 positions on the ring (adjacent carbon atoms)

Meta = the 1 and 3 positions on the ring (alternate carbon atoms)
Para = the 1 and 4 positions on the ring (opposite carbon atoms)

IV. Naming Functional Group Compounds

Derivatives are formed by replacing one or more of the hydrogens in a hydrocarbon by a

FUNCTIONAL GROUP. The functional group is responsible for giving what is ordinarily an
inactive compound the characteristic chemical and physical properties of another class of
compounds.

A. Halogen Derivatives of Hydrocarbons

Functional Group: - X (F, Cl, Br, I)

General Formula: R-X

Naming of Halides
Halogens attached to a hydrocarbon chain are named by replacing the -ine ending of the halogen
name with –o. When naming a compound, halogens are named in the same manner as alkyl group
branches.

8 159
 Examples: Cl Br

CH3-Br CH3CH2-I CH3CHCH3 CH3CH2CHCH2 Br

bromomethane iodoethane 2-chloropropane 1,2-dibromobutane

B. Oxygen Derivatives of the Hydrocarbons

These functional group compounds contain at least one oxygen atom in its structure.

1. Alcohols
Functional Group: OH

General Formula: R OH

Naming of alcohols:
Number the-longest carbon chain so that the -OH group is attached to the carbon atom with the
lowest possible number. Name the parent compound by using the alkane name and replacing
the -e ending with an -ol ending. Indicate the position of the hydroxyl. group with a number in
any alcohol containing three or more carbon atoms.

Examples:
OH

CH3OH CH3CH2OH CH3CH2CH2OH CH3CHCH3

methanol ethanol 1-propanol 2-propanol
(methyl alcohol) (ethyl alcohol) (propyl alcohol) (isopropyl alcohol)

OH
Aromatic alcohols are called phenols and contain the structure:

2. Ethers
Functional Group: O
General formula: R O R

Naming of ethers
Ethers are commonly named by naming each group attached to the oxygen followed by the word
ether. If one group has no simple name, the ether can be named as an alkoxy derivative of the
larger group.

Examples:

CH3-O-CH3 CH3-O-CH2CH3 CH3CH2-O-CH2CH3

dimethyl ether methyl ethyl ether diethyl ether
(methoxymethane) (methoxyethane) (ethoxyethane)

9 160
3. Carbonyl Compounds
Carbonyl compounds all contain a O

This includes several types of compounds:

Aldehydes
Ketones
Carboxylic acids
Esters
Amides

a) Aldehydes
O

Functional Group: C H
O

General formula: R C H or shorthand as CHO (The oxygen is bonded to a terminal carbon

atom)

Naming of aldehydes:
Number the-longest carbon chain starting with the -CHO group. Name the parent compound by
using the alkane name and replacing the -e ending with an -al ending.

Examples:
O O

H C H CH3 C H
methanal ethanal
(methyl aldehyde) (ethyl aldehyde also known as acetaldehyde)

b) Ketones
O

Functional Group: C

General formula: R C R (The oxygen is bonded to a carbon atom in the middle of the chain)

Naming of Ketones:
Number the-longest carbon chain starting so that the –C=O group is attached to the carbon atom
with the lowest number. Name the parent compound by using the alkane name and replacing the -
e ending with an -one ending.

10 161
Examples:
O O

CH3 C CH3 CH3 C CH2 CH3

propanone 2-butanone
(dimethyl ketone or (methylethyl ketone)
acetone)

c) Carboxylic acids
O

Functional Group: C OH

General formula: R C OH or shorthand as COOH (The carboxyl group is bonded to a terminal

carbon atom)

Naming of acids:
Number the-longest carbon chain starting with the -COOH group. Name the parent compound by
using the alkane name and replacing the -e ending with an –oic acid ending.

Examples:
O O

H C OH CH3 C OH
methanoic acid ethanoic acid
(formic acid) (acetic acid)

d) Esters
An ester is formed from the combination of a carboxylic acid and an alcohol. They are often
highly aromatic compounds and are used for flavors and fragrances.
O

Functional Group: C O

General formula: R C O R’ (The R’ may be the same or different from R)

Naming of esters
Esters are usually named by naming the R’ group [from an alcohol] as an akyl group first
followed by the acid name [the R-C group] with ending -oate. Esters are often called by their
common names.

Examples of esters and their flavor/odor properties are given in the table below.

11 162
Formula Common name IUPAC name Flavor/odor

HC-O-CH2-CH3 ethyl formate ethyl methanoate rum

H3C-C-O-CH2-(CH2)3-CH3 n-amyl acetate pentyl ethanoate pears, bananas

H3C-C-O-CH2-CH2-CH(CH3)2 isoamyl acetate 3-methylbutyl ethanoate pears, bananas

H3C-C-O-CH2-(CH2)6-CH3 n-octyl acetate octyl ethanoate oranges

H3C-CH2-C-O- CH2-CH(CH3)2 isobutyl propionate 2-methylpropyl propanoate rum

H3C-CH2-CH2-C-O-CH3 methyl butyrate methyl butanoate apples

H3C-CH2-CH2-C-O-CH2-CH3 ethyl butyrate ethyl butanoate pineapples

H3C-CH2-CH2-C-O-CH2-(CH2)2-CH3 n-butyl butyrate butyl butanoate pineapples

H3C-CH2-CH2-C-O-CH2-(CH2)3-CH3 n-amyl butyrate pentyl butanoate apricots

H3C-(CH2)3-C-O-CH2-CH2-CH (CH3)2 isoamyl valerate 3-methylbutyl butanoate apples

HO
O
C
methyl salicylate methyl 2-hydroxybenzoate oil of wintergreen
H3C O

e) Amides
O

Functional Group: C N:

General formula: R C NH2

12 163
 Naming of Amides
Amides are commonly named similar to a carboxylic acid, replacing the –oic acid suffix with
amide.

Examples:
O O

H C NH2 CH3 C NH2

formamide ethanamide
(methylamide) (ethylamide or acetamide)

A summary of the functional group compounds, their structures and names is listed in
tables on the next two pages.

13 164
14

165
15

166
CHAPTER 15: Hydrocarbons
15.1 Introduction to Alkanes
15.2 Reactions of Alkanes
15.3 Introduction to Alkenes
15.4 Reactions of Alkenes
15.5 Uses of Hydrocarbons

Learning outcomes:

(a) show awareness of the general unreactivity of alkanes, including towards polar reagents.
(b) describe the chemistry of alkanes as exemplified by the following reactions of ethane:
(i) combustion.
(ii) substitution by chlorine and by bromine.
(c) describe the mechanism of free-radical substitution at methyl groups with particular reference
to the initiation, propagation and termination reactions.
(d) describe the chemistry of alkenes as exemplified, where relevant, by the following reactions of
ethene and propene (including the Markovnikov addition of asymmetric electrophiles to
propene):
(i) addition of hydrogen, steam, hydrogen halides and halogens.
(ii) oxidation by cold, dilute, acidified manganate(VII) ions to form the diol.
(iii) oxidation by hot, concentrated, acidified manganate(VII) ions leading to the rupture of the
carbon-to-carbon double bond in order to determine the position of alkene linkages in
larger molecules.
(iv) polymerisation.
(e) describe the mechanism of electrophilic addition in alkenes, using bromine/ethene and
hydrogen bromide/propene as examples.
(f) explain the use of crude oil as a source of both aliphatic and aromatic hydrocarbons.
(g) suggest how ‘cracking’ can be used to obtain more useful alkanes and alkenes of lower Mr
from larger hydrocarbon molecules.
(h) describe and explain how the combustion reactions of alkanes led to their use as fuels in
industry, in the home and in transport.
(i) recognise the environmental consequences of:
(i) carbon monoxide, oxides of nitrogen and unburnt hydrocarbons arising from the internal
combustion engine and of their catalytic removal.
(ii) gases that contribute to the enhanced greenhouse effect.

167
15.1 Introduction to Alkanes
What is an alkane?

1) A hydrocarbon is a compound containing carbon and hydrogen atoms only.

Examples of hydrocarbons are alkanes, alkenes, alkynes and arenes.

2) Alkanes are saturated hydrocarbons, the carbon atoms are joined to each
other via single covalent bond only. They form the homologous series with a
general formula CnH2n+2.

3) Physical properties of alkanes:

i. Alkanes are non-polar, thus they are soluble in non-polar solvents like CCl4.
They are, in general, insoluble and less dense than water.

ii. The boiling point of straight-chain alkanes increases with the size of
molecule. This is because the number of electrons in each molecule
increases, resulting in the increased strength of van der Waals'. Thus more
energy is required to break these forces.

iii. For a branched alkane, it is more volatile and its boiling point is lower than
its counterpart with the same number of carbon atoms. This is because they
are more spherical and have a lower surface area. Thus less temporary dipoles
can be set up and the van der Waals' forces are weaker, less energy is required
to overcome it.

iv. The density of liquid alkanes increases slightly. The mass of each
succeeding molecule increases but due to the increased strength of van der
Waals' forces, the molecules are more closer together. This results in higher
ratio of mass/volume.

168
4) Cycloalkanes are alkanes that joined up as a ring. The
smallest possible cycloalkane is cyclopropane.
Cycloalkanes have two hydrogen less than the
corresponding straight-chai alkanes.

15.2 Reactions of Alkanes

Reactivity of alkanes

1) Alkanes are saturated and generally unreactive because they are non-polar,
hence they are unattractive towards nucleophiles and electrophiles.

2) Alkanes will only react with non-polar reagents in the presence of heat or
ultraviolet light.

Combustion

1) Alkanes undergo complete combustion under excess oxygen gas to give

carbon dioxide and water. For example:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g) ΔH° = -890 kJ mol⁻¹

2) In general,

3) Larger alkanes are more difficult to ignite. This is because alkanes only burn in
the gaseous state and larger alkanes have stronger van der Waals' forces that
hold them together. Therefore more energy is required to vaporise it.

4) When the supply of oxygen is limited, alkanes undergo incomplete

combustion. The possible products are carbon monoxide, carbon and water.
For example,
2CH4(g) + 3O2(g) → 2CO(g) + 4H2O(g) or
CH4(g) + O2(g) → C(s) + 2H2O(g)

169
Halogenation

1) Alkanes undergo halogenation via free-radical substitution to give a range

of products. In free-radical substitution, hydrogen atoms in the molecule are
gradually substituted by halogen atoms.

2) Reagent : Chlorine gas, Cl2 or bromine gas, Br2

Condition : The presence of ultraviolet(UV) light or sunlight
Product : Halogenoalkanes (alkanes with halogens)

3) Free-radical substitution proceeds via a chain reaction. During a chain

reaction, for every reactive species you start off with, a new one is generated at
the end, and this keeps the process going.

4) i. When methane reacts with chlorine in sunlight, the greenish-yellow colour

fades and steamy acidic fumes of hydrogen chloride can be observed.

ii. However, this is a chain reaction and does not end here. More hydrogen
atoms will be substituted as long as there are sufficient chlorine atoms.

5) The mechanism of free-radical substitution:

i. Step 1: Initiation step
The reaction is initiated by the homolytic fission of chlorine molecule in
the presence of UV light, forming chlorine free radicals.

ii. Step 2: Propagation step

The free radicals then attack the methane molecules, leading to a chain
reaction.

170
 iii. Step 3: Termination step
The reaction ends with the free radicals joining up with each other.

[ Note: All other alkanes react in a similar manner but the reactions involved
are getting more and more complicated. ]

6) To produce mainly tetrachloromethane, an excess of chlorine gas is used so that

all the hydrogen atoms eventually get substituted.

7) Bromine gas reacts in a similar manner but the reaction is slower.

15.3 Introduction to Alkenes

What is an alkene?

1) Alkenes are unsaturated hydrocarbons which contain at least one

carbon-carbon double bond(C=C) bond. They form the homologous series
with the general formula of CnH2n.

2) The physical properties of alkenes are similar to that of alkanes.

3) Alkenes can exhibit both structural and stereoisomerism. This is due to

the rotation-restricting double bond. The isomers of C4H8 are:

The structural isomers The geometrical isomers

171
15.4 Reactions of Alkenes
Electrophilic addition

1) Unlike alkanes, alkenes are more reactive because they are

unsaturated and contain a C=C bond. A C=C bond contains
a σ bond and a π bond. A π bond is a region of high
density of electron which is open to attack by something
that carries an amount of positive charge, electrophiles.

2) Alkenes mainly undergo electrophilic addition. An electrophilic addition

reaction is the addition of an electrophile across the C=C bond.

3) The general mechanism of electrophilic addition:

i. The electronegativity difference in an electrophile, say, XY causes the
molecule to be polar. Therefore it carries a δ+ and δ- end. The δ+ end of
the molecule behaves as an electrophile.
ii. The δ+ end is attracted to the π bond, a region with high electron density.
As it approaches the π bond, the electrons in the X-Y bond are repelled
further and further to the Y atom.

iii. Eventually the electrons are donated to Y, forming Y⁻ ion. The X atom forms
a single bond with carbon. The electrons needed for this bonding come from
the π bond. As a result, the adjacent carbon atom will carry a positive charge
because it has lost its π electron to the C-X bond.

172
 iv. The carbon-containing species which carries a positive charge is called
carbocation. The carbocation is attracted to the negative Y⁻ ion. These two
particles eventually bond together via a co-ordinate bond.

4) In the examination, the mechanism can be written like this. The curly arrows
show the movement of electrons.

5) The addition of unsymmetrical alkenes follows Markovnikov's rule:

" In the addition of H-X to a C=C bond of an unsymmetrical alkene,
the hydrogen atom attaches itself to the carbon atom that holds the
greatest number of hydrogen atoms. "
Minor product

Major product

6) Hydrocarbons can be classified as primary, secondary or tertiary depending on

the number of R groups attached to the positive carbon.

The Rs are alkyl groups, they can be the same or different. Carbocation is
formed as an intermediate when the electrophile bonds with the carbon
atom.

7) The alkyl groups have an electron-pushing effect, they tend to push the
electrons towards the carbon atom which carries a positive charge.

173
8) It follows that tertiary carbocation is the most stable because the positive
charge is neutralised by the negative charges. The charge density on the carbon
atom is the least.

9) Therefore, if the electrophile is bonded in such a way that a tertiary carbocation

is produced, the stability of the intermediate formed can be increased. This can
only happen if the hydrogen attaches itself with the carbon with most hydrogen
atom(normally at the ends of the molecule). Therefore Markovnikov's rule is
obeyed.

10) Reactions that alkenes undergo:

i. Addition of hydrogen, H2 (Hydrogenation)
ii. Addition of steam, H2O (Hydration)
iii. Addition of halogen, X2 (Halogenation) where X = A halogen
iv. Addition of hydrogen halide, HX where X = A halogen
v. Oxidation by cold and hot potassium manganate(VII), KMnO4
vi. Addition polymerisation

Addition of hydrogen, H2 (Hydrogenation)

1) Reagent : Hydrogen gas, H2

Condition : Heat in the presence of nickel, Ni catalyst at 150 °C
Product : Alkanes

2) In hydrogenation of ethene, two hydrogen atoms are added across the C=C
double bond. Ethane is produced.

3) In this case, although hydrogen molecule has no polarity, it is still able to behave
as an electrophile. This is because as the hydrogen molecule approaches the
double bond, a dipole is induced due to the repulsion between the two bond
pair of electrons(one from the C=C bond, another from the H-H bond).

174
Addition of steam, H2O (Hydration)

1) Reagent : Steam, H2O

Condition : Heat the gaseous alkene at 330 °C and 60 atm in the
presence of phosphoric(V) acid, H3PO4 as catalyst
Product : Alcohols (compounds that -OH group)

2) In the hydration of alkene, steam, H-OH is added across the double bond.
Ethanol is produced.

3) The detailed mechanism of the reaction is as follow:

The only way oxygen can have 3

bonds is by having a positive charge.

4) The addition of unsymmetrical alkene is as follow. Take propene as an example:

Minor product

Major product

175
Addition of halogen, X2 (Halogenation)

1) Reagent : Halogen, X2 (in tetrachloromethane or aqueous)

Condition : Room temperature in dark
Product : Halogenoalkanes (alkanes with halogens)

2) When ethene is bubbled into Br2 in CC4 at room temperature in dark, Br-Br is
added across the C=C bond. The brown colour of bromine is decolourised.
1,2-dibromoethane is produced.

Ethene

3) The mechanism of this reaction is as follow:

4) When ethene is bubbled into aqueous Br2 at room temperature in dark, two
products are obtained:

5) Br2 in CCl4 is used as a test to differentiate alkanes and alkenes as they

both are colourless. Alkene will decolourise the brown colour of
bromine whereas alkane will not.

Addition of hydrogen halide, HX

1) Reagent : Hydrogen halide, HX(g)

Condition : Room temperature
Product : Halogenoalkanes (alkanes with halogens)

2) When ethene reacts with hydrogen bromide, 1-bromoethane, a halogenoalkane

is produced.

176
3) The mechanism of this reaction is as follow:

4) The addition of unsymmetrical alkene is as follow. Take propene as an example:

Oxidation by cold and dilute potassium manganate(VII) solution, KMnO4

1) Reagent : Cold and dilute potassium manganate(VII) solution,

KMnO4
Condition : Room temperature
Product : Alcohols(diols)

2) When ethene is reacted with cold, dilute acidified KMnO4 solution, the purple
colour of KMnO4 is decolourised. Ethane-1,2-diol is produced.

3) This is a redox reaction, the carbon species is oxidised while the oxidising agent
is reduced.

4) This is another test used to differentiate alkanes and alkenes. Only

alkene will decolourise the purple colour of KMnO4 whereas alkane will
not.

177
Oxidation by hot and concentrated potassium manganate(VII) solution, KMnO4

1) Reagent : Hot and concentrated acidified potassium

manganate(VII) solution, KMnO4
Condition : Room temperature
Product : Carbon dioxide/carboxylic acids/ketones

2) When an alkene is reacted with hot and concentrated acidified KMnO4

solution, the C=C bond in the alkene ruptures. The purple colour of
KMnO4 is also decolourised. The product formed will differ according to the
position of the C=C bond.

3) i. If there are two alkyl groups at one end of the bond, that part of the molecule
will give a ketone. For example:

ii. If there are one alkyl group and one hydrogen at one end of the bond, that
part of the molecule will give a carboxylic acid. For example:

Ethanal(an aldehyde) is further oxidised to ethanoic acid(a carboxylic acid)

The net effect is as such:

iii. If there are two hydrogens at one end of the bond, that part of the molecule
will give carbon dioxide and water. For example:

4) This reaction is useful in determining the position of C=C bond in an alkene

molecule. This can be done by examining the product(s) formed.

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Addition polymerisation

1) Alkenes can open up its C=C bond and join with each other in a long chain to
form a polymer. A polymer is a long-chain molecule made of repeating units
called monomers.

2) i. Polymer : Poly(propene)
Monomer : Propene

ii. Polymer : Poly(chloroethene) (polyvinyl chloride or PVC)

Monomer : Chloroethane

iii. Polymer : Poly(ethene) (polythene or polyethylene)

Monomer : Ethene
The conditions required for this to happen are as follow:
Temperature - about 60°C
Pressure - a few atmospheres
Catalyst - Ziegler-Natta catalysts or other metal compounds

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15.5 Uses of Hydrocarbons
Sources of hydrocarbons

1) Crude oil is the main source of hydrocarbons, it is found trapped in layers

beneath the surface of the earth. Crude oil is a complex mixture of
hydrocarbons - alkanes, cycloalkanes and aromatic compounds.
[ Note: Aromatic compounds are compounds which have a benzene ring
attached to it ]

2) These substances can be separated by a technique called fractional

distillation. Fractional distillation is the separation of compounds by their boiling
points.

3) Different hydrocarbons have different molar masses, and so they have different
boiling points.

4) Crude oil enters the bottom of the fractionating column as liquid and vapour.
The liquids(less volatile hydrocarbons) are drawn off at the bottom while less
volatile ones rise up the column. They condense at different levels as the
temperature gradually falls and are collected as liquids.

5) The most volatile short-chain hydrocarbons, which are methane and butane,
leave the top as gases.

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Catalytic cracking

1) After the hydrocarbons are separated, oil companies found that hydrocarbons
from lighter fractions(such as gasoline) are in higher demand compared to the
ones from heavier fractions.

2) Therefore something must be done to convert those heavier hydrocarbons into

the more useful, lighter ones. This is done by cracking.

3) Cracking breaks less useful hydrocarbons(normally long-chain) into smaller and

more useful ones. Alkenes are normally produced as they are more industrially
useful. This is because starting from alkenes, a wide range of organic
compounds can be produced.

4) The larger hydrocarbons are fed into a chamber which contains no oxygen, so
combustion does not take place. The larger hydrocarbons are heated at high
temperature(about 500 °C) and passed over zeolite catalyst.

5) Cracking of a hydrocarbon is not unique, different molecules of hydrocarbons

can be broken in different ways, giving rise to different products. One possible
reaction of involving C15H32 is as follow:

Environmental consequences of using hydrocarbons

1) Alkanes are often used as fuels. This is because the combustion of alkanes is an
exothermic process and produces a lot heat energy. Alkanes are also readily
available and relatively cheap. The main uses of alkanes as fuels are:

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 - To generate electricity.
- To heat domestic houses and cook foods.
- To provide energy needed in industrial processes.
- To provide power for ships, aeroplanes, trains, lorries, buses, cars and
motorbikes.

2) However, the combustion of alkanes can produce some poisonous gases which
can act as pollutants.

3) One such example is carbon monoxide, CO which arises from the

incomplete combustion of alkane. Carbon monoxide is a toxic gas that will bind
readily to the haemoglobin molecules in the blood. This causes oxygen cannot
be transported to cells and the victim will die.

4) The carbon dioxide, CO2 produced from the complete combustion of alkane
can also act as a greenhouse gas. The increasing amount of these greenhouse
gases enhances global warming.

5) Burning fuels in car engines will also oxidise the nitrogen gas in air to produce
oxides of nitrogen(nitrogen monoxide, NO or nitrogen dioxide, NO2).
These oxides of nitrogen is believed to contribute in the formation of acid rain.
(For more details, refer Chapter 13)

6) Catalytic converters can be installed to remove carbon monoxide and the oxides
of nitrogen. More details about catalytic converters can be found in
Chapter 13.

182
CHAPTER 16: Halogen Derivatives
16.1 Introduction to Halogenoalkanes
16.2 Reactions of Halogenoalkanes
16.3 Uses of Halogenoalkanes

Learning outcomes:

(a) recall the chemistry of halogenoalkanes as exemplified by

(i) the following nucleophilic substitution reactions of bromoethane: hydrolysis, formation of
nitriles, formation of primary amines by reaction with ammonia.
(ii) the elimination of hydrogen bromide from 2-bromopropane.
(b) describe the mechanism of nucleophilic substitution (by both SN1 and SN2 mechanisms) in
halogenoalkanes.
(c) interpret the different reactivities of halogenoalkanes(with particular reference to hydrolysis and
to the relative strengths of the C-Hal bonds).
(d) explain the uses of fluoroalkanes and fluorohalogenoalkanes in terms of their relative chemical
inertness.
(e) recognise the concern about the effect of chlorofluoroalkanes on the ozone layer.

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16.1 Introduction to Halogenoalkaes
What are halogenoalkanes?

1) Halogenoalkanes(or alkyl halides) are compounds in which one or more hydrogen

atoms in an alkane have been replaced by halogen atoms (fluorine, chlorine,
bromine or iodine).

2) Halogenoalkanes can be classified as primary, secondary or tertiary

depending on the number of alkyl groups(R groups) attached to the carbon
atom holding the halogen atom.

3) Some examples of halogenoalkanes:

Chloropropane, 2-bromopropane, 1,2-diiodoethane, ICH₂CH₂I

CH₃CH₂CH₂Cl CH₃CHBrCH₃

Physical properties of halogenoalkanes

1) i. Boiling point of the halogenoalkanes

increases as the molecular size
increases. This is because there are
more electrons in larger molecules
and more temporary dipoles can
be set up, resulting in stronger van der
Waal's forces.
ii. Primary halogenoalkanes have higher boiling point compared to secondary
and tertiary halogenoalkanes of the same molecular weight. This is because
the surface area of primary halogenoalkanes is higher, more
temporary dipoles can be set up, resulting in stronger van der Waal's forces.

184
2) i. Halogenoalkanes are insoluble in water but soluble in organic
solvents.
ii. This is because when dissolved in water(polar solvents), the energy needed to
break the hydrogen bonds between water molecules is too high. The energy
released when halogenoalkane-water attraction is set up is not enough to
compensate it. This makes the structure to gain energy overall, making it less
stable.
iii. While when it is dissolved in organic solvents, the halogenoalkane-solvent
attraction is strong enough to compensate the energy needed to break the
weak van der Waal's forces between organic molecules.

16.2 Reactions of Halogenoalkanes

Chemical reactivity of halgenoalkanes

1) Fluoroalkanes are the least reactive while

iodoalkanes are the most reactive. This is because
the carbon-halogen bond strength decreases from fluorine
to iodine as the size of the halogen atoms increases.

2) Since reactions of halogenoalkanes involve the breaking of the carbon-halogen

bond, it follows that carbon-iodine bonds are the easiest to break, making them
the easiest to react.

Nucleophilic substitution

1) The signature reaction of halogenoalkanes is nucleophilic substitution.

Nucleophilic substitution is the substitution of an atom by a nucleophile.

2) A nucleophile is a species(an ion or a molecule) which is strongly attracted to a

region of positive charge in something else. It normally carries either a
partial or fully negative charge on the molecule. Some example of
nucleophiles are shown below:

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3) Nucleophilic substitution is possible due to polarity of the carbon-halogen
bond. Halogens are more electronegative than carbon, therefore the electron
pair in the carbon-halogen bond will be attracted towards the halogen end,
leaving the halogen slightly negative and the carbon slightly positive.

4) Since nucleophiles are negative, it is attracted to the positive carbon and this
initiates the substitution to occur.

5) For carbon-iodine bond, although there is no polarity, it is still possible

because the nucleophile can induce a dipole in the bond due to the electrons
repelling each other.

6) Nucleophilic substitution is done via two mechanisms, the SN1 or SN2

mechanism.
-Primary halogenoalkanes will use SN2.
-Tertiary halogenoalkans will use SN1.
-Secondary halogenoalkanes will use both.

The SN2 mechanism

1) In SN2 mechanism, the 'S' stands for substitution, the 'N' stands for nucleophilic
and the '2' stands for the initial step(rate-determining step) involves two
species(the halogenoalkane and the nucleophile).

2) The general mechanism of an SN2 reaction, using bromoethane, CH3CH2Br as

a typical primary halogenoalkane and Nu⁻ as a general nucleophile:
i. The carbon-bromine bond in bromoethane is polarised due to
the electronegativity difference between the two atoms. Carbon
carries a partial positive charge while bromine carries a partial
negative charge.
ii. The nucleophile, Nu⁻ is attracted towards the positive carbon,
beginning to form a co-ordinate bond with it. Meanwhile, the negative
bromine atom is repelled further due to the approaching nucleophile.
iii. Eventually, there is a state, called the transition state where the carbon-
bromine bond is just at the point of breaking and the carbon-nucleophile
bond is just at the point of forming. The transition state has five groups
attached to the central carbon atom.
iii. The movement goes on until the Nu⁻ is firmly attached to the carbon, and the
bromine has been expelled as a Br⁻ ion. The nucleophile has substituted the
bromine.

186
3) In the examination, the mechanism can be written like this:

....or a more simplified version:

4) Note:
i. When the nucleophile approaches the halogenoalkane, it approaches from
the opposite side of bromine because the negative bromine hinders the
attack from its side.
ii. It is crucial to get the orientation of the atoms right, the molecule has been
inverted at the end of the reaction. This is called the inversion of
configuration(product has a configuration opposite to the reactant).

5) It is unlikely for tertiary halogenoalkanes to react by SN2 mechanism. This is

because SN2 mechanism involves the nucleophile approaching and forming
bond from the opposite side of the halogen. In the case of tertiary
halogenoalkane, it is unlikely because the opposite of the halogen is cluttered
with CH3 group(s).

187
The SN1 mechanism

1) In SN1 mechanism, the '1' stands for the initial step(rate-determining step)
involves one species only(the halogenoalkane). The overall rate of
reaction is governed by the rate of the first step.

2) The general mechanism of an SN2 reaction, using 2-bromo-2-methylpropane,

(CH3)3Br as a typical tertiary halogenoalkane and Nu⁻ as a general nucleophile:
i. The reaction happens in two stages. In the first stage, a small proportion of
the halogenoalkane ionises to give a carbocation and a bromide ion.

ii. Once the carbocation is formed, it will react immediately when it comes
into contact with a nucleophile, Nu⁻. The lone pair of the nucleophile is
strongly attracted towards the positive carbon, and moves towards it to
create a new bond.

3) Tertiary halogenoalkanes react via SN1 because the tertiary carbocation

intermediate formed is relatively stable. If primary halogenoalkanes
were to react in the same manner, the primary carbocation formed would be
relatively unstable, resulting in high activation energy of the reaction.

4) Secondary halogenoalkanes can react using both SN1 and SN2 mechanisms
because:
i. The opposite of the halogen is not cluttered by CH3 group(s).
ii. The secondary carbocation formed is more stable than primary carbocation.

Summary of reactions that halogenoalkanes undergo

1) i. Substitution with hydroxide ions, OH⁻.

ii. Substitution with cyanide ions, CN⁻.
iii. Substitution with ammonia, NH3.
iv. Elimination

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Substitution with hydroxide ions, OH⁻ (Hydrolysis)

1) Reagent : Aqueous sodium hydroxide, NaOH or water

Condition : Heat under reflux
Product : Alcohols

2) When aqueous sodium hydroxide, NaOH is heated with bromoethane under

reflux, the bromine is substituted by hydroxide ion, OH. Ethanol is produced.
CH3CH2Br + NaOH → CH3CH2OH + NaBr
...or the ionic equation:
CH3CH2Br + OH⁻ → CH3CH2OH + Br⁻

3) Heating under reflux means heating with a condenser placed vertically in the
flask to prevent loss of volatile substances from the mixture.

4) The mechanism of this reaction is the same as the ones mentioned before for
primary halogenoalkanes, the nucleophile here is hydroxide ion, OH⁻.

5) Water can also be used as the nucleophile in this reaction. However, hydrolysis
using water occurs much slower. This is because the negatively-charged OH⁻ is
a more effective nucleophile than water. The mechanism is as shown:

6) For a particular alkyl group R, the rate of hydrolysis decreases in the order:

...as the strength of carbon-halogen bond increases progressively from iodine to

fluorine. In fact, the carbon-fluorine bond is so strong that fluoroalkanes do not
undergo hydrolysis.

189
Substitution with cyanide ions, CN⁻

1) Reagent : Potassium cyanide, KCN in ethanol

Condition : Heat under reflux
Product : Nitriles

2) When ethanolic potassium cyanide, KCN is heated with 2-bromo-2-

methylpentane under reflux, the bromine is substituted by cyanide ion, CN⁻.
2-methyl-2-propanenitrile is produced.
(CH3)3Br + KCN → (CH3)3CN + KBr
...or the ionic equation:
(CH3)3Br + CN⁻ → (CH3)3CN + Br⁻
3) The mechanism of this reaction is the same as the ones mentioned before for
tertiary halogenoalkanes, the nucleophile here is cyanide ion, CN⁻.

Step 1: Ionisation of the

halogenoalkane

Step 2: Rapid attack by CN⁻

4) This is a very useful reaction in organic synthesis.

i. It serves as a means of increasing the length of carbon chain(a step-up
reation).
ii. The nitrile produced can be converted to carboxylic acid by heating under
reflux with acid or alkali(hydrolysis reaction)
(CH3)3CN + 2H2O + H⁺ → (CH3)3COOH + NH4⁺ ; acidic hydrolysis
(CH3)3CN + H2O + OH⁻ → (CH3)3COO⁻ + NH3 ; alkaline hydrolysis

Substitution with ammonia, NH3

1) Reagent : Excess ammonia, NH3 in ethanol

Condition : Heat in sealed tube
Product : Amines

2) When ethanolic ammonia, NH3 is heated with bromoethane in a sealed tube,

the bromine is substituted by amine group, -NH2. The reaction occurs in two
stages. In the first stage, a salt, ethylammonium bromide is formed.
CH3CH2Br + NH3 → CH3CH2NH3⁺Br⁻

190
 ...In the second stage, a reversible reaction occurs between this salt and the
excess ammonia. Ethylamine, a primary amine is formed.
CH3CH2NH3⁺Br⁻ + NH3 ⇌ CH3CH2NH2 + NH4Br

3) The mechanism of the reaction is shown below, ammonia is behaving as a

nucleophile.

4) If the ammonia used is not in excess, a complicated mixture containing

secondary and tertiary amine is obtained. This is because ethylamine is a good
nucleophile and it can attack the unreacted bromoethane.

Elimination

1) Reagent : Sodium hydroxide, NaOH in ethanol

Condition : Heat under reflux
Product : Alkenes

2) In this alcoholic condition, the hydroxide ion, OH⁻ acts as a base rather than a
nucleophile. Hence it will accept a proton(hydrogen ion) from the carbon atom
next door to the one holding the bromine. The resulting re-arrangement of the
electrons expels the bromine as a bromide ion and produces ethene.

3) The mechanism of the reaction is shown below:

2 2

4) In unsymmetrical halogenoalkanes, a mixture of products of different isomers

is produced due to the choice of hydrogen being removed.

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16.3 Uses of Halogenoalkanes
The use of CFCs

1) CFCs are chlorofluorocarbons, compounds containing carbon with chlorine

and fluorine atoms attached. Two common CFCs are CFC-11(CCl3F) and
CFC-12(CCl2F2).

2) Some properties and uses of CFCs:

CFCs and the environment

1) CFCs have many uses in our daily life. However, due to their stability and
inertness, they are also large responsible for the destruction of the ozone
layer. Ozone layer prevents harmful ultraviolet radiation from reaching us.

2) Destruction of the ozone layer involves the conversion of ozone molecule,

O3 to oxygen molecule, O2. The detailed mechanism is as shown below:

192
3) Possible solutions to protect the ozone layer:
i. Reduce the use of CFCs. For example, replace aerosol spray with manual
pump spray.
ii. Collect and recycle CFCs for future use.
iii. Find alternatives for CFCs.

4) Possible alternatives for CFCs:

i. Use HCFCs(CFCs with at least one hydrogen atom, for example, CF3CHCl2)
- HCFCs have smaller effect on ozone depletion because they are more
readily destroyed in the troposphere.
- However, a disadvantage of using it is, it is flammable. Also, it could
potentially form toxic chemicals in the troposphere.
ii. Use LPG(liquid petroleum gas) as propellant in aerosol sprays.
iii. Use air-blowing agent in packaging and building industries.
iv. Use water-based cleaning system in electronic industries.

193
CHAPTER 17: Hydroxy Compounds
17.1 Introduction to Alcohols
17.2 Reactions of Alcohols

Learning outcomes:

(a) recall the chemistry of alcohols, exemplified by ethanol:

(i) combustion.
(ii) substitution to give halogenoalkanes.
(iii) reaction with sodium.
(iv) oxidation to carbonyl compounds and carboxylic acids.
(v) dehydration to alkenes.
(vi) formation of esters by esterification with carboxylic acids.
(b) (i) classify hydroxy compounds into primary, secondary and tertiary alcohols.
(ii) suggest characteristic distinguishing reactions, e.g. mild oxidation.

194
17.1 Introduction to Alcohols
What are alcohols?

1) Alcohols are compounds in which one or more hydrogen atoms in an alkane

have been replaced by an -OH group.

2) Alcohols can be classified as primary, secondary or tertiary depending on

the number of alkyl groups(R groups) attached to the carbon atom holding the
-OH group.

3) Some examples of alcohols:

Physical properties of alcohols

1) i. Alcohols are soluble in water because they can form

hydrogen bonds with water molecules.
ii. However, the solubility decreases as the number of
carbon atoms increases. This is because the presence of
long hydrocarbon tail disrupts the effectiveness of hydrogen bonding.

2) i. Alcohols have higher boiling points than the

alkanes with similar Mr due to the presence of
intermolecular hydrogen bonding in addition
of van der Waals' forces of attraction.
ii. The boiling point increases as the number of
carbon atoms increases. This is because there
are more electrons, hence more temporary
dipoles can be set up. More energy is required
to overcome these forces.

195
17.2 Reactions of Alcohols
Summary

1) Summary of reactions that alcohols undergo:

i. Combustion.
ii. Dehydration to give alkenes.
iii. Reaction with sodium.
iv. Substitution to give halogenoalkanes.
iv. Oxidation.
v. Esterification.

Combustion

1) Reagent : Oxygen supply

Condition : Heat
Product : Carbon dioxide(and carbon monoxide) and water

2) Alcohols undergo complete combustion under excess oxygen to give carbon

dioxide and water. Example:
C2H5OH + 3O2 → 2CO2 + 3H2O

3) When oxygen is limited, carbon monoxide and carbon soot might be formed.

Dehydration

1) Reagent/ : Excess concentrated sulfuric acid, H2SO4 or hot

Catalyst aluminium oxide, Al2O3
Condition : Heat at about 170 °C
Product : Alkenes

2) When ethanol is heated with concentrated sulfuric acid, the alcohol is

dehydrated, a water molecule is removed from the alcohol. Ethene is produced.

3) During dehydration, the -OH group gets removed together with a

hydrogen atom from the next-door carbon atom.

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4) i. Alternatively, dehydration can be carried
out by passing ethene through hot
aluminium oxide. The ethene gas
produced is collected over water.
ii. At the end of the reaction, the apparatus
is left to cool with the delivery tube out of
water. This is done so that the cold water would not be sucked back into the
hot delivery tube, cracking it eventually.

5) For more complicated alcohols, be careful of the possibility of more than one
product being formed and also the possibility of geometric isomers in
the alkenes. This is due to a different hydrogen being removed from the
alcohol. An example is butan-2-ol.

Reaction with sodium

1) Reagent : Sodium metal, Na

Condition : Room temperature
Product : Alkoxides and hydrogen gas

2) Acids react with metals to produce hydrogen gas and a salt. Alcohols are very
weak acids, so they undergo this reaction as well.

3) When sodium metal is added to ethanol, the sodium metal sinks and bubbles of
hydrogen gas are released. The salt formed is sodium ethoxide, a white solid.
2CH3CH2OH + 2Na → 2CH3H2O⁻Na⁺ + H2

4) This reaction can be used as a test for hydroxy, -OH group. Bubbles of
hydrogen gas is released if a hydroxy group is present.

5) Remember, in order to produce a hydrogen gas molecule, H2, two hydrogens

from two molecules of alcohols must be used.

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Substitution to give halogenoalkanes

1) The -OH group of the alcohol can be substituted by a halogen to produce a

halogenoalkane. The halogen can be obtained from three sources:
i. Hydrogen halide, HX ; where X = Cl/Br/I
ii. Phosphorus halide, PCl5 or PBr3 or PI3
iii. Thionyl chloride(or sulfur dichloride oxide), SOCl2

2) With hydrogen halide, HX:

i. The alcohol is refluxed with sodium halide, NaX and concentrated sulfuric
acid, H2SO4 to produce the hydrogen halide, HX.
NaX + H2SO4 → HX + NaHSO4 ; where X = Cl/Br
For iodine, phosphoric(V) acid, H3PO4 is used instead of sulfuric acid.
ii. The hydrogen halide, HX is the reacted with the alcohol. Take ethanol as an
example:
CH3CH2OH + HX → CH3CH2X + H2O ; where X = Cl/Br/I

3) With phosphorus halide, PCl5/PCl3/PBr3/PI3:

i. Alcohols react with phosphorus(V) chloride, to produce a halogenoalkane,
white fumes of hydrogen chloride gas is also observed. Take ethanol as
an example:
CH3CH2OH + PCl5 → CH3CH2Cl + POCl3 + HCl
ii. This can be used as a test for the hydroxy, -OH group. White fumes of
hydrogen chloride gas is observed if hydroxy group is present.
iii. For phosphorus(III) halides, a halogenoalkane is also obtained. The
phosphorus halides are prepared in situ by mixing red phosphorus and the
halogen.
3CH3CH2OH + PX3 → 3CH3CH2X + H3PO4 ; where X = Cl/Br/I

4) With thionyl chloride, SOCl2:

i. Alcohols react with thionyl chloride to produce a halogenoalkane. Sulfur
dioxide and hydrogen chloride are are given off as well.
CH3CH2OH + SOCl2 → CH3CH2X + SO2 + HCl ; where X = Cl/Br/I
ii. This reaction is useful in obtaining pure halogenoalkane. This is because the
other two products are gases, and they can be separated from the mixture
easily.

198
Oxidation

1) Reagent : Acidified potassium dichromate(VI), K2Cr2O7 or acidified

potassium manganate(VI), KMnO4
Condition : Heat under reflux
Product : Primary alcohol - Aldehydes and carboxylic acids
Secondary alcohol - Ketones
Tertiary alcohol - Will not be oxidised

2) Different class of alcohols(primary, secondary or tertiary) will behave differently

during oxidation. Therefore, it is a very useful test to distinguish them.

3) i. For primary alcohols, if the alcohol used is in excess and the

product formed is distilled off as soon as possible, aldehydes are
formed. Take ethanol as an example, ethanal is formed.
CH3CH2OH + [O] → CH3CHO + H2O

ii. If the alcohol used is limited and heated under reflux, the primary
alcohol will be oxidised to aldehyde then to carboxylic acid. Take ethanol
as an example, from the aldehyde formed, ethanoic acid is formed.
CH3CHO + [O] → CH3COOH

...or the full equation from ethanol to ethanoic acid:

CH3CH2OH + 2[O] → CH3COOH + H2O

4) For secondary alcohols, the secondary alcohol will be oxidised to a

ketone. Take propan-2-ol as an example, propanone is formed.
CH3CH(OH)CH3 + [O] → CH3COCH3 + H2O

5) For tertiary alcohols, they will not be oxidised. This is because there is no
hydrogen atom from the carbon atom holding the -OH group can be removed.

199
6) For observation:
i. If K2Cr2O7 is used as oxidising agent: colour of solution changes from
orange to green.
ii. If KMnO4 is used as oxidising agent : colour of solution changes from
purple to colourless.

7) Summary:

Esterification

1) Reagent : Carboxylic acid

Conditions : Heat under reflux with concentrated sulfuric acid, H2SO4
as catalyst
Product : Esters

2) Esters are derivatives of carboxylic acids. In an ester, the hydrogen from the
-COOH group of carboxylic acid is replaced by an alkyl group. The alkyl
group came from the alcohol. Some common esters and their naming:

4) Note that the name of an ester is 'alcohol + carboxylic acid'.

200
5) For example, to make methyl butanoate, methanol and butanoic acid are used.
Both of them are heated under reflux with the presence of catalyst. Esters can
be detected from a sweet-smelling odour.
CH3OH + CH3CH2CH2COOH ⇌ CH3CH2CH2COOCH3 + H2O

Methanol + butanoic acid

+ conc. sulfuric acid

Note:
1) To find out more about aldehydes and ketones, refer Chapter 18.
2) To find out more about carboxylic acids and esters, refer Chapter 19.

201
CHAPTER 20: Lattice Energy

20.1 Introduction to Lattice Energy

20.2 Born-Haber Cycles

20.3 Ion Polarisation

20.4 Enthalpy Changes in Solutions

Learning outcomes:

(a) explain and use the term lattice energy (∆H negative, i.e. gaseous ions to solid lattice).
(b) explain, in qualitative terms, the effect of ionic charge and of ionic radius on the numerical
magnitude of a lattice energy.
(c) apply Hess’ Law to construct simple energy cycles, and carry out calculations involving such
cycles and relevant energy terms, with particular reference to:
(i) the formation of a simple ionic solid and of its aqueous solution.
(ii) Born-Haber cycles (including ionisation energy and electron affinity).
(d) interpret and explain qualitatively the trend in the thermal stability of the nitrates and
carbonates in terms of the charge density of the cation and the polarisability of the large
anion.
(e) interpret and explain qualitatively the variation in solubility of Group II sulfates in terms of
relative magnitudes of the enthalpy change of hydration and the corresponding lattice energy.

202
20.1 Introduction to Lattice Energy
What is lattice energy?

1) In a solid ionic crystal lattice, the ions are bonded by strong

ionic bonds between them. These forces are only completely
broken when the ions are in gaseous state.

2) Lattice energy(or lattice enthalpy) is the enthalpy change when one mole of solid
ionic lattice is formed from its scattered gaseous ions.

3) Lattice energy is always negative. This is because energy is always released

when bonds are formed.

4) Use sodium chloride, NaCl as an example. It can be described as the enthalpy

change when one mole of sodium chloride is formed from its scattered gaseous
sodium and chloride ions. The value is -787 kJ mol⁻¹.

5) Lattice energy is a good indication of the strength ionic bonds. The higher the
magnitude of lattice energy, the stronger the ionic bond formed. This is because
more energy is released when strong bonds are formed.

Factors affecting lattice energy

1) There are two factors which govern the magnitude of lattice energy:
i. Charge on the ions.
ii. Radius of the ions.

2) i. The higher the charge on the ion, the higher the lattice energy.
ii. This is because ions of higher charge have stronger attraction towards each
other. Hence more energy is released when bonds are formed between them.

203
 iii. For example, magnesium oxide, MgO has a higher lattice energy than sodium
chloride. This is because Mg²⁺ and O²⁻ have higher charge than Na⁺ and Cl⁻
ions.

3) i. The larger the ionic radius, the lower the lattice energy.
ii. This is because the attraction between ions gets weaker as the distance
between them increases. Hence less energy is released when bonds are formed
between them.
iii. For example, the lattice energy of sodium halides gets lower from sodium
fluoride to sodium iodide. This is because as the size of the halide ion
increases, the distance between sodium and halide ions increases.

204
Electron affinity

1) The first electron affinity, ΔHea1 is the energy released when one mole of electrons is
added to each atom in one mole of the atoms of the element to form one mole
of gaseous 1- ions.
For example:
Cl(g) + e⁻ → Cl⁻(g) ; ΔHea1 = -349 kJ mol⁻¹

2) The use of electron affinities are almost always confined to Group 6 and 7
elements.

3) Generally, first electron affinities are exothermic, this is because there is an

attraction between the positive nucleus and the incoming electron. Energy is
released when this attraction is set up.

4) Electron affinity is a measure of the attraction between the incoming

electron and the nucleus - the stronger the attraction, the more energy is
released.

5) The factors that govern the magnitude of electron affinity is the same as the
ones for ionisation energy - nuclear charge, distance between nucleus
and incoming electron and shielding effect of electrons.

6) Going down a Group, the magnitude of first electron affinity decreases. This
is because the distance between incoming electron and the nucleus increases,
therefore the attractive force between them is less. The increasing nuclear
charge is offset by the increasing shielding effect by inner electrons.

7) Take Group 7 as an example, the elements follow

the pattern described, except for fluorine. This is
because fluorine is a very small atom with high
electron density. A repulsion between electrons
is created hence the attraction between nucleus
and incoming electrons is less. In Group 6, oxygen
and the rest follow the exact same trend.

8) Group 6 elements have a lower electron affinity compared to their

corresponding Group 7 elements. This is because the nuclear charge of Group
6 elements is lower, less attraction is set up between the nucleus and outer
electrons, therefore less energy is released.

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9) The second electron affinity, ΔHea2 is the energy released when one mole of
electrons is added to each gaseous 1- ions of to form one mole of gaseous 2-
ions.
For example:
O⁻(g) + e⁻ → O²⁻(g) ; ΔHea1 = +844 kJ mol⁻¹

10) Second electron affinities are usually endothermic, this is because energy is
required to add electrons into an already negative region due to the repulsion
between electrons.

Recall some enthalpy changes

1) Standard enthalpy change of formation, ΔH°f is the enthalpy change when one mole
of a compound is formed from its elements under standard condition.
The reactants and products must be in their standard states.
2Fe(s) + 1½O2(g) → Fe2O3(s) ; ΔH°f [ Fe2O3(s) ] = -824.5 kJ mol⁻¹

2) Standard enthalpy change of atomisation, ΔH°at is the enthalpy change when one mole
of gases atoms is formed from its element under standard conditions.
½H2(g) → H(g) ; ΔH°at [ ½H2 ] = +218 kJ mol⁻¹

20.2 Born-Haber Cycles

What are Born-Haber cycles?

1) Lattice energy cannot be determined experimentally, however, it can be

calculated using a special type of Hess' cycle, this is called the Born-Haber
cycle.

2) It assumes that the final product is the solid ionic compound. To make this
compound, we start with its elements in their standard states, and convert them
to ions in gaseous state. These ions are then converted to the solid lattice.
Lattice energy can be obtained by considering the energetics of the entire
process.

206
3) A typical Born-Haber cycle looks like this, take sodium chloride, NaCl as an
example:
Here, the final product is NaCl(s). To make
this, we begin with Na(s) + ½Cl2(g). This is
then converted step-by-step into Na⁺(g) +
Cl⁻(g). This is done using atomisation energy,
ionisation energy and electron affinity.

The energy released when the gaseous ions

join to form the lattice is the lattice energy.

By Hess' Law,
-411 = +107 + 496 + 122 - 349 + LE
LE = -411 - 107 - 496 - 122 + 349
LE = -787 kJ mol⁻¹

• -411 is the enthalpy change of formation.

• +107 is the enthalpy change of atomisation
of Na.
• +496 is the first ionisation energy of Na.
• +122 is the enthalpy change of atomisation
of ½Cl2.
• -349 is the first electron affinity of Cl.

Note:
1) Each level should only indicate one type of enthalpy change.

207
4) Another example, Born-Haber cycle of magnesium chloride, MgCl2.

The thing to note here is the

multiplication of atomisation
enthalpy and electron affinity
of Cl by 2 and also the use of
second ionisation energy for
Mg.

20.3 Ion Polarisation

Polarising power and polarisability

1) Not all ionic compounds are fully ionic, the same goes to covalent compounds.
Pure ionic and covalent bondings are extremes.

2) In an ionic compound, the positive charge on the

cation may attract the negative electron cloud of the
anion towards it. This results in distortion of the
electron cloud of the anion.

3) The factors which affect ion polarisation are:

i. the charge density of the cation.
ii. the size of the anion.

4) A cation is said to have a high charge density if it has a hogh charge spread
over a small volume. For example, Mg²⁺ has a higher charge density than Ba²⁺.

208
5) i. The higher the charge density of the cation, the higher the polarising power.
(Easier to polarise)
ii. The larger the size of the anion, the higher the polarisability. (Easier to be
polarised)

6) Ion polarisation causes ionic bonds to have a certain degree of covalent

character, making them impure.

Ion polarisation and thermal stability

Refer to Chapter 11: Group II, section 11.4.

20.4 Enthalpy Changes in Solutions

Recall enthalpy change of solution and hydration

1) Standard enthalpy change of solution, ΔH°sol is the enthalpy change when one mole
of ionic compounds is dissolved in water to form an infinitely dilute solution
under standard conditions.
MgCl2(s) + aq → MgCl2(aq) ; ΔH = ΔH°sol

2) Standard enthalpy change of solution can be exothermic or endothermic, that

is, some substance dissolve exothermically while others dissolve endothermically.
So, why is there a difference?

3) Standard enthalpy change of hydration, ΔH°hyd is the enthalpy change when one mole
of gases ions dissolves in water to form hydrated ions of infinite dilution under
standard conditions.
Ca²⁺(g) + aq → Ca²⁺(aq) ; ΔH = ΔH°hyd

4) Standard enthalpy change of hydration is

always exothermic, this is because when an
ion dissolves in water, bonds are formed between
the ions and water molecules. This bond is called
the ion-dipole bond.

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5) Factors affecting the magnitude of hydration enthalpy are:
i. the size of the ion.
ii. the charge on the ion.

6) i. The larger the size of the ion, the lower the hydration enthalpy. For example,
hydration enthalpy of the Group II ions decreases down the Group.
ii. The higher the charge of the ion, the higher the hydration enthalpy. For
example, Group II ions have higher hydration enthalpy compared to their
corresponding Group I ions.

The process of dissolving

1) i. The process of dissolving is imagined as if the solid ionic lattice is first

broken down to form gaseous ions. Lattice energy is absorbed.
ii. These gaseous ions are then dissolved in water, this is how they exist in
the final solution. The energy involved here is hydration enthalpy.
iii. The energy involved in the entire process(from solid ionic lattice to hydrated
ions) is the solution enthalpy.

2) Therefore, take sodium chloride, NaCl as an example:

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3) An example:

Solubility of Group II sulfates

1) The solubility of Group II sulfates decreases down the Group.

2) The solubility is governed by the sign of the enthalpy change of solution,

ΔH°sol. If ΔH°sol > 0, the sulfate is relatively insoluble. If ΔH°sol < 0, the sulfate is
relatively soluble.

3) The sign of ΔH°sol is governed by the relative magnitude of ΔH°hyd and ΔH°latt.

4) i. Going down the Group, if ΔH°hyd decreases faster than ΔH°latt, the
sulfates become more insoluble down the Group.
ii. Going down the Group, if ΔH°latt decreases faster than ΔH°hyd, the
sulfates become more soluble down the Group.

5) In the case of Group II sulfates, the former is true.

6) i. Hydration enthalpy decreases faster down the Group because the size of the
cations increases dramatically down the Group, the anion is a constant.
ii. Lattice energy decreases slower down the Group because the sulfate ion is
much larger than the Group II ions. As a result, the sulfate ion contributes to
a greater part in the magnitude of lattice energy. That is, the increase in size
of the cations is relatively insignificant.

211
CHAPTER 21: Electrode Potentials
21.1 Standard Electrode Potential
21.2 Measuring Standard Electrode Potential
21.3 Using E° Values
21.4 Cells and Batteries
21.5 Quantitative Electrolysis

(a) define the terms:

(i) standard electrode (redox) potential.
(ii) standard cell potential.
(b) describe the standard hydrogen electrode.
(c) describe methods used to measure the standard electrode potentials of:
(i) metals or non-metals in contact with their ions in aqueous solution.
(ii) ions of the same element in different oxidation states.
(d) calculate a standard cell potential by combining two standard electrode potentials.
(e) use standard cell potentials to:
(i) explain/deduce the direction of electron flow from a simple cell.
(ii) predict the feasibility of a reaction.
(f) construct redox equations using the relevant half-equations.
(g) predict qualitatively how the value of an electrode potential varies with the concentration of
the aqueous ion.
(h) state the possible advantages of developing other types of cell, e.g. the H2/O2 fuel cell and
improved batteries (as in electric vehicles) in terms of smaller size, lower mass and higher
voltage.
(i) state the relationship, F = Le, between the Faraday constant, the Avogadro constant and the
charge on the electron.
(j) predict the identity of the substance liberated during electrolysis from the state of electrolyte
(molten or aqueous), position in the redox series (electrode potential) and concentration.
(k) calculate:
(i) the quantity of charge passed during electrolysis.
(ii) the mass and/or volume of substance liberated during electrolysis, including those in the
electrolysis of H2SO4(aq), Na2SO4(aq).
(l) describe the determination of a value of the Avogadro constant by an electrolytic method.

212
21.1 Standard Electrode Potential
Electrode potentials and half-cells

1) i. When a metal, M is immersed into water, there is a tendency that it will lose
electrons and enter the water as metal ions, Mª⁺. Soon, the water becomes a
solution of the metal ions. This leaves the electrons on the metal and the
metal becomes more and more negative.
M(s) → Mª⁺(aq) + ae⁻ , electrons are left behind the metal
ii. The positive metal ions in the solution will be attracted towards the negative
metal. Eventually some will accept the electrons and re-form the metal.
Mª⁺(aq) + ae⁻ → M(s) , ions from solution deposited

2) When the rate of these two reactions becomes equal, an equilibrium is

established. At this equilibrium, the metal goes into the solution at a rate exactly
same as the ions depositing.
Mª⁺(aq) + ae⁻ ⇌ M(s)

3) Different metals will have different tendencies of doing so. Some will
lose electrons more readily than others. Reactive metals like magnesium prefer
to stay as ions, therefore the position of equilibrium lies further to the left.
Oppositely, unreactive metals like copper prefer to stay as metals, therefore the
position of equilibrium lies further to the right.

Mg²⁺(aq) + 2e⁻ ⇌ Mg(s)

Cu²⁺(aq) + 2e⁻ ⇌ Cu(s)

4) This arrangement of a metal dipping into a solution of its ions is called a

half-cell. The metal in a half-cell is called an electrode.

5) Since there is a difference in charge between the

negative metal and the positive metal ion solution, a
potential difference exists between them. This
potential difference is called the electrode potential, E.
Electrode potential is measured in volts, V.

213
6) Electrode potential is also a numerical method to express the tendency of a
metal to form ions.

7) The bigger the difference between the negativeness and positiveness, the greater
the electrode potential. However, this electrode potential is impossible to
measure.

8) However, the difference of electrode potentials between two half-cells is

measurable. This can be done by connecting a wire between the two electrodes
with a voltmeter between them.

9) Hence, to standardise, a standard half-cell must be chosen as the reference

electrode so that all electrode potentials measured are relative to this.

10) This standard half-cell is called the standard hydrogen electrode, SHE.

Standard hydrogen electrode, SHE

1) A standard hydrogen electrode has hydrogen gas in equilibrium with hydrogen

ions. The electrode potential of this half-cell is taken as 0 V.
2H⁺(aq) + 2e⁻ ⇌ H2(g) E=0V

2) Since hydrogen is not a metal, platinum foil covered in porous platinum is used
as the electrode. Platinum also catalyses the set up of the equilibrium.

3) Hydrogen gas at 100 kPa is bubbled over the platinum. On the surface of the
platinum, the equilibrium is set up. The concentration of hydrogen ions is
at 1 mol dm⁻³.

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Standard electrode potential, E°

1) Standard electrode potential, E° is the e.m.f. of a cell when a half-cell is connected to

a standard hydrogen electrode under standard conditions.

2) The standard conditions are:

i. A pressure of 100 kPa(approximately atmospheric pressure).
ii. A temperature of 298 K or 25 °C.
iii. The ions at a concentration of 1.0 mol dm⁻³.

3) A standard condition is required because all these factors will affect the position
of equilibrium of the reaction, therefore the magnitude of E° will also be
affected.

4) The standard electrode potential of a cell can be measured by connecting a

half-cell to a standard hydrogen electrode like this:

Note:
1) A high resistance voltmeter is used so that
no current flows through the external
circuit and the maximum voltage(the
e.m.f.) can be recorded.
2) A salt bridge physically separates the
half-cells but allows the passage of
electricity between the electrodes. It
contains ions that does not react with the
solution.
2) 1 bar = 100 kPa ≈ 1 atm

5) Recall that electrode potential measures the tendency of a metal to lose its
electrons. Standard electrode potential compares this tendency with the
tendency of hydrogen to release its electrons.

6) i. A negative value of E° implies that the metal loses electrons more readily than
hydrogen does. Therefore the position of equilibrium lies further to the left.
ii. A positive value of E° implies that the metal loses electrons less readily than
hydrogen does. Therefore the position of equilibrium lies further to the right.
Mª⁺(aq) + ae⁻ ⇌ M(s) ; E° = negative
2H⁺(aq) + 2e⁻ ⇌ H2(g) ; E° = 0 V
Nⁿ⁺(aq) + ne⁻ ⇌ N(s) ; E° = positive

215
7) Remember that standard electrode potential is all about comparing. A positive
E° does not mean the position of equilibrium is exactly at the right. It is further
to the right compared to the position of equilibrium of SHE.

8) i. The bigger the negative value, the further the position of equilibrium is to the
left and the more reactive that metal is.
ii. The bigger the positive value, the further the position of equilibrium is to the
right, and the less reactive that metal is.

The electrochemical series

1) The electrochemical series is built up by arranging various redox equilibria in

order of their standard electrode potentials.

2) The figures above show some common redox equilibria arranged according to
their standard electrode potentials. The full list can be found in the Data Booklet.

3) From the top to the ''bottom, the position of equilibrium shifts from right to left.
This is because the value of E° changes from the most positive to the most
negative.

4) This implies that the ease of losing electrons by the element increases
from top to bottom(or the ease of gaining electrons by the ion decreases
from top to bottom).

5) i. Ions at the top(with more positive E° value) gain electrons and get reduced
more readily, hence they are good oxidising agents.
ii. Elements(metals) at the bottom(with more negativ E° value) lose electrons and
get oxidised more readily, hence they are good reducing agents.

216
21.2 Measuring Standard Electrode Potential
The big picture

1) The standard electrode potential of the following system will be considered:

i. A metal/metal ion half-cell with SHE.
ii. A non-metal/non-metal ion half-cell with SHE.
iii. An ion/ion(with different oxidation states) half-cell with SHE.
iv. The combination of the above three half-cells.

Metal/metal ion half-cell

+ -
1) Take magnesium as an example of a metal.
The equilibrium set up on both electrodes
are:
Mg²⁺(aq) + 2e⁻ ⇌ Mg(s)
2H⁺(aq) + 2e⁻ ⇌ H2(g)

2) From the voltmeter reading, the E°cell = 2.34 V. Thus, the standard electrode
potential of Mg/Mg²⁺ half-cell is -2.34 V.

3) i. Cathode, which is the positive terminal is

platinum of the H2/H⁺ half-cell. This is because
more electrons are being accepted here due to
the position of equilibrium of the H2/H⁺ being
further to the right.
ii. Anode, which is the negative terminal is
magnesium of the Mg/Mg²⁺ half-cell. This is
because more electrons are being released here due to the position of
equilibrium of the Mg/Mg²⁺ half-cell being further to the left.

4) The full cell can be represented using a cell

diagram. A simple cell diagram is as
shown beside.
Note:
i. The positive electrode is always written on the right
side.
ii. The species with lowest oxidation state is written
next to the inert electrode.

217
5) A negative E° value implies that magnesium loses electrons more readily
than hydrogen does.

5) If magnesium is replaced by copper, the value of E° will be +0.34 V. Copper of

Cu/Cu²⁺ half-cell will be the positive terminal while platinum of H2/H⁺ half-cell
will be the negative terminal.

6) A positive E° value implies that copper ions gain electrons more readily
than hydrogen ions does.

Non-metal/non-metal ion half-cell

1) Take chlorine as an example of a

non-metal. The equilibrium set up
on both electrodes are:
2Cl⁻(aq) + 2e⁻ ⇌ Cl2(g)
2H⁺(aq) + 2e⁻ ⇌ H2(g)
2) Since chlorine is not a metal, the electrical contact with the solution is made by
using platinum as the electrode(same as SHE).

3) From the voltmeter reading, the E°cell = 1.36 V. Thus, the standard electrode
potential of Cl2/Cl⁻ half-cell is +1.36 V.

4) i. Cathode, which is the positive terminal is platinum of the Cl2/Cl⁻ half-cell.

This is because more electrons are being accepted here due to the position of
equilibrium of the Cl2/Cl⁻ being further to the right.
ii. Anode, which is the negative terminal is platinum of the H2/H⁺ half-cell. This
is because more electrons are being released here due to the position of
equilibrium of the H2/H⁺ half-cell being further to the left.

5) A positive E° value implies that chloride ions gain electrons more readily
than hydrogen ions does.

6) The cell diagram of this cell is:

218
Ion/ion half-cell

1) Two different ions of the same

element with two different
oxidation states can also be
used as a half-cell. Take
iron(II) and iron(III) ions as
example. The equilibrium set up on both electrodes are:
Fe³⁺(aq) + e⁻ ⇌ Fe²⁺(aq)
2H⁺(aq) + 2e⁻ ⇌ H2(g)

2) Since there is no solid metal as an electrode, electrical contact the solution is

made by using platinum as the electrode.

3) From the voltmeter reading, the E°cell = 0.77 V. Thus, the standard electrode
potential of Fe²⁺/Fe³⁺ half-cell is +0.77 V.

4) i. Cathode, which is the positive terminal is platinum of the Fe²⁺/Fe³⁺ half-cell.

This is because more electrons are being accepted here due to the position of
equilibrium of the Fe²⁺/Fe³⁺ being further to the right.
ii. Anode, which is the negative terminal is platinum of the H2/H⁺ half-cell. This
is because more electrons are being released here due to the position of
equilibrium of the H2/H⁺ half-cell being further to the left.

5) A positive E° value implies that iron(III) ions gain electrons more readily
than hydrogen ions does.

6) The cell diagram of this cell is:

Combination of half-cells

1) In fact, the SHE shown in previous examples can be replaced by other

half-cells.

2) When this happens, the standard cell potential, E°cell will also change, the new
E°cell is simply the difference between the E° values of the two half-cells.
E°cell = E°(bigger value) - E°(smaller value)

219
3) For example, when Zn/Zn²⁺ half-cell is connected
to Cu/Cu²⁺ half-cell, the equilibrium set up on
both electrodes are: (+)
(-)
Zn²⁺(aq) + 2e⁻ ⇌ Zn(s) ; E° = -0.76 V
Cu²⁺(aq) + 2e⁻ ⇌ Cu(s) ; E° = +0.34 V

4) From the voltmeter reading, the E°cell = 1.10 V.

This can also be calculated, using:
E°cell = 0.34 - (-0.76) = 1.10 V

4) i. Cathode, which is the positive terminal is copper of the Cu/Cu²⁺ half-cell.

This is because more electrons are being accepted here due to the position of
equilibrium of the Cu/Cu²⁺ being further to the right.
ii. Anode, which is the negative terminal is platinum of the Zn/Zn²⁺ half-cell.
This is because more electrons are being released here due to the position of
equilibrium of the Zn/Zn²⁺ half-cell being further to the left.

20.3 Using E° Values

The usage of E° values

1) The value of standard electrode potential, E° can be used in some ways:

i. To predict standard cell potentials, E°cell.
ii. To determine the direction of electron flow.
iii. To predict the feasibility of reactions.
iv. To determine the strength of reducing and oxidising agents.

Predicting standard cell potentials, E°cell

1) The standard cell potential, E°cell of a cell consisting of two half-cells can be
predicted by connecting them together using wires with a voltmeter.

2) i. Find from the Data Booklet the required equilibrium equation.

ii. Copy down the equilibrium equations and their corresponding E° values.
iii. Use the formula E°cell = E°(bigger value) - E°(smaller value).

220
Determining the direction of electron flow

1) When the high-resistance voltmeter of a cell is removed,

electrons will flow from one cell to another. The electron
will flow from the half-cell with more electrons(anode)
to the half-cell with less electrons(cathode).

2) For example, if the voltmeter in the Zn/Zn²⁺ half-cell and Cu/Cu²⁺ half-cell is
removed, electrons will flow from zinc electrode to copper electrode.

3) Due to the fact that the system is equilibrium, the decrease in electron
concentration in the Zn/Zn²⁺ equilibrium will be accompanied by some
changes. The same goes to the increase in electron concentration in Cu/Cu²⁺
half-cells. This comes from Le Chatelier's principle.

4) If the electrons continue to flow, the position of equilibrium keeps shifting,

eventually producing a one-way reaction.
Zn(s) → Zn²⁺(aq) + 2e⁻ , releases electrons to the Cu/Cu²⁺ half-cell
Cu²⁺(aq) + 2e⁻ → Cu(s) , accepts electrons from the Zn/Zn²⁺ half-cell
...combining these two equations:
Zn(s) + Cu²⁺(aq) → Zn²⁺(aq) + Cu(s)

5) Electrons will always flow from the half-cell with lower(more negative or
less positive) E° value to the half-cell with higher(less negative or more
positive) E° value.

221
6) Two more examples:

e⁻

Predicting the feasibility of reactions(two methods)

1) Reactions with positive E° value is said to be thermodynamically feasible.

2) Sometimes this prediction fails because:

i. the actual conditions of the reaction are not standard conditions.
ii. the reaction has high activation energy.

3) Remember:
i. E° value gives no information about the reaction rates.
ii. E° value applies to standard conditions only.

4) i. If you are given an equation, split the equation into two half-equations, the
find the corresponding E° values from the Data Booklet.
ii. Add the two E° values together and determine whether the sum is positive
or negative.
iii. Reverse the equation may be necessary, remember to reverse the sign too.

222
5) Examples:

6) Alternatively, it can also be predicted by looking at the reactants and products

of the equation.

7) Example 1: Will oxygen oxidise iron(II) hydroxide to iron(III) hydroxide under

alkaline conditions?
i. Find from the Data Booklet the equations involving the reactants and products
stated and write down their corresponding E° values.

ii. Determine the direction of electron flow. Remember that electrons flow from
the half-cell with more negative E° value to the half-cell with more positive E°
value.
iii. Determine the shift of position of equilibrium, and see whether it tallies with
the reactants and products.

e⁻

223
 iv. From the direction of electron flow and shift of equilibrium, we can deduce
that:
- iron(II) hydroxide will be oxidised to iron(III) hydroxide because the position
of equilibrium of first reaction shifts to the right.
- oxygen will accept electrons from the first reaction and will be reduced to
hydroxide ions because the position of equilibrium of second reaction shifts
to left.

8) Example 2: Will chlorine oxidise manganese(II) ions to manganate(VII) ions?

i. Find from the Data Booklet the equations involving the reactants and products
stated and write down their corresponding E° values.

ii. Determine the direction of electron flow. Remember that electrons flow from
the half-cell with more negative E° value to the half-cell with more positive E°
value.
iii. Determine the shift of position of equilibrium, and see whether it tallies with
the reactants and products.
e⁻

iv. From the direction of electron flow and shift of equilibrium, we can deduce
that:
- manganese(II) ions will not be oxidised to manganate(VI) ions because the
position of equilibrium of first reaction shifts to the left, it goes against the
equilibrium shift if it occurs.
- chlorine will not be reduced to chloride ions because the position of
equilibrium of the second reaction shifts to the right, it goes against the
equilibrium shift if it occurs.

224
Determining the strength of oxidising and reducing agents

1) From the last example, the scenario can also be interpreted as:
i. Chlorine is a weaker oxidising agent than manganate(VI) ion, hence it will
not oxidise manganese(II) ion to manganate(VI) ion.
ii. Manganese(II) ion is a weaker reducing agent than chloride ion, hence it will
not reduce chlorine to chloride ion.

2) From the second last example, the scenario can also be interpreted as:
i. Iron(II) hydroxide is a stronger reducing agent than hydroxide ion, hence it
will reduce oxygen to hydroxide ion.
ii. Oxygen is a stronger oxidising agent than iron(III) hydroxide, hence it will
oxidise iron(III) hydroxide to iron(III) hydroxide.

Effect of temperature, pressure and concentration on E° value

1) Since redox equilibria are equilibria, a change in temperature, concentration

and pressure will have an effect on its position of equilibrium. This will also
affect the value of E° because E° indicates the position of equilibrium of a
redox equilibrium.

2) i. If a change causes the position of equilibrium to shift to the right, the value
of E° increases.
ii. If a change causes the position of equilibrium to shift to the left, the value of
E° decreases.

21.4 Cells and Batteries

Rechargable and non-rechargeable cells

1) Batteries are electrochemical cells used as portable sources of electricity.

2) i. Primary cells cannot be recharged and are discarded once the supply of
electric current decreases. This happens when the concentration of reactants
becomes too low.
ii. Secondary cells can be recharged over and over again. This involves
converting the products back to the reactants produced when delivering the
current by electric current.

225
Dry cells

1)

Lead-acid accumulator

1)

Hydrogen-oxygen fuel cells

226
Electric cars

227
21.5 Quantitative Electrolysis
E° value in electrolysis

1) Recall that the selective discharge of ions during electrolysis is affected by:
i. the position of ions in the electrochemical series.
ii. the concentration of ions.

2) Cations lower in the electrochemical series will be

selectively discharged(reduced). This is because they
have a more positive E° value and hence it favours
reduction more.

3) Cations with higher concentration will be selectively

discharged(reduced). This is because the value of E°
becomes more positive as the concentration of ions
increases. A more positive E° favours reduction.

Faraday's laws of electrolysis

1) The quantity of charge,Q passed during electrolysis is given by this equation. Q

is measured in Coulombs, C
where I = Current/A
Q = It t = Time/s

2) Faraday's first law of electrolysis states that the mass of a substance liberated during
electrolysis is directly proportional to the quantity of charge passed through
during electrolysis.

3) Faraday's second law of electrolysis states that the number of Faradays required to
discharge one mole of ion at an electrode equals to the number of charges on
the ion.

4) Faraday, F is the amount of charge carried by one mole of electrons.

1 electron → 1.60 x 10⁻¹⁹ C
∴ 6.02 x 10²³ electrons → 96500 C

228
 Therefore, 1 F = 96500 C mol⁻¹

5) Calculation examples:

Determining the value of Avogadro's constant, L by means of electrolysis

1) The Avogadro's constant can be determined using electrolysis. This is done by

calculating the charge associated with one mole of electrons. Then, Avogadro's
constant can be calculated using:
charge on one mole of electrons
L=
charge on one electron

2) The charge on one electron is 1.60 x 10⁻¹⁹ C, this is done using physics
calculation.

3) The charge on one mole of electrons is then found from a simple electrolysis
experiment.

229
4) The procedure is
i. Weigh the pure copper anode and pure copper cathode separately.
ii. Arrange the apparatus as shown. The variable resistor is used to keep the
current constant.
iii. Pass a constant electric current for a measured time interval.
iv. Remove the cathode and anode and wash and dry them with distilled water
and then with propanone.
v. Reweigh the copper cathode and anode

5) The cathode increases in mass because copper is deposited, the anode decreases
in mass because the copper goes into the solution as ions. The decrease in mass
of anode is preferably measured, this is because copper does not always 'stick' to
the cathode very well, resulting in inaccurate gain in mass.

6) Suppose a sample set of experiment data is as shown below:

- Mass of anode at the beginning = 56.53 g
- Mass of anode at the end = 56.40 g
- Mass of copper removed from anode = 0.13 g
- Quantity of charge passed = 408 C

7) i. Cu²⁺(aq) + 2e⁻ → Cu(s)

ii. 0.13 g → 408 C
∴ 63.5 g → 63.5 x 408 ÷ 0.14 = 185057.143 C, for two moles of electrons
iii. Therefore, charge on one mole of electrons = 185057.143 ÷ 2
= 99600 C
iv. Therefore, L = 99600 ÷ 1.60 x 10⁻¹⁹ C = 6.2 x 10²³
v. This is a good agreement with the accurate value, 6.02 x 10²³.

230
CHAPTER 22: Ionic Equilibria
22.1 pH, Ka, pKa and Kw
22.2 Acid-base Titrations
22.3 Buffer Solutions
22.4 Solubility Equilibria

Learning outcomes:

(a) explain the terms pH, Ka, pKa, Kw and use them in calculations.
(b) calculate [H⁺(aq)] and pH values for strong and weak acids and strong bases.
(c) explain the choice of suitable indicators for acid-base titrations, given appropriate data.
(d) describe the changes in pH during acid-base titrations and explain these changes in terms of
the strengths of the acids and bases.
(e) (i) explain how buffer solutions control pH.
(ii) describe and explain their uses, including the role of HCO³⁻ in controlling pH in blood.
(f) calculate the pH of buffer solutions, given appropriate data.
(g) show understanding of, and use, the concept of solubility product, Ksp.
(h) calculate Ksp from concentrations and vice versa.
(r) show understanding of the common ion effect.

231
22.1 pH, Ka, pKa and Kw
The ionic product of water, Kw

1) Water is able to act as an acid as well as a base. Therefore whenever liquid

water is present, the following equilibrium occurs.
2H2O ⇌ H3O⁺ + OH⁻

Or the more simplified version(Note that H⁺ ≡ H3O⁺):

H2O ⇌ H⁺ + OH⁻

2) Therefore the ionic product of water is defined as:

3) It means that the product of hydrogen and hydroxide concentrations at a

certain temperature is constant, this is true no matter the water is pure or
impure.

4) At 25 °C, the value of Kw is 1.00 x 10⁻¹⁴ mol² dm⁻⁶.

5) Since the above reaction is an endothermic reaction, the value of Kw increases

with increasing temperature. At 100 °C, the value is 5.13 x 10⁻¹³ mol² dm⁻⁶.

pH of a substance

1) pH of a substance is defined as:

2) To calculate the pH of pure water at 25 °C:

i. Since the water is pure, the hydrogen ion concentration must be equal to the
hydroxide ion concentration. For every hydrogen ion formed, there is a

232
 hydroxide ion formed as well.
ii. So, the expression for Kw can be simplified to:
[H⁺]² = 1.00 x 10⁻¹⁴ ; since [H⁺] = [OH⁻]
[H⁺] = 1.00 x 10⁻⁷
iii. Therefore the pH of water is given by
pH = -log(1.00 x 10⁻⁷)
pH = 7.00
iv. This implies that at 24 °C, pH 7.00 is the neutral point of water, equal
amounts of hydrogen and hydroxide ions are present.

3) i. At 100 °C, the pH of pure water is 6.14. This does not mean the water is
more acidic at higher temperature.
ii. pH of 6.14 is the neutral point of water at 100 °C, there are still equal
amounts of hydrogen and hydroxide ions present.

Strong and weak acids

1) i. A strong acid ionises completely in the presence of water.

HA + H2O → H3O⁺ + A⁻
ii. Therefore the pH of strong monoprotic acid can be calculated using:
pH = -log[H3O⁺]
Since the acid ionises completely, [H3O⁺] = [HA]
pH = -log[HA]

2) i. A weak acid ionises partially in the presence of water.

HA + H2O ⇌ H3O⁺ + A⁻
ii. The pH of a weak acid is calculated using the acid dissociation constant, Ka.

Acid dissociation constant, Ka

1) i. For the dissociation of a weak acid, Kc can be written as:

ii. However, the concentration of water is fairly constant. This is because at any
one time, only about 1 % of the HA has reacted.
iii. Therefore a new equilibrium constant, Ka is defined as:

or

233
2) i. Ka can be used to measure the strength of weak acids.
ii. A stronger acid has the position of equilibrium further to the right,
therefore a higher Ka value.
iii. A weaker acid has the position of equilibrium further to the right, therefore
a lower Ka value.

3) To make the comparison easier to see, the strength of acids is measured on the
pKa scale. Just like pH, pKa is defined as:

4) The numbers now become:

5) Conclusion:
i. The stronger the acid, the higher the Ka and the lower the pKa.
ii. The weaker the acid, the lower the Ka and the higher the pKa.

Calculations on pH

1) To calculate the pH of a strong acid:

i. A strong acid ionises completely in the presence of water.
HA + H2O → H3O⁺ + A⁻
ii. Therefore the pH of a strong monoprotic acid can be calculated using:
pH = -log[H3O⁺]

234
 Since the acid ionises completely, [H3O⁺] = [HA]
pH = -log[HA] ; if [HA] is given
iii. For a diprotic acid, [H2A] = 2[H3O⁺]
iv. For a triprotic acid, [H₃A] = 3[H3O⁺]

2) To calculate pH of a weak acid:

i. A weak acid ionises partially in the presence of water.
HA + H2O ⇌ H3O⁺ + A⁻
ii. For example, if you have c mol dm⁻³ of weak acid, HA. Do a calculation to
find the concentration of H3O⁺ and A⁻ at equilibrium.

iii. Important approximations when calculating pH of a weak acid:

- So little acid has ionised that the concentration of HA at equilibrium is the
same as the initial concentration. That is, c - x ≈ c.
- If the acid is pure, then the concentration of hydrogen ions and the negative
ions are the same. That is, [H3O⁺] = [A⁻] = x.
iv. Then use the formula for Ka to obtain the concentration of hydrogen ions,
given the value of Ka.
v. Then use the pH formula to calculate the pH.

3) To calculate the pH of a strong base:

i. A strong base ionises completely in the presence of water.
B + H2O → BH⁺ + OH⁻
ii. Since the base ionises completely, [OH⁻] = [B] ; if [B] is given
iii. Obtain the concentration of hydrogen ions from the expression of Kw. This is
valid because the product of [H⁺] and [OH⁻] is constant at constant
temperature.
iv. Then use the pH formula to calculate its pH.
v. Alternatively, a quantity known as pOH can be calculated where
pOH = -log[OH⁻]
Then use the fact that pH + pOH = 14 to calculate its pH.

[ Note: Calculation involving weak bases is not required. ]

235
22.2 Acid-base Titrations
Titration curves

1) Titration curves or pH curves are curves that show the pH changes during
an acid-base titration.

2) Titration curve of a strong acid and strong base titration, take

hydrochloric acid and sodium hydroxide as an example:
i. Running the acid into alkali:
- pH changes by a small amount until the equivalence point, that is, the
point where the solutions have been mixed in exactly the right proportions
according to the equation.
- This is followed by a sharp decrease in pH when small amount of acid is
added.

ii. Running the alkali into acid:

- This is the same as above except the curves starts at pH 0, because the
curve shows the pH in the conical flask.

3) Titration curve of a strong acid and weak base titration, take hydrochloric
acid and ammonia as an example:

236
 i. Running the acid into alkali:
- The curve starts at pH 12 because a weak base is present.
- Initially, the pH falls rapidly. As more acid is added, the curve becomes less
steep because a buffer solution composed of excess ammonia and
ammonium chloride is set up. Buffer solutions resist changes pH when small
amount of acid is added.
- The equivalence point now is a bit acidic.
- When excess acid is added, the curve is the same as before.

ii. Running the alkali into acid:

- The beginning of curve is the same as before.
- After the equivalence point(which is also a bit acidic), the pH changes
by a small amount. This is because a buffer solution composed of excess
ammonia and ammonium chloride is set up. Buffer solutions resist changes
in pH when small amount of alkali is added.

4) Titration curve of a weak acid and strong base titration, take ethanoic
acid and sodium hydroxide as an example:
i. Running the acid into alkali:
- The beginning of curve is the same as before.
- After the equivalence point(which is a bit alkaline), the pH changes by a
small amount. This is because a buffer solution composed of excess sodium

237
 ethanoate and ethanoic acid is set up. Buffer solutions resists pH changes
when small amount of acid is added.

ii. Running the alkali into acid:

- The curve starts at pH 3 because a weak acid is present.
- Initially, the pH increases rapidly. As more alkali is added, the curve becomes
less steep because a buffer solution composed of excess sodium ethanoate
and ethanoic acid is set up. Buffer solutions resist changes pH when small
amount of alkali is added.
- The equivalence point now is a bit alkaline.
- When excess alkali is added, the curve is the same as before.

5) Titration curve of a weak acid and weak base titration, take ethanoic acid
and ammonia as an example:
i. Running the acid into alkali
- The curve starts at pH 12 because a weak base is present.
- Initially, the pH falls rapidly. As more acid is added, the curve becomes less
steep because a buffer solution composed of excess ammonia and
ammonium ethanoate is set up. Buffer solutions resist changes pH when
small amount of acid is added.
- There is no sharp decrease in pH at any volume.

238
 ii. Running the alkali into acid
- The curve starts at pH 3 because a weak acid is present.
- Initially, the pH increases rapidly. As more alkali is added, the curve becomes
less steep because a buffer solution composed of excess ammonium
ethanoate and ethanoic acid is set up. Buffer solutions resist changes pH
when small amount of alkali is added.

6) Titration curve of a polyprotic acid and base titration, take ethanedioic

acid and sodium hydroxide as an example:
i. Running the alkali into acid:
- Ethanedioic acid is a diprotic acid, it donates the two protons in two stages.
This is because one proton is more easier to remove than the other.

Stage 1:

Stage 2:

239
 - The curve will therefore show two sharp increase in pH.

Acid-base indicator

1) An indicator is a substance that changes colour as the pH of the solution which

it dissolves changes.

2) In an acid-base titration, an indicator is used to mark the end point of the

titration, that is, the point where the indicator changes colour.

3) Most indicators are weak acids. They have an acid colour and a base colour.

4) Consider a general indicator with the formula HIn. HIn has a different colour
from In⁻. The colour of HIn is called the acid colour while the colour of In⁻ is
called the base colour.
HIn ⇌ H⁺ + In⁻
i. When acid is added, the equilibrium position shifts to the left due to the
increasing concentration of H⁺ ions. The indicator exists predominantly as
HIn. Hence, the solution shows the acid colour.
ii. When base is added, the equilibrium position shifts to the right due to the
removal of H⁺ ions. The indicator exists predominantly as In⁻. Hence, the
solution shows the base colour.

5) Take methyl orange as an example, it has an acid colour of red and a base
colour of yellow.

i. When acid is added, the equilibrium position shifts to the left and the solution
looks red.
ii. When base is added, the equilibrium position shifts to the right and the
solution looks yellow

240
Importance of pKIn

1) Since the indicator is a weak acid, an expression of Ka can be written for it.
However, the Ka now is called KIn.

2) As acid/base is added, the colour changes. At half-way through the colour

changes, there will be equal amount of HIn and In⁻ present. The equilibrium
expression now becomes:

3) This means that the end point depends entirely on the pKIn of the indicator. At
pH = pKIn, the indicator is changing its colour.

4) However, the indicator usually changes its colour over a range of pH, usually
around pKIn ± 1, this is called the pH range of am indicator.

4) Some common examples:

Selecting a suitable indicator for titration

1) An indicator should be chosen such that it changes colour close to the

equivalence point of the titration to give an accurate titration result.

2) The indicator therefore should have a pH range close to the equivalence point
of the titration.

241
3) A guide to choose a suitable indicator:

Finding pKa from titration curves

1) Suppose during an acid-base titration, 25 cm³ of alkali is required to neutralise

a weak acid. Therefore at half-neutralisation, half-volume of the alkali has been
added, that is 12.5 cm³.

2) Half of the acid has been neutralised and half of the salt has been formed.
Therefore, [HA] = [A⁻].

3) According to the formula, log([HA]/[A⁻]) = 1 and pKa = pH.

4) Conclusion is, pKa is the pH of the solution at half-neutralisation.

22.3 Buffer Solutions

What is a buffer solution?

1) A buffer solution is a solution whose pH does not change significantly when small
amount of acid or base is added to it.

2) Buffer solutions should therefore contain:

i. large amount of acid to react with the base added.

242
 ii. large amount of base to react with the acid added.

3) Since the added acid and base can be removed, the pH does not change
significantly.

4) These conditions can be achieved if the solution contains a mixture of a

weak acid and its conjugate base, or a weak base with its conjugate
acid.

5) There are two types of buffer solutions, named acidic buffer solution and
alkaline buffer solution.

Acidic buffer solution

1) An acidic buffer solution is acidic and can be made by mixing a weak acid
and its conjugate base together. Take ethanoic acid and ethanoate ion as
an example.

2) Sodium ethanoate is added to ethanoic acid. Sodium ethanoate dissociates

completely according to the equation:
CH3COONa → CH3COO⁻ + Na⁺
...while ethanoic acid dissociates partially according to the equation:
CH3COOH ⇌ CH3COO⁻ + H⁺
3) The presence of ethanoate ions causes the equilibrium position to shift to the
left. The solution now contains:
i. large reservoir of ethanoic acid molecules.
ii. large reservoir of ethanoate ions.
iii. enough hydrogen ions to make the solution acidic.

4) When acid is added:

i. The hydrogen ions from the acid added will react with the large reservoir
of ethanoate ions.
H⁺ + CH3COO⁻ → CH3COOH
ii. The extra hydrogen ions are removed, and the pH drops very little.

5) When base is added:

i. The hydroxide ions from the base added will react with the large
reservoir of ethanoic acid molecules.
OH⁻ + CH3COOH → CH3COO⁻ + H2O

243
 ii. The extra hydroxide ions are removed, and the pH increases very little.

Alkaline buffer solution

1) An alkaline buffer solution is alkaline and can be made by mixing a weak

base and its conjugate acid together. Take ammonia and ammonium ion
as an example.

2) Ammonium chloride is added to ammonia. Ammonium chloride dissociates

completely according to the equation:
NH4Cl → NH4⁺ + Cl⁻
...while ammonia ionises partially according to the equation:
NH3 + H2O ⇌ NH4⁺ + OH⁻
3) The presence of ammonium ions causes the equilibrium position to shift to the
left. The solution now contains:
i. large reservoir of ammonia molecules.
ii. large reservoir of ammonium ions.
iii. enough hydroxide ions to make the solution alkaline.

4) When acid is added:

i. The hydrogen ions from the acid added will react with the large
reservoir of ammonia molecules.
H⁺ + NH3 → NH4⁺
ii. The extra hydrogen ions are removed, and the pH drops very little.

5) When base is added:

i. The hydroxide ions from the base added will react with the large
reservoir of ammonium ions.
OH⁻ + NH4⁺ → NH3 + H2O
ii. The extra hydroxide ions are removed, and the pH increases very little.

Calculating the pH of buffer solutions

1) For an acidic buffer solution:

CH3COOH ⇌ CH3COO⁻ + H⁺
i. Make the following assumptions:
- Concentration of ethanoate ions is equal to the concentration of
sodium ethanoate added. This is done by ignoring the negligible amount
of ethanoate ions coming from the dissociation of ethanoic acid.

244
 - Concentration of ethanoic acid is equal to its original
concentration. This is done by ignoring the negligible amount of ethanoic
acid dissociated.
ii. The Ka expression of ethanoic acid now becomes:

iii. Given the value of Ka of ethanoic acid, concentration of hydrogen ions and
hence the pH of the buffer solution can be found.

2) For an alkaline buffer solution:

NH3 + H2O ⇌ NH4⁺ + OH⁻
i. Adjust the point view to the ammonium ion rather than ammonia.
This is possible because ammonium ions are weak acids. Therefore:
NH4⁺ ⇌ NH3 + H⁺
ii. Make the following assumptions:
- Concentration of ammonium ions is equal to the concentration of
ammonium chloride added. This is done by ignoring the negligible
amount of ammonium ions coming from the ionisation of ammonia.
- Concentration of ammonia is equal to its original concentration.
This is done by ignoring the negligible amount of ammonia ionised.
iii. The Ka expression of ammonium ion now becomes:

iv. Given the value of Ka of ammonium ion, concentration of hydrogen ions and
hence the pH of the buffer solution can be found.

245
Importance of buffer solutions in biological systems

1) Most biological reactions(especially those involving enzymes) are very sensitive

to pH, since enzymes can only function within a narrow range of pH.

2) For example, if the pH of human blood(pH 7.4) is changed by as little as 0.4

unit, it could prove fatal.

3) There are two important buffer systems in the human blood:

i. The carbonic acid/hydrogen carbonate system.
ii. The phosphate system.

4) The carbonic acid/hydrogen carbonate system:

i. The following equilibrium is involved:
H2CO3 ⇌ H⁺ + HCO3⁻
ii. When a little acid is added:
H⁺ + HCO3⁻ → H2CO3
iii. When a little base is added:
OH⁻ + H2CO3 → HCO3⁻ + H2O

5) The phosphate system:

i. The following equilibrium is involved:
H2PO4⁻ ⇌ HPO4²⁻ + H⁺
ii. When a little acid is added:
H⁺ + HPO4²⁻ → H2PO4⁻
iii. When a little base is added:
OH⁻ + H2PO4⁻ → HPO4²⁻ + H2O

246
22.4 Solubility Equilibria
Solubility product, Ksp

1) Solubility product, Ksp is the product of the concentrations of each ion in a

saturated solution of a sparingly soluble salt at 298 K, raised to the power of
their relative concentrations.

2) For any so called 'insoluble salt', a tiny amount of it do dissolve in water.

3) i. Solubility product only apply if the solution is in equilibrium with its solid, in
other words, the solution is saturated.
ii. It means that in a saturated solution at 298 K, when the concentrations of the
ions are multiplied together, the value is the solubility product.

4) The higher the value of Ksp, the more soluble the salt is.

5) Solubility product can be used to predict precipitation:

i. If the product of the concentrations of ions is less than the solubility product,
the solution is not saturated, no precipitate will be formed.
ii. If the product of the concentrations of ions is equal to the solubility product,
the solution is saturated, no precipitate is formed yet.
iii. If the product of the concentrations of ions is more than the solubility
product, the solution is saturated, precipitation occurs to reduce the
concentrations to a value equal to the solubility product.

247
Calculations on solubility product

1) To calculate solubility product from solubility of ions:

2) To calculate the solubility of ions from the solubility product

Common ion effect

1) Consider the equilibrium of barium sulfate and its ions:

BaSO4(s) ⇌ Ba²⁺(aq) + SO4²⁻(aq)
If sulfuric acid, H2SO4 is added, the concentration of sulfate ions increases and
the position of equilibrium shifts to the left. More precipitate is formed and
barium sulfate becomes less soluble.

248
2) The common ion effect is therefore the reduction in the solubility of a dissolved
salt by adding a solution of a compound which has an ion in common with the
dissolved salt, this often results in precipitation.

3) The solubility of an ionic compound in aqueous solution containing a common

ion is less than its solubility in water.

Calculations on common ion effect

1) To calculate the solubility of an ionic compound in different solvents:

2) To predict precipitation on mixing two solutions:

249
250
CHAPTER 23: Reaction Kinetics
23.1 Orders of Reaction and Rate Equations
23.2 Reaction Mechanisms
23.3 Catalysis

Learning outcomes:

(a) explain and use the terms: rate equation, order of reaction, rate constant, half-life of a
reaction, rate-determining step.
(b) construct and use rate equations of the form rate = k[A]m[B]ⁿ (limited to simple cases of
single step reactions and of multistep processes with a rate-determining step, for which m and
n are 0, 1 or 2), including:
(i) deducing the order of a reaction from concentration-time graphs, by the initial rates
method and half-life methods.
(ii) deducing, for zero- and first-order reactions, the order of reaction from concentration-time
graphs.
(iii) verifying that a suggested reaction mechanism is consistent with the observed kinetics.
(iv) predicting the order that would result from a given reaction mechanism (and vice versa).
(c) calculating an initial rate using concentration data. [integrated forms of rate equations are
not required]
(d) (i) show understanding that the half-life of a first-order reaction is independent of
concentration.
(ii) use the half-life of a first-order reaction in calculations.
(e) calculate a rate constant, for example by using the initial rates or half-life method.
(f) devise a suitable experimental technique for studying the rate of a reaction, from given
information.
(g) outline the different modes of action of homogeneous and heterogeneous catalysis, including:
(i) the Haber process.
(ii) the catalytic removal of oxides of nitrogen in the exhaust gases from car engines.
(iii) the catalytic role of atmospheric oxides of nitrogen in the oxidation of atmospheric sulfur
dioxide.
(iv) catalytic role of Fe³⁺ in the I⁻/S2O8²⁻ reaction.

251
23.1 Orders of Reaction and Rate Equations
Rate Equation

1) The rate of reaction is dependent on the concentration of the reactants.

Doubling the concentration may double or triple the rate of reaction, just to
name a few.

2) A rate equation shows this relationship mathematically.

3) A rate equation can only be obtained experimentally, it cannot be

deduced from the stoichiometric equation and it may not include all reactants
written in the equation.

4) For a general reaction:

A+B→C+D
The rate equation is:

5) k is known as the rate constant, it is only a constant for a given reaction at a

particular temperature. The unit of k depends on the rate equation and orders
of reaction.

6) Note that the unit of rate is mol dm⁻³ s⁻¹ while the units of [A] and [B] are
mol dm⁻³.

Order of reaction

1) The values m and n are known as the orders of reaction. Common values are
0, 1 and 2.

2) The order of reaction with respect to a reactant is the power to which the
concentration of that reactant is raised in the experimentally determined rate
equation.

3) Like rate equations, orders of reaction must be determined experimentally.

252
4) If a reaction is zero-order with respect to a reactant A:
i. m = 1 and the rate equation becomes rate = k[A]⁰[B]ⁿ
= k[B]ⁿ
ii. The rate of reaction is independent of the concentration of A
because [A]⁰ = 1 and it disappears from the equation. Changing the
concentration of A will not alter the rate of reaction.
iii. - The rate-concentration graph is a horizontal line showing the rate of
reaction does not change.
- The concentration-time graph is a straight line with constant gradient
showing that rate is constant.

5) If a reaction is first-order with respect to a reactant A:

i. m = 1 and the rate equation becomes rate = k[A][B]ⁿ.
ii. The rate of reaction is proportional to the concentration of A. If [A]
increases five times, the rate of reaction will increase five times as well.
iii. - The rate-concentration graph will show a straight line through origin.
- The concentration-time graph will show a curve with constant half-life.

iv. Half-life, t½ is the time taken for the initial concentration of reactant to
decrease to half of its original value.
v. Only a first-order concentration-time graph will show a curve with constant
half-life. That is, t1 = t2 = t3 = t½.
vi. The relationship between half-life and rate constant is given by:

6) If a reaction if second-order with respect to a reactant A:

i. m = 2 and the rate equation becomes rate = k[A]²[B]ⁿ.
ii. The rate of reaction is proportional to the square of concentration
of A. If [A] increases five times, the rate of reaction will increase 5² = 25

253
 times.
iii. - The rate-concentration graph is a quadratic curve.
- The concentration-time graph is a curve with non-constant half-life.

Deducing orders of reaction

1) Order of reaction must be determined experimentally, it can be deduced by

either graphically or using initial rate experiments.

2) Deducing graphically involves plotting either a rate-concentration graph or

concentration-time graph, and the order of a reaction
may be deduced by looking at the pattern.

3) Using initial rate experiments, the rate of reaction is

measured at the very beginning of the
experiment. This is done by calculating the gradient
of a concentration-time graph at the beginning.

4) A guide to find the order of reaction from the processed data:

Example 1:

254
Example 2:

255
23.2 Reaction Mechanisms
Rate-determining step

1) In any chemical change, some bonds are broken and new ones are made. Quite
often, these changes are too complicated to happen in one simple stage. Instead,
the reaction may involve a series of small changes one after the other.

2) A reaction mechanism describes the one or more steps involved in the reaction
in a way which makes it clear exactly how the various bonds are broken and
made.

3) The overall rate of reaction is governed by the rate of the slowest step. The
slow step is therefore called the rate-determining step.

4) For example, the reaction between 2-bromo-2-methylpropane(a tertiary

halogenoalkane) and hydroxide ion happens in two stages.

Stage 1:

Stage 2:

256
 The overall equation is:

5) In this example, Step 1 is the rate-determining step because the rate of reaction
depends entirely on the rate of this step. Increasing the rate of the already fast
step 2 will not increase the overall rate of reaction.

6) By doing experiments, it can be found that the the rate equation is:
rate = [(CH3)3CBr]
The rate therefore does not depend on the hydroxide ion, which takes part in
the second stage of the reaction.

7) Another example is the reaction between 1-bromoethane(a primary

halogenoalkane) and hydroxide ion. This reaction happens in a single step.

8) The rate equation for this reaction is rate = [CH3CH2Br][OH⁻] because the rate
of reaction depends on these two reactants.

Molecularity of reaction

1) Molecularity of a reaction is the number of species taking part in a (stage of)

reaction.

2) i. In the first example above, Stage 1 has a molecularity of one because only one
species is involved in this stage. Therefore Stage 1 is said to be
unimolecular.
ii. Stage 2 involves two molecules colliding and therefore it has a molecularity of
two. Stage 2 is said to be bimolecular.

3) In the second example, two species are involved, therefore it is a bimolecular

reaction having a molecularity of two.

257
Order and mechanism

1) Given the rate equation and the orders of reaction, it is possible to deduce the
reaction mechanism and vice versa.

2) i. For example, given:

rate = k[A][B]
And given two possible reaction mechanisms. It can be deduced that
mechanism 2 might be correct. This is because the rate equation tells us both
A and B are involved in the rate-determining step(slow step) of the reaction.
ii. If we know that mechanism 2 is correct. We can deduce that the above rate
equation might be the correct one, since two species are involved in the slow
step.

Mechanism 1 Mechanism 2

3) i. If the rate-determining step is not the first step, for example:

ii. It can be deduced that the rate equation might be

rate = k[A][X]
iii. However, X is only an intermediate. Its concentration can be expressed in
terms of concentrations of A and B, using the fact that the first step is in
equilibrium.
iv. The steps are:

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23.3 Catalysis
Phase and physical state

1) A phase is a region of space, throughout which all physical properties of a

material are essentially uniform.

2) Examples of phases:

Heterogeneous catalysis

1) Heterogeneous catalysis involves the use of a catalyst which is in different

phase than the reactants. Most often, the reactants are in gaseous state while
the catalyst is in solid state.

2) In heterogeneous catalysis, the reactants are often adsorbed onto the surface
of the active site of the catalyst.

3) Adsorption means 'sticking onto the surface'. A good catalyst should adsorb
reactants strong enough but not so strong that the products cannot break away.

4) For example, the reaction between ethene and hydrogen is catalysed by nickel
catalyst. Both ethene and hydrogen are gases while nickel is a solid.
i. Ethene molecules are adsorbed on the surface of the nickel. The double
bond between the carbon atoms breaks and the electrons are used to bond it
to the nickel surface.

259
 ii. Hydrogen molecules are also adsorbed on to the surface of the nickel. When
this happens, the hydrogen molecules are broken into atoms. These can move
around on the surface of the nickel.

iii. If a hydrogen atom diffuses close to one of the bonded carbons, the bond
between the carbon and the nickel is replaced by one between the carbon and
hydrogen.

iv. That end of the original ethene now breaks free of the surface, and eventually
the same thing will happen at the other end.

v. As before, one of the hydrogen atoms forms a bond with the carbon, and that
end also breaks free. There is now space on the surface of the nickel for new
reactant molecules to go through the whole process again.

5) Most heterogeneous catalysts are transition elements or their compounds. This

is because in transition elements, there are empty/partially filled d-orbitals
available for the molecules to be adsorbed to.

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Homogeneous catalysis

1) Homogeneous catalysis involves the use of a catalyst which is in the same

phase as the reactants.

2) i. For example, the reaction between persulfate ions and iodide ions:
S2O8²⁻ + 2I⁻ → 2SO4²⁻ + I2
ii. This reaction proceeds very slowly because it involves two negative ions
colliding.
iii. Iron(III) ions, Fe³⁺ is used as a catalyst. It oxidises the iodide ions into iodine
molecules and itself is reduced to iron(II) ions, Fe²⁺.
Fe³⁺ + 2I⁻ → Fe²⁺ + I2
iv. The persulfate ions will oxidise the iron(II) ions into iron(III) ions and itself is
reduced to sulfate ions.
S2O8²⁻ + 2Fe²⁺ → 2SO4²⁻ + 2Fe³⁺

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CHAPTER 24: Group IV
24.1 Physical Properties of Group IV Elements
24.2 Group IV Chlorides
24.3 Group IV Oxides
24.3 Relative Stability of +2 and +4 Oxidation States

Learning outcomes:

(a) outline the variation in melting point and in electrical conductivity of the elements and
interpret them in terms of structure and bonding.
(b) describe and explain the bonding in, molecular shape and volatility of the tetrachlorides.
(c) describe and explain the reactions of the tetrachlorides with water in terms of structure and
bonding.
(d) describe and explain the bonding, acid-base nature and thermal stability of the oxides of
oxidation states II and IV.
(e) describe and explain the relative stability of higher and lower oxidation states of the elements
in their oxides and aqueous cations including, where relevant, E values.

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24.1 Physical Properties of Group IV Elements
Introduction to Group IV elements

1) Group IV elements are p-block elements with a characteristic outer shell

configuration of ns²np².

2) Group IV elements exist in two different oxidation states, +2 and +4 states.

The +2 state compounds become more stable going down the Group while the
+4 state compounds become less stable going down the Group. The reasons will
be explained later.

Variation in structure

1) Going down the Group, there is a trend of non-metal to semi-metal to metal.

2) Carbon exists in two different allotropes, diamond and graphite(for the structures,
refer to Chapter 5), they are both giant covalent compounds.

3) Silicon and germanium have the same type of structure as diamond. They
are both giant covalent compounds.

4) There are two types of tin:

i. Grey tin or alpha-tin has a giant covalent structure, same as the one diamond
has.
ii. White tin or beta-tin(the more common one) has a distorted 12-co-ordinated
metallic structure with metallic bonds.

5) Lead is a metal and it has a simple 12-co-ordinated metallic structure.

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Variation in melting and boiling point

1) From carbon to germanium, the melting

point decreases. This is because going down
the Group, the covalent bond length
increases. Longer bonds have lower bond
energies. Less energy is required to overcome
the covalent bonds, therefore melting point is
lower.

2) i. Tin has a lower melting point than lead. This is because in the solid state,
metallic tin has a distorted structure, resulting the metallic bonds being
less effective. This factor outweighs the larger atomic size of lead.
Therefore, less energy is required to overcome the metallic bond in tin.
ii. Tin has a higher boiling point than lead, this is because in the liquid state,
there is no ordered arrangement between the atoms. The larger atomic
size of lead resulting the metallic bond being longer and weaker.
Therefore, less energy is required to overcome the metallic bond in lead.

Variation in electrical conductivity

1) The electrical conductivity increases down the Group as the nature of the
elements changes from non-metal to semi-metal to metal.

2) i. Carbon(diamond form) does not conduct electricity. This is because

all the outer electrons are used in covalent bonding. Therefore there are no
free and moving electrons to conduct the electricity.
ii. However, carbon(graphite form) conducts electricity. This is because in
the graphite structure each atom donates one electron to a delocalised system
of electrons(for more details, refer to Chapter 5). Therefore there are free electrons
present to conduct the electricity.

3) Silicon and germanium are semi-conductors, whose conductivity is

between that of metals and non-metals.

4) Tin and lead are metals, hence they are good conductors of electricity.
This is because each atom involved in metallic bonding donates electrons into
the sea of delocalised electrons. Therefore free electrons are present to conduct
electricity.

264
24.2 Group IV Chlorides
Introduction to Group IV chlorides

1) All Group IV chlorides are simple covalent molecules which exist as liquid at
room temperature with the general formula of XCl4, where
X = A Group IV element.

2) All of them have a tetrahedral shape with a bond

angle of 109.5°. A typical example is carbon
tetrachloride:

3) The boiling point of Group IV tetrachlorides increases

down the Group. This is because as the number of
electrons increases, more temporary dipoles can be set up
between the molecules. Hence the van der Waals' forces
of attraction are stronger.

Note: Carbon tetrachloride, CCl4 is an exception.

Reaction with water, H2O(Hydrolysis)

1) i. Carbon tetrachloride does not react with water. If carbon tetrachloride is

added to water, two immiscible layers are formed.
ii. There are two reasons for this:
- Carbon is a small atom cluttered with big chlorine atoms. This
causes the water molecule to have difficulty approaching
the bulky molecule. Even if the water molecule successfully
gets in, the transition state is very cluttered and unstable, the
activation energy is very high.
- Also, there isn't any convenient orbital on the carbon that the lone pair
of the water molecule can attaches itself to.

2) i. Silicon, germanium and tin tetrachlorides(also called silicon(IV)

chloride, germanium(IV) chloride and tin(IV) chloride) hydrolyses in water to
form an oxide and steamy fumes of hydrogen chloride.
XCl4 + 2H2O → XO2 + 4HCl ; where X = Si/Ge/Sn/Pb
ii. Unlike carbon tetrachloride, this is possible because the Group IV atoms are
bigger, the molecules are less bulky.

265
3) Lead(IV) chloride behaves similarly as silicon, germanium and tin
tetrachlorides. However, the heat released during the reaction would tend to
decompose lead(IV) chloride, PbCl4 to lead(II) chloride, PbCl2.
PbCl4 → PbCl2 + Cl2

4) The hydrolysis reactions become more vigorous going down the Group. This
is because going down the Group, the X-Cl bond becomes longer. A longer
bond has a lower bond energy and it is more easy to be broken.

Relative stability of the oxidation states of Group IV chlorides

1) A fact about Group IV elements is as such:

i. Going down the Group, compounds with a +2
oxidation state Group IV element become more stable.
ii. Going up the Group, compounds with a +4 oxidation
state Group IV element become more stable.

2) This means that the +4 oxidation is less favourable down the Group while the
+2 oxidation state is more favourable down the Group.

3) From carbon to tin, the +4 oxidation state is more stable than +2 oxidation
state. However, for lead, the +2 oxidation is more stable. This is why lead(IV)
chloride decomposes to lead(II) chloride on heating.

24.3 Group IV Oxides

Introduction to Group IV oxides

1) Group IV elements form two types of oxides: monoxide and dioxide. This is
because the elements have two possible oxidation states, +2 and +4.

2) Monoxides include:
i. carbon monoxide, CO
ii. silicon monoxide/silicon(II) oxide, SiO
iii. germanium monoxide, GeO

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 iv. tin(II) oxide, SnO
v. lead(II) oxide, PbO

3) Dioxides include:
i. carbon dioxide, CO2
ii. silicon dioxide/silicon(IV) oxide, SiO2
iii. germanium dioxide, GeO2
iv. tin(IV) oxide, SnO2
v. lead(IV) oxide, PbO2

4) i. Carbon monoxide and carbon dioxide is a simple covalent

molecule which exists as a gas at room temperature.

5) i. Silicon monoxide and silicon dioxide has a giant covalent structure(for

more details, refer to Chapter 5).
ii. The difference in structure between carbon dioxide and silicon dioxide is due
to silicon atom being larger. When the atom is larger, the overlapping of p
orbitals to form a π bond is less complete and a π bond as such is very
unstable. So, silicon bonded with the oxygen atoms in such a way that π bonds
are not formed.

6) Germanium monoxide and germanium dioxide have the same structure

as silicon monoxide and silicon dioxide respectively.

7) Tin(II) oxide and tin(IV) oxide have a giant ionic lattice structure with ionic
bonds between the Sn²⁺/Sn⁴⁺ and O²⁻.

8) Lead(II) oxide and lead(IV) oxide have a giant ionic lattice structure with
ionic bonds between the Pb²⁺/Pb⁴⁺ and O²⁻.

Group IV monoxides

1) Carbon monoxide is a slightly acidic oxide which is only slightly soluble in

water. It reacts with hot and concentrated sodium hydroxide, NaOH to give a
solution of sodium methanoate.
CO + NaOH → HCOONa

2) i. Germanium, tin and lead monoxides are amphoteric oxides. They

can act as an acid as well as a base.

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 ii. As a base : XO + 2HCl → XCl2 + H2O ; where X = Ge/Sn/Pb
iii. As an acid : XO + 2NaOH → Na2XO2 + H2O ; where X = Ge/Sn/Pb

Group IV dioxides

1) Carbon dioxide is a slight acidic oxide which is only slightly soluble in

water. It reacts with cold sodium hydroxide, NaOH to give either sodium
carbonate or sodium hydrogencarbonate solution, depending on the proportion.
CO2 + 2NaOH → Na2CO3 + H2O or
CO2 + NaOH → NaHCO3

2) Silicon dioxide is weakly acidic. It reacts with hot and concentrated sodium
hydroxide to give sodium silicate. However, it does not react with water due to
the strong covalent bonds need to be broken.
SiO2 + 2NaOH → Na2SiO3 + H2O

3) i. Germanium, tin and lead dioxides are amphoteric oxides. They can
act as an acid as well as a base.
ii. As a base : XO2 + 4HCl → XCl4 + 2H2O ; where X = Ge/Sn/Pb
For germanium and tin dioxides, hot and concentrated hydrochloric acid is
used. However, for lead dioxide, cold hydrochloric acid is used. This is
because lead dioxide will decompose if the temperature increases.
iii. As an acid : XO2 + 2NaOH → Na2XO3 + H2O ; where X = Ge/Sn/Pb
For all reactions, hot and concentrated sodium hydroxide is used.

Thermal stability of Group IV oxides

1) Carbon, silicon and germanium oxides will disproportionate on

heating.
2XO → X + XO2 ; where X = C/Si/Ge

2) Tin and lead monoxide are stable on heating.

3) This reflects the stability of +2 oxidation state of Group IV elements increases

down the Group.

4) All dioxides are stable on heating except lead dioxide(lead(IV) oxide). This
decomposes on heating to give lead(II) oxide and oxygen.
2PbO2 → 2PbO + O2

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5) This shows the stability of +4 oxidation state of Group IV elements decreases
down the Group.

24.3 Relative Stability of +2 and +4 Oxidation

States
The stability of +2 and +4 oxidation states

1) i. +4 compounds at the top of the Group is more stable than at the bottom.
ii. +2 compounds at the bottom of the Group is more stable than at the top.

2) For carbon, carbon dioxide(+4) is more stable than carbon monoxide(+2).

Therefore, carbon monoxide is readily oxidised to carbon dioxide, it is a
good reducing agent. For example, it reduces iron(III) ions to iron.
Fe2O3 + 3CO → 2Fe + 3CO2

3) For lead, lead(II) oxide(+2) is more stable than lead(IV) oxide(+4). Therefore,
lead(IV) oxide is readily reduced to lead(II) oxide, it is a good oxidising
agent. For example, lead(II) oxide oxidises hydrochloric acid to chlorine.
PbO2 + 4HCl → PbCl2 + Cl2 + 2H2O

4) Between these extremes, there is a gradual change in stability of the +2

compared with the +4 state.
i. The +4 state of germanium compounds is more stable than the +2 state.
Therefore, germanium(II) compounds are good reducing agents.
ii. The +4 state of tin compounds is slightly more stable than the +2 state.
Therefore, tin(II) compounds are weak reducing agents.

5) This can be interpreted from the E° values of the ions of Group IV elements in
aqueous solutions.

269
6) i. The more positive the value of E°, the easier it is to reduce the species on the
left of the half-equation.
ii. The less positive the value of E°, the easier it is to oxidise the species on the
right of the half-equation.

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CHAPTER 25: Transition Elements
25.1 Introduction to Transition Elements
25.2 Oxidation States of Transition Elements
25.3 Complex Ions

Learning outcomes:

(a) explain what is meant by a transition element, in terms of d-block elements forming one or
more stable ions with incomplete d orbitals.
(b) state the electronic configuration of a first row transition element and of its ions.
(c) contrast, qualitatively, the melting points and densities of the transition elements with those of
calcium as a typical s-block element.
(d) describe the tendency of transition elements to have variable oxidation states.
(e) predict from a given electronic configuration, the likely oxidation states of a transition element.
(f) describe and explain the use of Fe³⁺/Fe²⁺, MnO4⁻/Mn²⁺ and Cr2O7²⁻/Cr³⁺ as examples of
redox systems.
(g) predict, using E values, the likelihood of redox reactions.
(h) explain the reactions of transition elements with ligands to form complexes, including the
complexes of copper(II) ions with water, hydroxide, ammonia and chloride ions
(i) (i) define the term ligand as a species that contains a lone pair of electrons that forms a dative
bond to a central metal atom/ion.
(ii) define the term complex as a molecule or ion formed by a central metal atom/ion
surrounded by one or more ligands.
(iii) describe transition metal complexes as linear, octahedral, tetrahedral or square planar.
(j) explain qualitatively that ligand exchange may occur, including the complexes of copper(II)
ions with water, hydroxide, ammonia and chloride ions.
(k) describe the shape and symmetry of the d orbitals, and the splitting of degenerate d orbitals
into two energy levels in octahedral complexes using the complexes of copper(II) ions with
water and ammonia as examples.
(l) explain the origin of colour in transition element complexes resulting from the absorption of
light energy as an electron moves between two non-degenerate d orbitals.
(m) describe, in qualitative terms, the effects of different ligands on absorption, and hence colour,
using the complexes of copper(II) ions with water, hydroxide, ammonia and chloride ions as
examples.
(n) apply the above ideas of ligands and complexes to other metals, given information.

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25.1 Introduction to Transition Elements
Transition and d-block elements

1) A transition element is one which forms one or more stable ions with incompletely
filled orbitals.

2) A d-block element is one which has electrons filling the d-orbitals.

3) From the above definition, scandium and zinc are not counted as transition
elements, although they are d-block elements. This is because:
i. scandium forms Sc³⁺ ion, which does not have any d-electrons.
ii. zinc forms Zn²⁺ ion, which has a completely-filled d-orbitals.

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Physical properties of transition elements

1) i. Transition elements are all metals which are hard and denser than s-block
elements.
ii. This is because the relative atomic masses of transition elements are higher
and their radii are smaller compared to s-block elements. Hence, there are
more mass per unit volume and the density is higher.
iii. For example, iron has a density of 7.9 g cm⁻³ while calcium has a density of
1.6 g cm⁻³.

2) i. Transition elements have higher melting points than s-block elements.

ii. This is because the metallic bond of transition elements is stronger as both 3d
and 4s electrons are involved in the bonding. In calcium, for example, only 3s
electrons are involved.
iii. This is possible because 3d and 4s and very similar energy levels.
iv. For example, iron has a melting point of 1538 °C while calcium has a melting
point of 839 °C.

Characteristic properties of transition elements

1) The characteristic properties of transition elements are:

i. they have variable oxidation states.
ii. they form coloured ions.
iii. they form complex ions which are surrounded by ligands.
iv. they often act as catalysts.

25.2 Oxidation States of Transition Elements

Variable oxidation states

1) i. One characteristic property of transition elements is that they have variable

oxidation states.
ii. For example, iron can exist in 0, +2 or +3 oxidation state.

2) This is because the 4s and 3d electrons have very similar energy levels, therefore
the transition element can easily lose or gain electrons to form ions/compounds
of roughly the same stability.

273
3) All the possible oxidation states of the transition elements are shown below, the
most common ones are bolded.

4) An oxidation state of +2 implies that two electrons have been lost from the
neutral element. The same goes for other oxidation states.

5) The maximum oxidation state of a compound can be obtained by counting

the number of 4s electrons and the number of unpaired 3d electrons.
Only copper breaks this pattern.

6) i. For small oxidation states, the transition element normally exists as simple
Mª⁺ ions.
ii. For large oxidation states, the transition element normally exists in oxo-
compounds. This is because the ions formed would have a very high charge
density and it will polarise adjacent molecules(water, oxygen) to form the oxo-
compounds.
iii. For example, Cr⁶⁺ does not exist, chromium with oxidation state +6 exists as
CrO4²⁻.

Redox reactions of transition elements.

Note: 1) There is no point learning this here, you should already have a decent
knowledge on the Fe³⁺/Fe²⁺, MnO4⁻/Mn²⁺ and Cr2O7²⁻/Cr³⁺ systems up to
this point of the syllabus.
2) You need to know how to:
i. construct redox equations.
ii. calculate oxidation states.
iii. calculate the amount of substance(mass/volume) from a titration that
involves oxidation and reduction.
iv. select suitable oxidising and reducing agents.
v. calculate cell potentials.

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25.3 Complex Ions
Ligand and complex

1) A ligand is a molecule or ion with a lone pair of electrons, capable of forming a

co-ordinate bond to a metal atom or ion. Some examples of ligands are water,
ammonia and chloride ion.

2) A complex is a molecule or ion containing a central metal ion surrounded by one

or more ligands. Some examples are [Al(H2O)6]³⁺ and [Fe(H2O)6]³⁺.

Formation of a complex

1) A complex is formed when ligands bond with the central metal ion via
co-ordinate bonding.

2) Take [Fe(H2O)6]³⁺ as an example:

i. Fe ion has an electronic structure of [Ar]3d⁶4s². When
it loses electrons to become Fe³⁺, the electronic
structure becomes [Ar]3d⁵.
ii. The ion then uses 6 orbitals from the 4s, 4p and 4d
levels to accept lone pairs from the water molecules.

3) Note: i. For small ligands such as water and ammonia, six is the maximum
number of ligands it can bond to the central metal ion.
ii. For larger ligands such as chloride ions, it can only form four co-
ordinate bonds with the central metal ion.

275
4) The co-ordination number of a complex is the total number of co-ordinate
bond the ligands formed with the central metal ion. For example,
[Fe(H2O)6]³⁺ has a co-ordination number of 6.

5) Some other co-ordination numbers and the geometry of the complex:

6) A ligand is said to be unidentate if it forms one co-ordinate bond with the

central metal ion only. Water, ammonia and chloride are unidentate ligands.

7) i. A ligand is said to be bidentate if it forms two co-ordinate bonds with the

central metal ion. 1,2-diaminoethane and ethandioate ion are bidentate
ligands.

ii. A complex ion which has bidentate ligands attached to it exhibits optical
isomerism.

276
 iii. In addition, a complex ion which has the ligands arranged in a square planar
structure exhibits geometrical isomerism.

Naming complexes

1) Naming complexes is very similar in naming organic compounds.

2) Each ligand is given a code:

3) Some examples:
i. [Fe(H2O)6]³⁺ is hexaaquairon(III) ion
- hexa shows there are six ligands.
- aqua shows the ligands are water molecules.
- iron shows the name of the central metal ion.
- (III) shows the the oxidation number of the central metal ion.

4) If there are more than one type of ligands, the ligands are named according to
alphabetical order, ignoring the prefixes. For example, [Cu(NH3)4(H2O)2]²⁺ is
called tetraamminediaquacopper(II) ion.

5) i. For cationic complex, the name of the central metal ion is the same as its ooo
original name.
ii. For anionic complex, the name of the central metal ion follows this coding:

277
 iii. For example, [CuCl4]²⁻ is called tetrachlorocuprate(II) ion. (It is yellow colour)

Ligand exchange

1) A ligand exchange reaction is a reaction in which one ligand in a complex

ion is replaced by a different one.

2) Example 1: Replacing water with chloride ions.

i. When concentrated hydrochloric acid is added to a solution containing
hexaaquacobalt(II) ions, the solution turns from pink to dark rich blue. The
six water molecules are replaced by four chloride ions.

ii. Only four chloride ions are attached because chloride ions are larger,
therefore six chloride ions cannot fit in around the central metal ion.
iii. The co-ordination number of the complex changes from 6 to 4. The
geometry of ligands around changes from octahedral to tetrahedral.
iv. By Le Chatelier's principle, the process can be reversed by adding water to it.

3) Example 2: Replacing water with ammonia.

i. The ammonia can act as a base and also a ligand. This is because
hexaaqua- ions are acidic.
ii. The acidity of hexaaqua- ions is due to the electron pair in the water
molecule being pulled towards the central positive charge, making the
hydrogen more positive, and easily lost.

278
 Stage 1: Ammonia as a base(Acid-base reaction)
iii. When small amount of ammonia is added, hydrogen ions from the water are
pulled out, leaving hydroxide ions.

iv. A precipitate will be formed when two hydrogen ions have been
removed. This is because a neutral complex is produced and it is
unattractive to water molecules. Hence, it is no longer soluble in water.
Stage 2: Ammonia as a ligand(ligand exchange reaction)
v. When excess ammonia is added, the precipitate dissolves. The ammonia
replaces water as a ligand to give tetraamminediaquacopper(II) ions. Notice
that only 4 of the 6 water molecules are replaced.

Overall reaction:

4) Certain ligands are stronger than other and central metal ions generally
prefer to be bonded to stronger ligands. Therefore a ligand exchange
reaction may not happen if the new ligand is weaker than the original ligand.

279
Colour of complexes

1) Visible light is the visible part of the electromagnetic spectrum which has
wavelengths between 400 nm to 700 nm.

2) White light is composed of all the wavelengths in the visible part of the
electromagnetic spectrum. When white light is passed through a prism, it splits
into its constituent colours. This phenomenon is known as dispersion of light.

3) When white light passes through copper(II) sulfate, CuSO4 solution, visible light
with wavelengths in the red and yellow region is absorbed. The unabsorbed
ones combine to given a pale blue(cyan) colour.

4) The colour we see is the complementary colour of the

wavelength(colour) of the light absorbed by the substances. The
complementary colour wheel can be used to estimate the colour of a
substance. Colours on opposite sites are complementary colours.

280
Shapes of d-orbitals

1) There are five types of d-orbitals, named dxy, dxz, dyz, dz² and dx²-y².

2) i. dxy, dxz and dyz have the 'lobes' in the x-y, x-z and y-z planes respectively. Note
that the 'lobes' does not touch the axes, they are located between the axes.

ii. dz² has the 'lobes' along the z-axis, with a 'collar'.

iii. dx²-y² has the 'lobes' along the x- and y-axes.

Factors affecting the colour of complexes

1) The colour of a complex ion depends on the wavelength(or frequency) of the

visible light absorbed. This in turn depends on the energy gap, ∆E between
the two groups of d-orbitals(see below).

281
2) For an octahedral complex:
i. The central metal ion has five degenerate d-orbitals. They split into two
groups, two with higher energy and the other three with lower when
ligands are attached to it.
ii. This is because as the lone pairs on the ligands approach the central metal
ion, the d-electrons in the central metal ion are repelled.
iii. Due to the shape of the octahedral complex, the d-electrons repelled are the
ones in the dz² and dx²-y² orbitals, and these orbitals will have higher energy.

3) Other shapes have the splitting as below(not required in A-levels).

4) The size of the energy gap, ∆E depends on:

i. the oxidation number of the central metal ion.
- In general, the higher the oxidation state of the central metal ion, the larger
the size of ∆E.
ii. the nature of ligands.
- In general, the splitting, ∆E is larger if the lone pair comes from a less
electronegative atom.

282
5) The origin of colour of complexes:
i. As the electromagnetic radiation(photons) with frequencies within the visible
region of the electromagnetic spectrum passes through the complex, some of
the photons are absorbed.
ii. The photon absorbed must have energy equal to the energy gap of the
two groups of d-orbitals, which is given by ∆E = hf.
iii. The absorbed energy is used to promote an electron from a lower
energy d-orbital to a higher energy one. This is called d-d transition.

iv. The colour of the complex is the result of the unabsorbed frequencies of light
combining. It can then be estimated using the complementary colour wheel.

6) The reason why different complexes have different colours is because they all
have different energy gap size, ∆E. The incoming photon must have
frequency exactly equal to ∆E/h to be absorbed and be used to promote an
electron. Different colours and wavelengths of light have different frequencies,
which is why they have different colours.

7) Non-transition metal complexes are often not coloured because they do not
have partly-filled d-electrons. Hence no photon is absorbed and no
electron is promoted.

8) Note: for non-physics students:

i. The higher the frequency, f of light(photon), the higher its energy, which is
given by ∆E = hf, where h is the Planck's constant.
ii. There is an inverse relationship between frequency, f and wavelength, λ, which
is given by c = fλ, where c is the speed of light.
iii. In the visible spectrum, red light has the lowest energy and violet the highest.

283
CHAPTER 26: Benzene and Its Compounds
26.1 Introduction to Aromatic Compounds
26.2 Reactions of Benzene and Alkylbenzene
26.3 Introduction to Phenols
26.4 Reactions of Phenols

Learning outcomes:

(a) describe the chemistry of arenes as exemplified by the following reactions of benzene and
methylbenzene:
(i) substitution reactions with chlorine and with bromine.
(ii) nitration.
(iii) complete oxidation of the side-chain to give a benzoic acid.
(iv) hydrogenation of the benzene ring to form a cyclohexane ring
(b) (i) describe the mechanism of electrophilic substitution in arenes, as exemplified by the
formation of nitrobenzene and bromobenzene.
(ii) suggest the mechanism of other electrophilic substitution reactions, given data.
(iii) describe the effect of the delocalisation of electrons in arenes in such reactions.
(c) predict whether halogenation will occur in the side-chain or aromatic nucleus in arenes
depending on reaction conditions.
(d) apply the knowledge of positions of substitution in the electrophilic substitution of arenes.
(e) recall the chemistry of phenol, as exemplified by the following reactions:
(i) with bases.
(ii) with sodium.
(iii) with diazonium salts.
(iv) nitration of, and bromination of, the aromatic ring
(f) describe and explain the relative acidities of water, phenol and ethanol.
(g) deduce the presence of a CH3CH(OH)– group in an alcohol from its reaction with alkaline
aqueous iodine to form tri-iodomethane.
(h) describe the reaction of CH3CO– compounds with alkaline aqueous iodine to give
tri-iodomethane.

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26.1 Introduction to Aromatic Compounds
Aliphatic and aromatic compounds

1) i. Aliphatic compounds are organic compounds that have carbon atoms joined
together in straight chains, branched chains or non-aromatic rings.
ii. Aromatic compounds are organic compounds that contain one or more
benzene ring(in A-level). Examples of aromatic compounds:

The structure of benzene

1) Benzene is a hexagonal and planar molecule with the formula C6H6.

2) In benzene, each carbon atom undergoes sp² hybridisation

to give three hybrid orbitals and an unchanged p orbital
which is perpendicular to the plane containing the three
hybrid orbitals.

3) Two of the hybrid orbitals overlap with two other hybrid orbitals of carbon
atoms and the other overlaps with the orbital of hydrogen. The unchanged p
orbitals overlap with one another via a system of π bond to give a giant
molecular orbital. This orbital is above and below the plane containing the
carbon atoms.

4) The six electrons from each p orbital are then delocalised around the ring. A
delocalised electron does not belong to any carbon atom. This delocalisation of
electrons gives benzene a relatively stable structure.

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5) In a benzene molecule, all the C-C bonds are identical, with a bond length
of 140 pm. This bond length is longer than a double bond but shorter than a
single bond. The bond angle between carbon atoms is 120º.

6) The stability of benzene is shown in its reluctance to undergo addition

reactions. This is because when electrons are added, the delocalisation will
be broken and so does the stability.

7) There are two common symbols for benzene, the right one is
generally preferred over the left one because it indicates that
the electrons are delocalised.

8) Before this modern structure was discovered, the Kekulé structure(right) was
used. However, the Kekulé structure could not account for the unexplained
properties of benzene.
i. The structure has three double bonds, so it should undergo addition
reactions like other alkenes do. However for real benzene, it does not
undergo addition reactions easily.
ii. Single and double bonds have different bond length, therefore Kekulé's
benzene should have a distorted hexagonal shape. However in real
benzene, all the C-C bonds are identical and it is a perfect hexagon.

Introduction to arenes

1) Arenes are aromatic hydrocarbons, that is, hydrocarbon that contains at least
one benzene ring.

2) Arenes have higher melting and boiling points than aliphatic

hydrocarbons.
i. This is because in aromatic hydrocarbons, temporary dipoles can be
easily set up between the delocalised electrons. Hence the van der Waals'

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 forces are stronger.
ii. Benzenes with side chains also have permanent dipole forces between them.
This is because the presence of side chains makes them a polar molecule.

26.2 Reactions of Benzene and Alkylbenzene

Reactivity of benzene

1) Unlike alkenes, benzene is resistant to addition reactions. This is because it

involves breaking the delocalised electron system and thus losing its stability.

2) Instead, benzene undergoes substitution reactions. This involves replacing one

or more hydrogen atoms with another group of atoms.

3) Benzene is particularly attractive to electrophiles due to its high electron density.

Therefore benzene mainly undergoes electrophilic substitution.

4) The reactivity of benzene is also affected by the presence of other group(s) in

the benzene ring. This is known as substituent group effect, and it will be
explained later.

Electrophilic substitution

1) Electrophilic substitution is the replacement of an atom or a group of

atom by an electrophile. In benzene, the electrophile replaces the hydrogen
atom(s).

2) The general mechanism of electrophilic substitution:

i. Suppose, an electrophile X⁺ is generated from a compound XY. The
electrophile is attracted to the electron-rich region of the benzene ring.
ii. Two electrons from the delocalised electron system are used to form a
co-ordinate bond with the electrophile.

iii. An intermediate with the delocalised electron system partially broken is

formed.

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 iv. Y⁻ ion, from XY has a lone pair of electrons on it and it forms a bond with the
hydrogen ion. The hydrogen loses its electrons to the delocalised electron
system to bond with Y⁻. The delocalised electron system is now
restored.

3) Summary of reactions that benzene and alkylbenzene undergoes:

i. Halogenation(addition of halogen) into the ring and side chain.
ii. Nitration(addition of nitro group, NO2).
iii. Oxidation of side chain.
iv. Hydrogenation.

Reaction of benzene - halogenation

1) Reagent : Chlorine/bromine gas, Cl2/Br2

Condition : Aluminium chloride, AlCl3 or iron(III) chloride, FeCl3
Product : Halobenzene

2) Benzene reacts with chlorine/bromine in the presence of halogen carriers

such as aluminium chloride, AlCl3 to form chloro- or bromobenzene,
respectively. One hydrogen atom in the benzene ring is substituted by the
halogen.

3) Use chlorine as an example of halogen:

C6H6 + Cl2 → C6H5Cl + HCl

4) The mechanism of this reaction - electrophilic substitution.

i. Aluminium chloride polarises the Cl-Cl bond to create the electrophile Cl⁺.
Cl2 + AlCl3 → Cl⁺ + AlCl4⁻
ii. The electrophile is attracted to the benzene, it then bonds with the benzene
using two electrons from the delocalised electron system. Note that the
delocalised electron system is partially broken in the intermediate.

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 iii. A hydrogen ion is expelled from the ring by AlCl4⁻ and leaving its electrons in
the ring. The delocalised electron system is now restored. Steamy fumes of
hydrogen chloride is also observed.

Reaction of benzene - nitration

1) Reagent : Concentrated nitric acid, HNO3

Condition : Reflux at a temperature lower than 50 ºC and the
presence of concentrated sulfuric acid, H2SO4 as catalyst
Product : Nitrobenzene

2) Nitration happens when one or more hydrogen atoms in benzene is replaced by

a nitro group, NO2.

3) Benzene reacts with nitric acid in the presence of concentrated sulfuric acid to
give nitrobenzene.
C6H6 + HNO3 → C6H5NO2 + H2O

4) The mechanism of this reaction - electrophilic substitution.

i. The electrophile, nitronium ion, NO2⁺ is formed by the reaction of nitric acid
and sulfuric acid.
HNO3 + 2H2SO4 → NO2⁺ + 2HSO4⁻ + H3O⁺
ii. As before, the electrophile is attracted to the benzene ring and forms a bond
with it. The delocalised electron system is partially broken.

iii. Hydrogen ion is expelled and it bonds with HSO4⁻ to regenerate the catalyst.
The delocalised electron system is restored.

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5) If the temperature exceeds 50 ºC, 1,3-dinitrobenzene will be formed as well.
Notice that the second nitro group is added to the 3 position of the ring.

Substituent group effect

1) If a benzene already has a first substituent in it, second incoming substituent is

affected by the nature of the first substituent.

2) The first substituent has an effect on:

i. the position of the incoming second substituent.
- If X is an electron-withdrawing group, it deactivates the ring
and it is 3-directing.
- Examples are -NO2, -CN, -COOH, -CHO and -COR.
- If X is an electron-donating group, it activates the ring and it is
2,4-directing.
- Examples are -OH, -NH2, -C6H5 and alkyl groups.
- The only exception are halogens, they are electron-withdrawing but
they are 2,4-directing.
ii. the rate at which the second substituent is introduced.
- If X is an electron-withdrawing group, it deactivates the ring and the
rate of reaction decreases
- If X is an electron-donating group, it activates the ring and the rate of
reaction increases.

Reaction of alkylbenzene - halogenation

1) Reagent : Chlorine/bromine gas, Cl2/Br2

Condition : Into the ring - Aluminium chloride, AlCl3 or iron(III)
chloride, FeCl3 as catalyst, absence of UV
light
Into the alkyl group - Absence of catalyst but presence of
UV light
Product : Halo-alkylbenzene

2) In the presence of halogen carriers and the absence of UV light at

room temperature, the halogen is substituted into the ring via electrophilic
substitution.

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3) Take methylbenzene as an example, since methyl group is electron-donating
and 2,4-directing, the incoming halogen is substituted at the 2 or 4 position.
2-chloro and 4-chloromethylbenzene are produced.
C6H5CH3 + Cl2 → C6H4ClCH3 + HCl

4) In the presence of UV light and the absence of halogen carriers, the

halogen is substituted into the alkyl group via free-radical substitution. Take
methylbenzene as an example, (chloromethyl)benzene is produced.
C6H5CH3 + Cl2 → C6H4(CH3Cl) + HCl

5) Further substitutions are possible, producing (dichloromethyl)benzene and

(trichloromethyl)benzene.

Reaction of alkylbenzene - nitration

1) Reagent : Concentrated nitric acid, HNO3

Condition : Reflux at a temperature lower than 30 ºC and the
presence of concentrated sulfuric acid, H2SO4 as catalyst
Product : Nitro-alkylbenzene

2) Since methyl group activates the ring, making the ring more reactive, the
temperature has to be lowered to 30 ºC to prevent multiple substitutions.

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3) Methyl group is an electron-donating group, it activates the ring and is
2,4-directing, therefore the nitro group is substituted at the 2 or 4 positions

4) Take methylbenzene as an example, 2-nitro and 4-nitromethylbenzene is

produced.

5) If the temperature exceeds 30 ºC, multiple substitutions by nitro groups is

possible. However, each time a nitro group substitutes, the rate of reaction of
the next substitution decreases because nitro group is electron-withdrawing.
Therefore, 2,4,6-trinitromethylbenzene is rare.

Reaction of alkylbenzene - oxidation

1) Reagent : Acidified potassium manganate(VII), KMnO4

Condition : Heat or reflux
Product : Benzoic acid

2) When methylbenzene is heated under reflux with acidified potassium

manganate(VII), side-chain oxidation occurs. Benzoic acid is produced.

3) Any carbon side-chain group is oxidised to -COOH group under these

conditions.

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Reaction of alkylbenzene - hydrogenation

1) Reagent : Hydrogen gas, H2

Condition : Heat in the presence of nickel, Ni catalyst at 150 °C
Product : Cyclohexanes

2) In hydrogenation, hydrogen atoms are added to the benzene ring. The

delocalised electron system is permanently broken.

3) With benzene:

4) With methylbenzene:

26.3 Introduction to Phenols

What are phenols?

1) Phenols are benzene compounds which have an -OH group

attached directly to it.

2) In a phenol molecule, one of the lone pairs on the oxygen overlaps with
the delocalised electron system to give a structure like this:

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3) This increases the electron density of the delocalised electron system. It
makes phenols much more reactive than benzene itself. Also, it increases
the acidity of phenol as well.

4) Physical properties of phenols:

i. Phenol has a higher melting and boiling points than methylbenzene.
- This is because phenols can form hydrogen bonds between them in
addition of van der Waals' forces and permanent dipole-dipole forces.

ii. Phenol itself is more soluble in water than other phenols.

- This is because a small phenol molecule can form more effective hydrogen
bonds with water molecules.
- However, most phenols are generally insoluble in water.

Acidity of phenols

1) Compounds like alcohols and phenols which contain an -OH group attached to
a hydrocarbon are very weak acids.

2) Alcohol's strength as an acid is so weak that it is ignored under normal

situations. However, phenols have recognisable acid strength.

3) This is because phenol can donate a proton to form a phenoxide ion. The
presence of hydroxonium ions makes it acidic.

Comparing the strength of organic acids

1) The strength of organic acids depends on:

i. The strength of the O-H bond which is to be broken.
ii. The stability of the anion formed.

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2) The strengths of the acids are as follow. The lower the value of pKa, the stronger
the acid is.

3) Ethanoic acid is the strongest because of the stability of ethanoate ion formed.
In an ethanoate ion, the negative charge is spread throughout the -COO
group. This delocalisation of electron and negative charge stabilises it to a
greater extent. However, since oxygen atoms are the most electronegative, more
negative charge will still be concentrated here.

4) Phenol is a weaker acid. This is because electron delocalisation of the

phenoxide ion is not as great as in ethanoate ion. Although the delocalised ring
electrons are involved, the electrons are still heavily distorted towards
the one electronegative oxygen atom rather than two in the ethanoate ion
case.

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5) i. If an electron-withdrawing group is attached to phenol, its acidity
increases. This is because the electron-withdrawing group can attract
electrons away from the oxygen, stabilising the phenoxide ion formed.
ii. If an electron-donating group is attached to phenol, its acidity
decreases. This is because the electron-donating group increases the
electron density in the benzene ring, intensifying the charge on oxygen atom.

6) Ethanol is the weakest acid among all. This is because the

ethoxide ion formed has no spreading of its negative
charge to other parts, all the negative charge is
concentrated on the oxygen atom. This makes it
very attractive to hydrogen ions and it can easily accept
one.

7) On the other hand, water is a stronger acid than ethanol but weaker
than phenol. This is because in ethoxide ion, the presence of an alkyl
group intensifies the negative charge on the oxygen atom. In a
hydroxide ion, no such thing happens.

26.4 Reactions of Phenols

Reaction with sodium metal, Na

1) Reagent : Sodium metal, Na

Condition : Room temperature
Product : Alkoxides and hydrogen gas

2) Like alcohols, phenol will react with a reactive metal such as sodium to give
sodium phenoxide and hydrogen gas.
2C6H5OH + 2Na → 2C6H5O⁻Na⁺ + H2

3) The observation is that the sodium sinks and bubbles of hydrogen gas is
produced. This reaction is more vigorous than the one with alcohol because
phenol is more acidic.

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Reaction with sodium hydroxide, NaOH

1) Reagent : Sodium hydroxide, NaOH solution

Condition : Room temperature
Product : Alkoxides and water

2) Phenol is a strong enough acid to react with sodium hydroxide solution to give
sodium phenoxide and water.
C6H5OH + NaOH → C6H5O⁻Na⁺ + H2O

3) Since alcohols will not react with sodium hydroxide, this can be used as
a test to distinguish alcohols from phenols.

4) However, phenol will not react with sodium carbonate and sodium
hydrogencarbonate because it's not acidic enough to react with these.

Halogenation

1) Reagent : Chlorine gas/bromine water

Condition : Room temperature
Product : 2,4,6-trihalophenol

2) Phenol will react with halogens even without the presence of halogen
carriers. This proves that phenol is more reactive than benzene itself.

3) Take bromine as an example, 2,4,6-tribromophenol is produced.

4) The observations are:

i. The reddish-brown of bromine decolourises.
ii. A white precipitate is formed, this is 2,4,6-tribromophenol.
iii. Steamy fumes of hydrogen bromide is observed.

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Nitration

1) Reagent : Nitric acid, HNO3

Condition : Room temperature
Product : Nitrophenols

2) Unlike benzenes, concentrated sulfuric acid is not needed for nitration to

occur. This proves that phenol is more reactive than benzene itself.

3) i. With dilute nitric acid, mono-substituion occurs. 2-nitrophenol and

4-nitrophenol is produced.

ii. With concentrated nitric acid, tri-substituion occurs. 2,4,6-trinitrophenol

is produced.

Tri-iodomethane(iodoform) test for alcohols

1) This is a test used to identify the presence of

CH3CH(OH)- group in an alcohol. The R can be a
hydrogen or an alkyl group.

2) i. Iodine solution is added to a small amount of an alcohol, followed by just

enough sodium hydroxide solution to remove the colour of the iodine.
ii. If the alcohol contains the CH3CH(OH)- group, then a pale yellow
precipitate of tri-iodomethane, CHI3 is produced.

3) i. Ethanol is the only primary alcohol to give the tri-iodomethane

(iodoform) reaction.

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 ii. If R is a hydrocarbon group, then you have a secondary alcohol. Lots of
secondary alcohols give this reaction, but those that do all have a methyl
group attached to the carbon with the -OH group.
iii. No tertiary alcohols can contain this group because no tertiary alcohols
can have a hydrogen atom attached to the carbon with the -OH group. No
tertiary alcohols give the triiodomethane (iodoform) reaction.

4) The flow scheme is as such:

5) The overall equation is:

Tri-iodomethane(iodoform) test for carbonyl compounds

1) This is a test used to identify the presence of CH3CO-

group in carbonyl compounds. The R can be a hydrogen or
an alkyl group.

2) i. Iodine solution is added to a small amount of an alcohol, followed by just

enough sodium hydroxide solution to remove the colour of the iodine.
ii. If the alcohol contains the CH3CH(OH)- group, then a pale yellow
precipitate of tri-iodomethane, CHI3 is produced.

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3) i. Ethanal is the only aldehyde to give the triiodomethane(iodoform)
reaction.
ii. If R is a hydrocarbon group, then you have a ketone. Lots of ketones give
this reaction, but those that do all have a methyl group on one side of the
C=O bond.

4) The overall equation is:

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