Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

01 Atomic Structure & Physical Periodicity

GUIDING QUESTIONS
 What makes up an atom?
 How has the understanding of atomic structure developed and evolved?
 What is the evidence to show electrons in an atom exist in discrete energy levels?
 What do you understand by electronic configuration? How are the electrons arranged in the
atoms of a given element?
 How is the arrangement of electrons of an element and its position in the Periodic Table related?
 What are the trends and variations in the physical properties in elements?
 How can the trends and variations in atomic and physical properties be explained?
 What are transition elements?
 Are there any trends/patterns in the properties of transition elements?

LEARNING OUTCOMES
Students should be able to:
1(a) identify and describe protons, neutrons and electrons in terms of their relative charges and
relative masses
1(b) deduce the behaviour of beams of protons, neutrons and electrons in an electric field
1(c) describe the distribution of mass and charges within an atom
1(d) deduce the numbers of protons, neutrons and electrons present in both atoms and ions given
proton and nucleon numbers (and charge)
1(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
1(f) 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
1(g) describe the shapes of s, p and d orbitals (Refer also to Topic 22 Chemistry of the Transition
Elements) [knowledge of wave functions is not required]
1(h) state the electronic configuration of atoms and ions given the proton number (and charge)
1(i) explain the factors influencing the ionisation energies of the elements (see the Data Booklet)
1(j) deduce the electronic configurations of elements from successive ionisation energy data
1(k) interpret successive ionisation energy data of an element in terms of the position of that
element within the Periodic Table
5(a) recognise variation in the electronic configurations across a Period and down a Group
5(b) describe and explain qualitatively the general trends and variations in atomic radius, ionic
radius, first ionisation energy and electronegativity (Refer also to Topic 2 Chemical Bonding
for more on electronegativity)
(i) across a Period in terms of shielding and nuclear charge,
(ii) down a Group in terms of increasing number of electronic shells, shielding and nuclear
charge
6(a) define the terms relative atomic, isotopic, molecular and formula mass (Refer to Topic 4
Reactions and Stoichiometry for molecular and formula mass)

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

6(c) calculate the relative atomic mass of an element given the relative abundances of its
isotopes
13(a) explain what is meant by a transition element, in terms of d-block elements forming one
or more stable ions with partially filled d subshells
13(b) state the electronic configuration of a first row transition element and its ion
13 (c) explain why atomic radii and first ionisation energies of the transition elements are relatively
invariant

REFERENCES

1. Peter Cann, Peter Hughes, Chemistry for Advanced Level , 1st Edition, John Murray, Chapter 2
2. E.N. Ramsden , A-level Chemistry, 4th Edition, Nelson Thornes, Chapter 2
3. Martin S. Silberberg, Chemistry: The Molecular Nature of Matter and Change, 3rd Edition,
McGraw Hill, Chapter 8
4. Gary L. Miessler, Donald A. Tarr, Inorganic Chemistry, 3rd Edition (international edition), Pearson
Prentice Hall, Chapter 2, sections 2.2.3 & 2.2.4, pp. 34 to 43

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

1 THE STRUCTURE OF THE ATOM

1.1 The Discovery of the Subatomic Particles (Background Info)

The 5th century B.C. Greek philosopher Democritus proposed that one
couldn’t divide a piece of gold wire forever until there isn't any gold left
as all matter consists of very small, indivisible particles. He called these
particles atomos, meaning "uncuttable" or "indivisible". This concept
remained undeveloped until nineteenth century.

In 1808, an English scientist and school

teacher, John Dalton formulated the atomic
theory that all matter is made up of atoms.

In 1897, J.J. Thomson proposed a model that

described atoms as negatively charged
electrons embedded in a sphere of positive
charge, which was then known as the 'plum
pudding' model.
Figure 1. The plum-pudding model
In 1910, Rutherford observed that the
majority of the α-particles passing through a
thin sheet of gold foil went through with little
deflection. But every now and then, he would
observe great deflection. In some instances
the particle actually bounced back. This surprising discovery led to the
theory that the positive charge in the atom is concentrated into an
incredibly small nucleus right in the middle of it. The diameter of the
nucleus is less than 10–5 of the atom.
Figure 2. The gold foil experiment

Not until 1932 did the English physicist James Chadwick finally discover the neutron. He found it to be
electrically neutral, having about the same mass as a proton. Together, the proton and neutron
received the name "nucleon."

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

1.2 Atoms and the Properties of the Three Subatomic Particles

LO 1(a): identify and describe protons, neutrons and electrons in terms of their relative charges and relative masses
LO 1(c): describe the distribution of mass and charges within an atom
LO 1(d): deduce the numbers of protons, neutrons and electrons present in both atoms and ions given proton and nucleon
numbers (and charge)
LO 1(e)(i): describe the contribution of protons and neutrons to atomic nuclei in terms of proton number and nucleon
number

An atom is the smallest component of an element Electron

having the chemical properties of the element. d ≈ 10−16 m

All atoms are made up of the same three subatomic

particles - the electron, the proton and the neutron.
The nucleus contains
The protons and neutrons make up the nucleus of the protons and neutrons
atom while the electrons surround the nucleus. The d ≈ 10−13 m

protons and neutrons are sometimes referred to as Atom

d ≈ 10−10 m
nucleons.
Figure 3. A schematic representation of an atom

The nucleus contains over 99.99% of the mass of an atom. This is due to the relatively large masses of
the proton and neutron compared with the mass of the electron.

Table 1. Properties of the three subatomic particles.

property proton electron neutron
relative charge +1 −1 0
1
relative mass 1 1
1836

All atoms can be identified by the number of protons they contain. The chemical symbol is represented
as

X
A A Nucleon number
X Symbol for element
Z Z Proton number

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E.g., 8 O has 8 protons, 8 electrons and 8 neutrons.

The proton number (Z) is the number of protons in the nucleus of each atom of an element.

In a neutral atom, the number of protons is equal to the number of electrons, so the proton number
also indicates the number of electrons present in the atom. The chemical identity of an atom can be
determined solely from its proton number.

The nucleon number (A), also called mass number, is the total number of neutrons and protons in
the nucleus of an atom of an element.

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

1.3 Isotopes
LO 1(e)(ii): distinguish between isotopes on the basis of different numbers of neutrons present

Atoms of the same element do not all have the same mass.
Isotopes are atoms of an element that have the same
proton number but different nucleon numbers (or same
number of protons but different number of neutrons).

Isotopes of an element have the same electronic

configuration and chemical properties. They have different Figure 4. The nuclei of the three isotopes of
relative isotopic masses and physical properties. hydrogen

Some common isotopes include: hydrogen (1H, 2H, 3H), carbon (12C, 13C), oxygen (16O, 18O), sulfur (32S,
34
S) and nitrogen (14N, 15N).

Isotopes may be stable or unstable (radioactive). E.g. the isotope 14C decays by -emission with a half-
life of 5730 years.

When writing the chemical symbol for an element, it is not always necessary to write either or both
the nucleon and proton numbers. E.g. 11 H may be written as 1 H or H. We assume the most abundant
isotope is referred to when simply writing ‘H’ for example. However, when it is necessary to refer to
a particular isotope of an element, the nucleon number as well as the proton number must be
indicated e.g. if we want to refer to deuterium, then we should write 12 H for clarity’s sake.

Exercise 1.1 (Worked Example)

Complete the following table with the no. of protons, neutrons and electrons for each particle.
no. of protons no. of electrons no. of neutrons
(a) 28
14 Si

(b) 70
31 Ga3
(c) 31 3
15 P

Comments:
For each case, the subscript refers to the proton number (i.e. the number of protons present).

For (a), since it is a neutral atom, no. of protons = no. of electrons.

For (b), since it is positively charged, there should be 3 less electrons than protons. Hence, no. of
electrons = 31 – 3 = 28.
For (c), since it is negatively charge, there should be 3 more electrons than protons. Hence, no. of
electrons = 15 + 3 = 18.

The superscript refers to the nucleon number (i.e. the total number of protons and nucleons
present). Thus, no. of neutrons = nucleon number – no. of protons.
For (a), no. of neutrons = 28 – 14 = 14
For (b), no. of neutrons = 70 – 31 = 39
For (c), no. of neutrons = 31 – 15 = 16

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

Answer:
no. of protons no. of electrons no. of neutrons
(a) 28
14 Si 14 14 14
(b) 70
31 Ga3 31 28 39
(c) 31 3
15 P 15 18 16

Exercise 1.2
(a) Give the symbols of the elements (showing the nucleon numbers and charges) of the
following three particles in the last column.
particle protons neutrons electrons answer

P 6 8 6

Q 7 7 10

R 8 7 7

(b) Use the Data Booklet to identify which are not the usual isotopes of the elements
concerned.
[J00/I/1b]

Exercise 1.3 (Worked Example)

In 1999 Russian chemists claimed to be the first to identify atoms of a new element of proton
number 114. This was produced by bombarding atoms of plutonium, Pu, with atoms of an isotope
of a Group 2 element, X. The reaction taking place is as shown below.

244 289 1
94 Pu + X 114 [new element] + 3 neutrons ( 0 n )
What is X?

A Mg B Ca C Sr D Ba
[N03/I/4]

Answer: B

Comments:
244
Interpreting the numbers given for the atom of plutonium, 94 Pu , we know that there are 94
protons (from the number at the bottom) and there are 150 neutrons.

If we look at the new element formed, we know that 20 protons (114 – 94) have been added into
the new element. Referencing the periodic table, we can conclude that the element with proton
number 20 is Calcium. The number of neutrons do not matter since the identity of an element is
established by the number of protons.

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

1.4 Ions and deflection of charged particles

LO 1(b): deduce the behaviour of beams of protons, neutrons and electrons in an electric field

A negative ion (anion) has more electrons than protons. It is represented by AZ Xn where the number
of electrons = Z + n.
E.g.,
16
8 O2 has 8 + 2 = 10 electrons, 8 protons and 8 neutrons.

A positive ion (cation) has fewer electrons than protons. It is represented by AZ Xn where the number
of electrons = Z – n.
E.g., 24
12 Mg2 has 12 − 2 = 10 electrons, 12 protons and 12 neutrons.

Because of their relative masses and charges, protons, electrons and neutrons behave differently
when placed in an electric field. Protons are deflected to the negative plate, electrons deflected to
the positive plate, and neutrons being neutral pass straight through.

Similarly, cations are deflected to the negative plate and anions are deflected to the positive plate.

Figure 5. The behaviour of protons, neutrons and electrons in an electric field

In Figure 5, why is 1 greater than 2?

The electron has a much lower mass than the proton and is deflected to a much greater extent.

In general, we expect that the angle of deflection () of a charged particle passing through an electric
field to be directly proportional to the size of the charge (q), and inversely proportional to the mass
(m).
q

m

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

Exercise 1.4 (Worked Example)

In a particular experimental set-up, protons are deflected through an angle of +15o. Assuming an
identical set of experimental conditions, by what angles will the following particles be deflected?
(D is deuterium, 2H, and T is tritium, 3H)
 D–
 T+
 He2+ [N12 /III/4(a)]

Strategy:
q
Since the angle of deflection is dependent on the ratio, you can present your answer in the form
m
of a table, using the given angle of deflection of a proton as the reference point:

q
species ratio angle of deflection ()
m
q 1
proton, 1H+   = + 15o (given)
m 1
D– (= 2H–)

T+ (= 3H+)

He2+

q
Both D– and He2+ have a ratio that is halved of that of 1H+, thus the angle of deflection will be
m
halved of that of 1H+. However, as D– is negatively charged, it will be deflected towards the positive
plate (opposite to that of 1H+). He2+ is positively charge and will be deflected towards the negative
plate (similar to that of 1H+).

q
T+ has a ratio that is 1/3 of that of 1H+, thus the angle of deflection will be 1/3 of that of 1H+.
m
Having a positive charge, it will be deflected to the negative plate.

Answer:
q
species ratio angle of deflection ()
m
q 1
proton, 1H+   = + 15o (given)
m 1
q 1 1
D– (= 2H–)   =   15  7.5
m 2 2
q 1 1
T+ (= 3H+)   =   15  5.0
m 3 3
q 2 1 1
He2+    =   15  7.5
m 4 2 2

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

Exercise 1.5
A plasma is a gaseous mixture in which the atoms have been completely stripped of their electrons,
leaving bare nuclei. Because of possible use in controlled nuclear fusion reactions, plasma
behaviour has been intensively studied. When passed between two plates carrying a certain electric
charge, 1H and 4He nuclei are deflected as follows:
1
H
4
A He
o
4

2o

sourc e
B

Giving reasons for your answers, suggest

(i) the polarity of plate A,
(ii) why 1H is deflected twice as much as 4He,
(iii) the angles of deflection (to 1 decimal place) of I: 2H nuclei,
II: 3He nuclei.
[J00/I/1 (c)]

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

2 QUANTIFYING THE MASSES OF ATOMS

In Section 1.2, we have looked at the composition of the atom. While the protons, neutrons and
electrons have masses, they are so small such that it is impossible to weigh atoms individually except
for highly specialised equipment. For day-to-day use in a laboratory, an easier way to quantify the
masses of atoms is needed. And so we usually measure the relative masses of atoms, or how heavy
one atom is compared to another atom.

2.1 Relative Masses of Atoms

LO 6(a)part: define the terms relative atomic, isotopic masses
We call this relative mass the relative atomic mass of an atom. We measure all relative masses against
the mass of carbon-12, the most abundant isotope of carbon. Hence, the definition of relative atomic
mass would look like the following:

average mass of one atom of an element

Relative atomic mass, Ar 
1
x the mass of one atom of 12 C
12

Note that the word ‘average’ is used in the definition above as the atomic mass of an atom takes into
account the relative abundance of all possible isotopes of that element. We will deal with the idea of
relative abundance of isotopes in the next section.

In cases where we want to deal very specifically with the atomic mass of one of the possible isotopes
of an element, then we would call this the relative isotopic mass. The definition would look like the
following:

mass of one atom of an isotope of an element

Relative isotopic mass 
1
x the mass of one atom of 12 C
12

2.2 Relative Abundance of Isotopes

LO 6(c): calculate the relative atomic mass of an element given the relative abundances of its isotopes

Most elements consist of mixtures of isotopes. The abundance of each isotope in a mixture is called
the isotopic abundance or the relative abundance.

For instance, chlorine has two isotopes: 35Cl and 37Cl (note that isotopes of the same element have
the same atomic number). Naturally occurring samples of chlorine are found to contain 35Cl and 37Cl
in a ratio of 3:1. Hence, the relative abundance of 35Cl is 75% and the relative abundance of 37Cl is 25%.

The relative atomic mass of an element is also the sum of the relative isotopic masses of each isotope
multiplied by their relative abundances.

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

Using chlorine as an example, 17

Relative atomic mass, Ar of Cl =  (relative isotopic mass x isotopic abundance) Cl
chlorine
= (35 x 0.75) + (37 x 0.25)
35.5
= 26.25 + 9.25
= 35.5 (1 d.p.)

Exercise 2.1 (Worked Example)

10 11
The relative atomic mass of boron, which consists of the isotopes 5B and 5B is 10.8. What is the
11
percentage of 5B atoms in the isotopic mixture?

Solution:
Let a be the relative abundance of 11B atoms.
Relative abundance of 10B atoms = (1  a)

a(11) + (1  a)(10) = 10.8

11a + 10  10a = 10.8
a = 0.8
Percentage of 11B atoms in the mixture = 80.0%

Comments:
10 11
The relative abundances of 5B and 5B should add up to 1.
The sum of the relative isotopic masses of each isotope multiplied by their relative abundances
will give the relative atomic mass of 10.8.

Exercise 2.2
1. The five isotopes of krypton occur in the following abundances:

isotopic mass % abundance

80 2
82 12
83 12
84 57
86 17

Use these data to calculate a value, to one decimal place, for the Ar of atmospheric krypton.

2. Naturally occurring gallium, Ga, is a mixture of two isotopes, gallium-69 and gallium-71. Use
this information, together with the Data Booklet, to calculate the percentage abundance of
each isotope.

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

3 THE ARRANGEMENT OF THE ELECTRONS

LO 1(f): 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

3.1 Principal Quantum Shell

In order to understand chemical reactions, one must understand how electrons are arranged in atoms.
Much about what we know of electrons comes from quantum theory, which states that electrons can
be described by four quantum numbers. (The only one required in the A-level syllabus is the principal
quantum number, n, of only integer value of 1, 2, 3, …)

The principal quantum number, n, describes the main energy level of an electron. It also indicates the
relative size of the orbital and therefore relative distance of the electron from the nucleus. The larger
the value of n, the higher the energy level and the further the electron is from the nucleus.

Third principal
All atomic orbitals of the same value of n are said to
quantum shell
be in the same quantum shell.
(n = 3)

The maximum number of electrons that can occupy Second principal

each principal quantum shell can be obtained by the quantum shell
(n = 2)
formula 2n2.
First principal quantum
shell (n = 1)

Figure 6. Principal quantum shells of an atom

Table 2 - Maximum number of electrons for each principal quantum shell.

principal quantum number (n) 1 2 3 4
2
maximum number of electrons (2n ) 2 8 18 32

3.2 Subshells

Each principal quantum shell can be subdivided into one or more subshells (or sub levels). The number
of subshells in a principal quantum shell is the same as its principal quantum number.

Table 3 - The subshells in each principal quantum shell

principal quantum
number of subshell types of subshells notation for subshells
number, n
1 1 s 1s
2 2 s, p 2s , 2p
3 3 s, p, d 3s , 3p , 3d,
4 4 s, p, d, f 4s , 4p, 4d, 4f

Subshells within a given quantum shell differ slightly in energy, with the energy of the subshell
increasing according to the following order: s, p, d, f, i.e., energy of 4s < 4p < 4d < 4f.

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3.3 Atomic Orbitals

Electrons are not randomly distributed in the region of space around the nucleus. They occupy specific
volume regions, called orbitals, which have specific energies associated with them. According to the
current quantum mechanical model of the atom, electrons in an atom do not remain in specific
positions. They move in spaces defined by the Schrödinger's equation and Heisenberg's Uncertainty
Principle (NOT in A-level syllabus). Instead of predicting the precise location for each electron in an
atom, each electron is assigned to an energy level and orbital as it can only possess specific quantities
of energy.

An atomic orbital is defined as the region of space with a 90% probability (or more) of finding an
electron. This distribution of the probability of finding an electron at a certain position is the electron
density.

 Each subshell (s, p, d, f) has one or more orbitals at the same energy level (degenerate) but
different orientations in space.
 Each orbital can contain up to a maximum of 2 electrons. These electrons are of opposite
spins.

Table 4.The number of orbitals and maximum number of electrons in each subshell
subshell number of orbitals maximum number of electrons in each subshell
s 1 2
p 3 6
d 5 10
f 7 14

The table below summarises the relationships among principal quantum shells, subshells, orbitals and
number of electrons.

Table 5. Summary of the relationship between principal quantum shells, subshells and orbitals
principal quantum maximum number of electrons in
subshell number of orbitals
number, n each principal quantum shell, 2n2
1 1s 1 2
2s 1
2 8
2p 3
3s 1
3 3p 3 18
3d 5
4s 1
4p 3
4 32
4d 5
4f 7

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LO 1(g): describe the shapes of s, p and d orbitals (Refer also to Topic 22 Chemistry of the Transition Elements) [knowledge
of wave functions is not required]

3.3.1 The s Orbital

Each s subshell has only one s orbital. All s orbitals are spherical in shape with no nodal plane (region
of zero electron density). The probability of finding an electron at a given distance from the nucleus is
the same regardless of the direction from the nucleus. The size of s orbitals increases with the principal
quantum number, i.e., 1s < 2s < 3s,…

Electron Density Plot Schematic Representation

1s orbital 2s orbital

Figure 7. The s orbital

3.3.2 The p Orbital

Each p subshell has three p orbitals. Since each orbital can hold up to 2 electrons, each p subshell can
hold up to 6 electrons. There are no p orbitals in the first quantum shell.

The p orbital is dumb-bell in shape. Each p orbital consists of two lobes with a region of zero electron
density (node) between them centered on the nucleus.

The three p orbitals in a certain quantum shell are identical in size and shape but differ in their spatial
orientation. The three p orbitals are represented as px, py, pz, where the subscripts denote the axes
along which the orbitals are orientated. The three p orbitals are degenerate, i.e. at the same energy
level. The size of p orbitals increases with the principal quantum number, i.e. 2p < 3p < 4p.

Electron Density Plot Schematic Representation

Figure 8. The p orbital

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

3.3.3 The d Orbital

Each d subshell has five d orbitals. Since each orbital can hold a maximum of 2 electrons, each d
subshell can hold up to 10 electrons. There are five d orbitals: dxy, dxz, dyz, dz2, dx2–y2. The five d orbitals
are also degenerate. The size of d orbitals increases with the principal quantum number, i.e. 3d < 4d
< 5d …

Electron Density Plot

Schematic Representation

Figure 9. The d orbitals (Note: It is not necessary to colour/shade the orbitals)

Exercise 3.1
What kind of orbital must an electron with the principal quantum number n = 2 occupy?
A a spherically-shaped orbital
B either an s or p orbital
C the orbital closest to the nucleus
D a dumb-bell-shaped orbital [N1995/IV/3; N2000/III/2]

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3.4 Electronic Configuration

The electronic configuration of an atom shows the distribution of electrons in various orbitals in an
atom.

Rule 1: The Aufbau or ‘Building-up’ Principle

Electrons in their ground states (i.e. when they are not excited) occupy orbitals in order of energy
levels. The orbital with the lowest energy is always filled first.

Figure 10. Relative energies of the orbitals for the first 20 elements

Figure 11 below shows the sequence in which the electron orbitals are populated with electrons in an
atom as the proton number increases.
The 1s subshell is the first to be filled, then the
2s orbital, the 2p orbitals and then the 3s orbitals
and so on. Electrons only enter higher energy
levels after lower energy levels have been filled.

For example, nitrogen, N, with atomic number 7

will have 2 electrons in 1s orbital and 2 electrons
in 2s orbital and 3 electrons in 2p orbitals.

The electronic configuration of N is represented

as 1s2 2s2 2p3.

Figure 11. Mnemonic for the order of filling electrons into the orbitals

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Rule 2: Hund's Rule of Multiplicity

When filling subshells that contain more than one orbital with the same energy (p, d and f subshells),
each orbital must be singly occupied before electrons are paired.

E.g. for 7N, each of the three 2p orbitals will be filled with 1 electron. To reflect this, we can write the
electronic configuration of N as 1s2 2s2 2px1 2py1 2pz1.

Rule 3: Pauli Exclusion Principle

An orbital cannot hold more than two electrons and the two electrons sharing the same orbital must
have opposite spins. This can be shown in an electron-in-box diagram where the box represents the
orbital and the arrows within it represent the electrons. The direction of the arrow (up or down)
indicates the spin of the electron.
Thus,

allowed not allowed

or
1s 1s 1s

Exercise 3.2 (Worked Example)

electronic
Element
configuration electron-in-box diagram

6C 1s22s22p2
1s 2s 2p 2p 2p

8O 1s22s22p4
1s 2s 2p 2p 2p

12Mg
2 2 6 2
1s 2s 2p 3s
1s 2s 2p 2p 2p 3s
2 2 6 2
1s 2s 2p 3s
21Sc 3p63d14s2 1s 2s 2p 2p 2p 3s 3p 3p 3p 3d 3d 3d 3d 3d 4s
1s22s22p63s2
25Mn 3p63d54s2 1s 2s 2p 2p 2p 3s 3p 3p 3p 3d 3d 3d 3d 3d 4s
2 2 6 2
1s 2s 2p 3s
24Cr* 3p63d54s1 1s 2s 2p 2p 2p 3s 3p 3p 3p 3d 3d 3d 3d 3d 4s
1s22s22p63s2
27Co 3p63d74s2 1s 2s 2p 2p 2p 3s 3p 3p 3p 3d 3d 3d 3d 3d 4s
1s22s22p63s2
29Cu* 3p63d104s1 1s 2s 2p 2p 2p 3s 3p 3p 3p 3d 3d 3d 3d 3d 4s
1s22s22p63s2
35Br 3p63d104s24p5 1s 2s 2p 2p 2p 3s 3p 3p 3p 3d 3d 3d 3d 3d 4s 4p 4p 4p

Chromium and copper are two exceptions to this general pattern:

 Electronic configuration of Cr is 1s2 2s2 2p6 3s2 3p6 3d5 4s1 (not 1s2 2s2 2p6 3s2 3p6 3d4 4s2)
 Electronic configuration of Cu is 1s2 2s2 2p6 3s2 3p6 3d10 4s1 (not 1s2 2s2 2p6 3s2 3p6 3d9 4s2)

The explanation for these exceptions are not required in the A-level syllabus but they are a result of
the effects of increasing nuclear charge on the 3d and 4s orbitals and the repulsions between electrons
sharing the same orbital. For a full explanation with references to the published papers, please refer
to ‘Inorganic Chemistry, 3rd Ed, G.L. Miessler & D.A. Tarr, Pearson, Prentice Hall, Chapter 2, sections
2.2.3 & 2.2.4, pgs 34 to 43.

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

LO 1(h): state the electronic configuration of atoms and ions given the proton number (and charge)

When writing the electronic configuration of a cation:

 first write the electronic configuration of the atom,
 then remove the number of electrons equal to the positive charge, starting from the highest
energy (outermost) subshell.
 From Scandium onwards, the 4s electrons are removed first in the formation of positive ions.
E.g., the electronic configuration of 29Cu is 1s2 2s2 2p6 3s2 3p6 3d10 4s1 while that of 29Cu2+ is
1s2 2s2 2p6 3s2 3p6 3d9.

When writing the electronic configuration of an anion:

 first write the electronic configuration of the atom,
 then add number of electrons equal to the negative charge, starting from orbitals of lowest
energy available.
E.g., the electronic configuration of 16S is 1s2 2s2 2p6 3s2 3p4, while that of 16S2– is 1s2 2s2 2p6 3s2 3p6.

Exercise 3.3 (Worked Example)

Complete the table below.
electronic configuration of electronic configuration of
ion
atom ion
+
11Na

2+
26Fe

–
17Cl

Comments:
The electronic configurations of the atoms and ions can be obtained by applying the rules stated
above.

For Na+ and Fe2+, remove 1 and 2 electrons respectively from the highest energy subshell. One 3s
electron will be removed from Na and two 4s electrons will be removed from Fe.

Answer:

electronic configuration of electronic configuration of

ion
atom ion
+ 2 2 6 1 2 2 6
11Na 1s 2s 2p 3s 1s 2s 2p
2+
26Fe 1s22s22p63s23p63d64s2 1s22s22p63s23p63d6
–
17Cl 1s22s22p63s23p5 1s22s22p63s23p6

Exercise 3.4
Which of the following particles would, on losing an electron, have a half-filled set of p orbitals?
A C B N– C O+ D O–
[J93/IV/2]

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3.5 Electronic Configuration and Periodicity

LO 5(a): recognise variation in the electronic configurations across a Period and down a Group

In the Periodic Table, the arrangement of the elements was proposed according to their electronic
configurations. It is divided into the s-block, the d-block and the p-block. The electronic configurations
of elements will affect their physical and chemical properties.

Table 6(a). The valence electronic configuration of each group in the periodic table
group Number valence shell electronic configuration block
1 ns1
s-block
2 ns2
13 ns2np1
14 ns2np2
15 ns2np3
p-block
16 ns2np4
17 ns2np5
18 ns2np6

Table 6(b). The valence electronic configuration for elements in Periods 2 & 3
Period Li Be B C N O F Ne
2 [He]2s1 [He]2s2 [He]2s22p1 [He]2s22p2 [He]2s22p3 [He]2s22p4 [He]2s22p5 [He]2s22p6

Period Na Mg Al Si P S Cl Ar
3 [Ne]3s1 [Ne]3s2 [Ne]3s23p1 [Ne]3s23p2 [Ne]3s23p3 [Ne]3s23p4 [Ne]3s23p5 [Ne]3s23p6

Note: For simplicity, [He] and [Ne] are used to represent the configuration 1s2 and 1s22s22p6
respectively. Do not use these symbols when asked to write electronic configuration in examinations.

Figure 12. Periodic table illustrating how elements are grouped according to their valence subshells

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

LO 13(a): explain what is meant by a transition element, in terms of d-block elements forming one or more stable ions with
partially filled d subshells
LO 13(b): state the electronic configuration of a first row transition element and its ion

By definition,
A transition metal is a d-block element that form one or more stable ions with a partially-filled d-
subshell.

As a result, d-block elements such as scandium and zinc are not considered to be transition elements
because:
 scandium forms only the Sc3+ which has the 3d0 configuration
 zinc forms only Zn2+ ion which has 3d10 configuration

Exercise 3.5
Which of the following corresponds to the configuration of the three electrons of highest energy for
the ground state of an element in Group 13?
A 1s2 2s1 B 2s1 2p2 C 3p3 D 4s2 4p1
[N1985/III/3; J1989/III/3]

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

4 PERIODIC TRENDS IN ATOMIC AND IONIC RADII

LO 5(b)part: describe and explain qualitatively the general trends and variations in atomic radius, ionic radius, first ionisation
energy
(i) across a Period in terms of shielding and nuclear charge,
(ii) down a Group in terms of increasing number of electronic shells, shielding and nuclear charge

In explaining periodic trends in atomic and ionic radii, two fundamental considerations are important:
(i) number of quantum shells
The number of quantum shells determine how far the outermost electron is from the nucleus. The
further the outermost electron is from the nucleus, the weaker the attraction between the outermost
electron and the nucleus.

(ii) effective nuclear charge

The effective nuclear charge, Zeff, is the net nuclear charge experienced by an outer electron. It is
dependent on:

(a) Nuclear charge (Z): The nuclear charge is dependent on the number of protons. The larger the
number of protons, the greater the nuclear charge and the attraction for the outermost electrons
by the nucleus.

(b) Shielding or screening effect (S): Presence of inner-shell electrons reduces the electrostatic
attraction between the outermost electrons and the nucleus.

Hence, Zeff = Z – S

Electrons in the same quantum shell do exert some shielding effect on each other.*
*For example, shielding of p electrons by s or p electrons in the same quantum shell does occur.
However this shielding effect is small compared to that by the inner core electrons.
*Order of shielding effect by electrons in the same quantum shell: s > p > d > f.

4.1 Trend in Atomic Radius

Down the Group:

General Trend:
Atomic radius increases down the group.

Reason:

 As the number of quantum shells

increases the outermost electrons are
further away from the nucleus, hence the
Figure 13. Atomic radii of Group 1 elements atomic radius increases. Both the nuclear
charge and shielding effect increase down
the group, hence the effective nuclear
charge differs little down the group.

Hence the number of quantum shells is the

more important factor.

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

Across Periods 2 and 3:

General Trend:

Atomic radius decreases across the period.

Reason:

 nuclear charge increases due to the

increase in the number of protons
in the nucleus

 shielding effect remains relatively

Figure 14. Atomic radii of period 2 & 3 elements constant (as the electrons are added
to the same outermost shell)
Why are the atomic radii of the noble gases so large?
 effective nuclear charge increases,
The term atomic radius does not mean the same thing resulting in stronger electrostatic
for every element. The atomic radii given for He, Ne forces of attraction between the
and Ar in the Data Booklet are labelled van der Waals’ nucleus and the outermost electron
radii, rather than covalent radii (see Chapter 02 Section
4.2 for explanation). Ar, for instance, does not form  outermost electrons are pulled
compounds, so it will not have a covalent radius. The closer to the nucleus and hence a
van der Waals’ radius of an atom is always larger than decrease in the atomic radius
the covalent radius, which explains the anomalously
high atomic radii of the noble gases in the graph above.

Across the First Row Transition Elements:

General Trend:

Atomic radius is relatively invariant.

Reason:

 nuclear charge increases due to

increasing number of protons

 electrons are added to the inner

3d subshell, which contributes to
the shielding effect

 shielding effect increases thereby

nullifying, to a considerable
extent, the influence of each
Figure 15. Atomic radii across periods 2, 3 and the first row
additional proton in the nucleus
transition elements

 effective nuclear charge remains

almost constant

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

4.2 Trend in Ionic Radius

Ionic radius of cations:

Na+ > Mg2+ > Al3+ > Si4+

Ionic radius of anions:

P3 > S2 > Cl−

Na+ Mg2+ Al3+ Si4+ P3 S2− Cl−

Figure 16. Ionic Radii across Period 3

The ions, Na+, Mg2+, Al3+ and Si4+ are said to
be isoelectronic as they have the same
number of electrons, which is 10. Similarly
P3-, S2- and Cl− are isoelectronic as they
have 18 electrons each. Across the two
isoelectronic series (Na+ to Si4+ and P3− to
Cl−), nuclear charge increases and
shielding effect is the same (due to same
number of electrons).

This results in an increase in the effective

nuclear charge and a stronger attraction
between the outermost electrons and the
nucleus, hence a decrease in ionic size
across each series.

There is a sharp increase in ionic radius

from the cationic series of Na+ to Si4+ to
the anionic series of P3 to Cl, because the
anions have one more quantum shell of
electrons than the cations.

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

5 Ionisation Energy (IE)

5.1 Definitions

First ionisation energy is the energy needed to remove 1 mole of electrons from 1 mole of gaseous
atoms to form 1 mole of unipositively charged gaseous ions.

X(g)  X+(g) + e – 1st IE

Examples: Na(g)  Na+(g) + e– 1st IE of Na

Fe(g)  Fe+(g) + e– 1st IE of Fe

Second ionisation energy is the energy required to remove 1 mole of electrons from 1 mole of
unipositively charged gaseous ions to form 1 mole of gaseous ions with double positive charge.

X+(g)  X2+(g) + e– 2nd IE

Examples: Na+(g)  Na2+(g) + e– 2nd IE of Na

Fe+(g)  Fe2+(g) + e– 2nd IE of Fe

Similarly, nth ionisation energy is the energy needed to remove 1 mole of electrons from 1 mole of
gaseous ions with (n1)+ charge to form 1 mole of gaseous ions with n+ charge.

X(n–1)+(g)  Xn+(g) + e– nth IE

Factors affecting ionisation energy of an atom:

 number of quantum shells
The larger the number of quantum shells in an atom, the further the electron is from the
nucleus and hence experiences weaker nuclear attraction and is easier to remove, hence the
lower the ionisation energy.
 effective nuclear charge, Zeff
The higher the effective nuclear charge, the stronger the attractive forces between the
nucleus and the electrons to be removed, hence the greater the ionisation energy.

5.2 Trend in the Successive Ionisation Energies of the Same Element

For the same element, ionisation energies always increase in the following order:

IE1 < IE2 < IE3 < IE4 < …

Reason:
When an electron is removed from a neutral atom, the number of protons that exert an attraction for
the remaining electrons remains the same. However, the shielding effect (or mutual electrostatic
repulsion) among the remaining electrons in the outermost shell is reduced since there is now one
less electron. Hence effective nuclear charge increases. More energy is needed to remove another
electron from the more positively charged ion, and hence a higher ionisation energy.

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

Application of successive ionisation energy values

LO 1(j): deduce the electronic configurations of elements from successive ionisation energy data
LO 1(k): interpret successive ionisation energy data of an element in terms of the position of that element within the
Periodic Table

Successive ionisation energy values can be used to determine the electronic configuration of atoms
and hence the identity of the element.

E.g., the ground state electronic configuration of magnesium is 1s2 2s2 2p6 3s2.

1s  the first big increase from the 2nd

to 3rd ionisation energies:
Ionisation Energy / kJ mol-1

- implies that the third electron is

in an inner quantum shell, and
thus there are two electrons in the
outermost or valence 3s subshell.
2s
2p Conclusion: Mg is a Group 2
element.
3s

1 2 3 4 5 6 7 8 9 10 11 12
 the gradual increase from the 3rd
Number of Electrons Removed
to 10th ionisation energies:

Figure 17. Successive ionisation energies of magnesium - implies that the next 8 electrons
are removed from the second
quantum shell.

- a slightly greater increase from

the 8th to 9th ionisation energies as
more energy is required to remove
the 2s electrons, which are closer
to the nucleus compared to the 2p
electrons.

 the second big increase from the

10th to 11th ionisation energies

- implies that the last two

electrons are in the first (inner
most) quantum shell.

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

Exercise 5.1 (Worked Example)

Identify the group number of the element for each set of ionisation energies.
(i) A:

Ionisation Energy

first IE

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
Successive Ionizations

(ii) B: successive ionisation energies (in kJ mol−1): 1060, 1900, 2920, 4960, 6280, 21 200

(iii) C: successive ionisation energies (in kJ mol−1): 687, 1577, 3232, 4355, 16 091, 19 784.

Answers:
(i) A: Group 17
(ii) B: Group 15
(iii) C: Group 14

Comments:
For this question, look for the first big increase in ionisation energy which would signal that there is
a change in quantum shell.

In (i), the first big increase in ionisation energy between electron 7 and 8, indicating that there are
7 electrons in the outer most shell of A.

For (ii) and (iii) find the difference between each successive ionisation.
For (ii), the biggest increase in ionisation energy occurs between electron 5 and 6. This shows that
there are 5 electrons in the outermost quantum shell.
Similarly for (iii), there are 4 electrons in the outermost quantum shell.

Exercise 5.2
The use of the Data Booklet is relevant to this question.
The successive ionisation energies, in kJ mol–1, of an element X are given below:

870 1800 3000 3600 5800 7000 13200

What is X?

A 33As B 40Zr C 52Te D 53I

[J92/IV/4; N2002/I/14; J2003/I/4]

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

5.3 Trend in the First Ionisation Energies of Different Elements

LO 1(i): explain the factors influencing the ionisation energies of the elements (see the Data Booklet)

Down the Group:

General Trend:
Ionisation Energy / kJ mol-1

In general, first ionisation energy of elements

decreases down a group.
Reason:
Down the group, the number of quantum shells
of electrons increases, hence the outermost
electrons are further from the nucleus.
Therefore, the electrostatic forces of attraction
Li Na K Rb Cs between the nucleus and the outermost
electron is weaker and less energy is required
Figure 18. First ionisation energy trend down a group
to remove this electron.
Both the nuclear charge and shielding effect increase down the group, so the effective nuclear charge
differs little down the group. Hence, the number of quantum shells is the more important factor.

Across Periods 2 and 3:

He
Period 2 Period 3
Ne

F
Ionisation Energy / kJ mol-1

Ar
N
O
Cl
C
H P S
Be
B Si
Mg
Al

Li Na K

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
Figure 19. First ionisation energy trend across Periods 2 & 3
General Trend:
In general, first ionisation energy of elements increases across a period.

Reason:
Across the period, nuclear charge increases and shielding effect remains relatively the same. Hence
the effective nuclear charge increases and the electrostatic forces of attraction between the
outermost electrons and the nucleus become stronger, so more energy is required to remove the
outermost electron.

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

Two Anomalies:
 Small dip between Group 2 and Group 13 elements
Al has lower 1st ionisation energy than Mg.

Mg: 1s2 2s2 2p6 3s2 Al: 1s2 2s2 2p6 3s2 3p1

The 3p subshell of Al is further away from the nucleus than the 3s subshell. There is weaker
attraction between the nucleus and the outermost electron. Hence less energy is required to
remove the 3p electron from Al, resulting in a lower ionisation energy for Al.

 Small dip between Group 15 and Group 16 elements

S has lower 1st IE than P.

Consider the electronic configurations of P and S.

P: 1s2 2s2 2p6 3s2 3p3 S: 1s2 2s2 2p6 3s2 3p4

1s 2s 2p 3s 3p 1s 2s 2p 3s 3p

All the 3p electrons in P are unpaired. In S, two of the 3p electrons are paired. There is some inter-
electronic repulsion between the paired electrons in the 3p subshell in S. Thus, less energy than
expected is required to remove one of these paired electrons from S.

Across Transition Elements:

LO 13(c): explain why atomic radii and first ionisation energies of the transition elements are relatively invariant

Figure 20: First ionisation energy trend across the first transition elements series

General Trend:
First ionisation energy remains relatively invariant.
Reason:
 1st ionisation energy involves removal of a 4s electron
 The nuclear charge increases due to increasing number of protons while additional electrons are
added to the inner 3d subshell, which contributes to the shielding effect. The shielding effect
increases thereby nullifying, to a considerable extent, the influence of each additional proton in
the nucleus

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

 Effective nuclear charge remains almost constant. Thus, energy required to remove the outermost
electron of each succeeding element remains relatively invariant

Exercise 5.3 (Worked Example)

The diagram shows part of the Periodic Table.

H He

Li Be B C N O F Ne

Na Mg Al Si P S Cl Ar

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Which element in the diagram has the largest atomic radii?

A Br B K C Kr D Sc
[N10/I/1]

Answer: B

Comments:
The atomic radius of an atom decreases across the period due to the increasing effective nuclear
charge. K is the only group 1 element here, thus the answer is B.

Exercise 5.4
Use of the Data Booklet is relevant to this question.
The bar chart gives some information about the first ionisation energies of elements, numbering
from 1 to 4.

The elements are adjacent to one another in the Periodic Table with increasing proton number
either across a period from left to right, or down a group.

First ionisation
energy (arbitrary
units)
1 2 3 4

What could these elements be?

A B, C, N, O
B Co, Ni, Cu, Zn
C Mg, Ca, Sr, Ba
D Si, P, S, Cl
[N09/I/17]

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Hwa Chong Institution 2023 01 – Atomic Structure & Physical Periodicity

LOOKING AHEAD

In this topic, we have looked at the structure of the atoms, the shapes and energies of the atomic
orbitals, as well as the energies associated with removal of electrons from isolated gaseous atoms. In
the following topic, we will be applying these concepts to help us understand how atoms interact to
form chemical bonds.

A particularly important and useful concept is that of effective nuclear charge. We have used this
concept of effective nuclear charge quite extensively in this last section of Topic 1. So far, we have
only considered isolated gaseous atoms and discussed the impact of the effective nuclear charge on
removing electrons from these atoms. In reality, the electrostatic forces due to the effective nuclear
charge of the atom extend beyond its outermost electron.

When two atoms are in proximity, the nucleus of each atom exerts an attractive force on its own
electrons as well as the electrons of the other atom. The same nucleus also exerts a repulsive force on
the nucleus of the other atom. This attraction and repulsion on the electrons and nucleus of the other
atom by the first atom result in a net attractive force on the electrons of the other atom. It is quite
clear then that the effective nuclear charge of the first atom would play a significant role in attracting
the electrons of the other atom.

This attraction was first referred to as ‘oxygenicity’ in 1809 by Avogadro and Bezelius adopted the
term ‘electronegativity’ in 1811. The concept of ‘electronegativity’ was finally defined and quantified
by Linus Pauling in 1932. (Interesting fact: Linus Pauling is the only person to be awarded two unshared
Nobel Prizes.)

Electronegativity quantifies the attractive force one atom exerts on the electrons of another atom in
a chemical bond. A larger number implies a larger force of attraction towards the electrons. We will
have a more thorough discussion of the concept of electronegativity when we deal with chemical
bonding in Topic 2.

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Hwa Chong Institution 2023 02 – Chemical Bonding

02 Chemical Bonding
GUIDING QUESTIONS
● What holds particles together?
● What are the different models that describe the forces that hold particles together?
● How do these models explain the properties of matter?
● How do we determine the shapes of molecules?
● What are the trends and variations in physical properties in compounds?
● How can the trends and variations in physical properties be explained?

LEARNING OUTCOMES
Students should be able to:
2(a) show understanding that all chemical bonds are electrostatic in nature and describe:
(i) ionic bond as the electrostatic attraction between oppositely charged ions
(ii) covalent bond as the electrostatic attraction between a shared pair of electrons
and positively charged nuclei
(iii) metallic bond as the electrostatic attraction between a lattice of positive ions and
delocalized electrons
2(b) describe, including the use of ‘dot-and-cross’ diagrams:
(i) ionic bonding as in sodium chloride and magnesium oxide
(ii) covalent bonding as in hydrogen; oxygen; nitrogen; chlorine; hydrogen chloride;
carbon dioxide; methane; ethene
(iii) co-ordinate (dative covalent) bonding, as in formation of the ammonium ion and
in the Al2Cl6 molecule
7(e) explain, in qualitative terms, the effect of ionic charge and of ionic radius on the numerical
magnitude of a lattice energy (Refer to Topic 5 Chemical Energetics)
2(c) describe covalent bonding in terms of orbital overlap (limited to s and p orbitals only),
giving σ and π bonds
2(d) explain the shapes of, and bond angles in, molecules such as BF3 (trigonal planar); CO2
(linear); CH4 (tetrahedral); NH3 (trigonal pyramidal); H2O (bent); SF6 (octahedral) by using
the Valence Shell Electron Pair Repulsion theory
2(e) predict the shapes of, and bond angles in, molecules analogous to those specified in (d)
2(f) explain and deduce bond polarity using the concept of electronegativity [quantitative
treatment of electronegativity is not required]
2(g) deduce the polarity of a molecule using bond polarity and its molecular shape (analogous
to those specified in (d));
2(h) describe the following forces of attraction (electrostatic in nature):
(i) intermolecular forces, based on permanent and induced dipoles, as in CHC l3(l);
Br2(l) and the liquid noble gases
(ii) hydrogen bonding, using ammonia and water as examples of molecules containing
–NH and –OH groups
2(i) outline the importance of hydrogen bonding to the physical properties of substances,
including ice and water

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Hwa Chong Institution 2023 02 – Chemical Bonding

2(j) explain the terms bond energy and bond length for covalent bonds
2(k) compare the reactivities of covalent bonds in terms of bond energy, bond length and bond
polarity
2(l) describe, in simple terms, the lattice structure of a crystalline solid which is:
(i) ionic, as in sodium chloride, magnesium oxide
(ii) simple molecular, as in iodine
(iii) giant molecular, as in graphite; diamond
(iv) hydrogen-bonded, as in ice
(v) metallic, as in copper
[the concept of the ‘unit cell’ is not required]
2(m) describe, interpret and/or predict the effect of different types of structure and bonding
on the physical properties of substances
2(n) suggest the type of structure and bonding present in a substance from given information
5(b) describe and explain qualitatively the general trends and variations in atomic radius, ionic
radius, first ionization energy and electronegativity,
(i) across a Period in terms of shielding and nuclear charge,
(ii) down a Group in terms of increasing number of electronic shells, shielding and
nuclear charge
(Refer to Topic 1 Atomic Structure & Physical Periodicity for trends and variations in atomic
and ionic radii, and first ionization energy.)
5(c) interpret the variation in melting point and in electrical conductivity across a Period in
terms of structure and bonding in the elements (metallic, giant molecular, or simple
molecular) (Refer to Topic 21 Chemical Periodicity)
5(d) describe and explain the trend in volatility of the Group 17 elements in terms of
instantaneous dipole-induced dipole attraction (Refer to Topic 21 Chemical Periodicity)
11.1(d) describe sp3 hybridisation, as in ethane molecule, sp2 hybridisation, as in ethene and
benzene molecules, and sp hybridisation, as in ethyne molecule (Refer to Topic 12 Arenes
with regards to benzene)
11.1(e) explain the shapes of, and bond angles in, the ethane, ethene, benzene and ethyne
molecules in relation to σ and π carbon-carbon bonds (Refer to Topic 12 Arenes with
regards to benzene)

REFERENCES
1. Peter Cann and Peter Hughes, Chemistry for Advanced Level, 1st Edition, John Murray (Publishers)
Ltd, Chapters 3 & 4.
2. Martin S. Silberberg, Chemistry: The Molecular Nature of Matter and Change, Global Edition,
Chapter 9 to 12.
3. http://www.chemguide.co.uk/index.html

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Hwa Chong Institution 2023 02 – Chemical Bonding

1 INTRODUCTION

LOOKING BACK
The discovery of electrons by J. J. Thomson and the development of the atomic model, led to the
development of the concept of a chemical bond. As you uncover the nature of the chemical bond,
consider the following questions:
● Which parts of the atom is responsible for chemical bonding?
● How does the structure of the atom affect the chemical bonding it participates in?

1.1 Nature of a Chemical Bond

LO 2(a): show understanding that all chemical bonds are electrostatic in nature
(i) ionic bond as the electrostatic attraction between oppositely charged ions
(ii) covalent bond as the electrostatic attraction between a shared pair of electrons and positively charged nuclei
(iii) metallic bond as the electrostatic attraction between a lattice of positive ions and delocalized electrons

All chemical bonding arises from electrostatic attractions between positive and negative charges.
Electrostatic attraction is present in the three major types of bonding – ionic, covalent and metallic.

Types of chemical bonding Lecture Notes

Ionic bond is the electrostatic forces of attraction between oppositely charged Section 3
ions.

In sodium chloride, the Na+ cations and the Cl anions are held by ionic bonds.

Covalent bond is the electrostatic forces of attraction between the positively Section 4
charged nuclei (of both bonded atoms) and their shared electrons.

In the hydrogen molecule (H2), the two shared negatively charged electrons are
attracted by the positive nuclei of both hydrogen atoms.

Metallic bond is the electrostatic forces of attraction between the metal Section 2
cations and the sea of delocalised electrons.

In calcium, the Ca2+ cations and delocalised electrons are held by metallic bonds.

delocalised
cation
valence electron
(a) ionic bonding in NaCl (b) covalent bonding in H2 (c) metallic bonding in Ca

Figure 1. Ionic, covalent and metallic bonding are all electrostatic in nature

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Hwa Chong Institution 2023 02 – Chemical Bonding

In addition to ionic, covalent and metallic bonding, we will also be looking at other forces of attractions
summarised in Table 1.

Table 1. Comparison of the different types of chemical bonding

Types of chemical bonding Basis of attraction Energy /kJ mol–1 Example

ionic cation – anion 400 – 4000 NaCl

covalent nuclei – shared electrons 150 – 1100 H–H

metallic cations – delocalised electrons 75 – 1000 Mg

ion-dipole attraction ion charge – dipole charge 40 – 600

hydrogen bonding Between lone pair on F or O or N 10 – 40

and H on F or O or N

permanent dipole-permanent dipole charges 5 – 25

dipole (pd-pd) attraction

permanent dipole- dipole charge 2 – 10

induced dipole (pd-id) – polarisable electron cloud
attraction

instantaneous dipole-induced polarisable electron clouds 0.05 – 40

dipole (id-id) attraction

also called dispersion forces

1.2 Electronegativity

Electronegativity of an atom is a measure of its ability to attract the electrons in a covalent bond
to itself.

In the hydrogen molecule (Figure 1b), the bonding electrons are equally shared between the two
hydrogen atoms as they have the same electronegativity.

When the covalent bond is formed by two different atoms of different electronegativities, the bonding
electrons are not shared equally. For example in hydrogen chloride molecule (HCl), electron density
is pulled closer to the more electronegative Cl atom.

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Hwa Chong Institution 2023 02 – Chemical Bonding

LO 5(b)part: describe and explain qualitatively the general trends and variations in electronegativity, (i) across a Period i n
terms of shielding and nuclear charge, (ii) down a Group in terms of increasing number of electronic shells, shielding and
nuclear charge

Factors affecting electronegativity (same as those that affect ionisation energy)

 Across the Period

Nuclear charge increases while shielding effect remains relatively constant.

Effective nuclear charge increases, hence electronegativity increases across the period.

 Down the Group

Elements in the same group experience roughly the same effective nuclear charge as both nuclear
charge and shielding effect increase down the group.
However, as the number of quantum shells increases, atomic radius increases. Hence,
electronegativity decreases down the group.

Pauling’s Electronegativity Scale (Background info)

Electronegativity is a concept introduced by Linus Pauling which quantifies attractive force one atom
exerts on the electrons of another atom in close proximity. He assigned numerical values to the
elements on a scale of 0 to 4 and a larger number implies a larger force of attraction towards electrons.

electronegativity decreases down a group

electronegativity increases across a period

Figure 2. Electronegativity values for the elements; to which group of elements do you think Pauling assigned an
electronegativity value of zero?

You are not required to memorise the electronegativity values!

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1.3 Electronegativity and Types of Chemical Bonding

The difference in electronegativity between two atoms can be used to predict the type of bond
formed between them.

similar electronegativity
between atoms electron sharing covalent bonding

large difference in
electronegativity electron transfer ionic bonding
between atoms

In general,
 Covalent bonds are formed between atoms of non-metals of similar electronegativity.
 Ionic bonding occurs between a metal and non-metal with a large difference in
electronegativity.

Table 2. Some trends in Period 3 elements

Element Na Mg Al Si P S Cl Ar

metal metalloid non-metal

1 2 13 14 15 16 17 18
Group
Electronic [Ne] [Ne] [Ne] [Ne] [Ne]
[Ne] 3s1 [Ne] 3s2 [Ne] 3s2 3p2
structure 3s2 3p1 3s2 3p3 3s2 3p4 3s23p5 3s2 3p6
No. of
valence 1 2 3 4 5 6 7 8
electrons
Types of giant simple
giant metallic simple molecular
structure molecular atomic
Electrical semi-
good conductors non-conductors
conductivity conductor

Exercise 1.1
Identify the type of chemical bonding in the following
a) barium, Ba b) oxygen, O2
metallic bonding covalent bonding
c) barium oxide, BaO d) nitrogen dioxide, NO2
ionic bonding covalent bonding

However, it is possible for a metal and non-metal to form covalent bonds (rather than ionic bonds).
For example, the bonds in AlCl3 are considered covalent.

Most chemical bonds are neither purely covalent nor purely ionic but have characteristics of both ionic
and covalent bonding (see section 7).

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2 METALLIC BONDING & PHYSICAL PROPERTIES OF METALS

2.1 Metallic Lattice

LO 2(l) part: describe, in simple terms, the lattice structure of a crystalline solid which is: (v) metallic, as in copper

Metals in the solid state have a giant metallic lattice structure which is a lattice of metal cations and
the sea of delocalised electrons held together by metallic bonding.

Figure 3 shows the structure and bonding in calcium metal.

Figure 3. Structure and bonding in calcium metal

In solid calcium, Ca2+ cations are arranged in a regular manner. Each Ca atom contributes two valence
electrons into the sea of delocalised electrons. These delocalised electrons are no longer attracted to
only one specific atom but can move freely throughout the lattice. These delocalised electrons are
responsible for the characteristic physical properties of metals such as good electrical and thermal
conductivity.

Note: The metal is electrically neutral as the number of positive and negative charges balance out.

2.2 Strength of Metallic Bonding

The strength of the attraction between the metal cations and the delocalised electrons depends on:

 number of valence electrons contributed per metal atom

The larger the number of valence electrons contributed per atom, the greater the number of
delocalised electrons, the stronger the metallic bonding.

 charge and radius of the metal cation

The higher the charge and the smaller the radius of the metal cation, the higher its charge
density*, and the stronger the metallic bonding.

*Charge density of an ion, sometimes called surface charge density, is the amount of charge per
unit surface area of that ion. For simplicity, we can compare the charge densities of two ions by
ionic charge
comparing their ratio.
ionic radius

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2.3 Physical properties of metals

LO 2(m): describe, interpret and/or predict the effect of different types of structure and bonding on the physical properties
of substances
LO 2(n): suggest the type of structure and bonding present in a substance from given information

2.3.1 High melting and boiling points

Metals have high melting and boiling points as a large amount of energy is needed to overcome the
strong attraction between the metal cations and the delocalised electrons.

The stronger the metallic bonding, more energy is needed to overcome the metallic bonding, the
higher the melting and boiling points.

Exercise 2.1 (Worked Example)

Explain why the melting point of Mg (650 C) is higher than that of Na (98 C), quoting relevant data
from the Data Booklet.

Answer: Strategy:
Each Mg atom has two valence electrons while each Na atom has one  compare the no. of
valence electron. Hence, magnesium has a larger number of delocalised valence electron
electrons.  compare the
Mg2+ (0.065 nm) has a larger charge and smaller ionic radius than Na+ charge and radius
(0.095 nm). Mg2+ has a higher charge density than Na+.  compare strength
More energy is needed to overcome the stronger metallic bonding in of metallic bond &
magnesium than that in sodium. energy needed

(Useful information)
When a solid metal melts, the closely packed cations become further apart but the metallic bonding
is not completely broken, unlike during boiling. Hence, the boiling point is a better indicator of the
strength of metallic bonding than the melting point.

2.3.2 Good electrical and thermal conductivity

In order for a material to conduct electricity, it must have mobile charge carriers which are typically
electron or ions. Metals are good electrical conductors because the delocalised electrons act as mobile
charge carriers.

The delocalised electrons also explain why metals are good conductors of heat. Thermal energy causes
the electrons to move more quickly. The energy is then transferred to the other parts of the metal by
the mobile electrons.

Exercise 2.2
Why does copper wire conduct electricity when a potential difference is applied?
A Bonding electrons in the crystal lattice move.
B Copper(II) ions move to the cathode.
C The atoms of copper become ionised.
D The crystal lattice breaks down. [J2002/I/5]

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2.3.3 Malleable and ductile

Metals are usually malleable (easily beaten or rolled into sheets) and ductile (easily drawn into rods,
wires and tubes). When a large stress (e.g. hammering) is applied to a piece of solid metal, the layers
of ions will slide over one another into new positions. The overall shape of the metal changes (the
metal deforms) but it does not break apart because the 'sea' of delocalised electrons prevents
repulsion between the cations as they move past one another, and metallic bonding remains intact.

Figure 4. The metallic lattice when subjected to shear stress

2.3.4 Hardness
The hardness of a solid material depends on how easily we can move the particles from their fixed
positions in the solid lattice. In metals, this depends on the strength of metallic bonding.

Metals are usually hard, although the Group 1 and 2 metals are soft. Iron is hard and does nor deform
easily while sodium can be easily cut with a pen knife.

Alloys & their uses (Application example)

Most metals used in practical applications such as aluminium aircraft frames are in the form of an
alloy instead of the pure metal.

Alloys are mixtures of metals involving incorporation of small quantities of other element(s) into the
pure metal. Alloying makes metals harder. This is because atoms of the added element(s) have a
different size. This will disrupt the orderly arrangement of the main metal atoms such that they can
no longer slide over each other easily when a force is applied. This increases the hardness and strength
of the alloy compared to the pure metal.

Figure 5. Arrangement of atoms in an alloy

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3 IONIC BONDING & PHYSICAL PROPERTIES OF IONIC COMPOUNDS

3.1 Ionic Lattice

LO 2(l) part: describe, in simple terms, the lattice structure of a crystalline solid which is: (i) ionic, as in sodium chloride,
magnesium oxide

Ionic compounds in the solid state have a giant ionic lattice structure which is a lattice of cations and
anions held together by ionic bonding.

Figure 6 shows the structure and bonding in sodium chloride.

C l–
–
Na+

Na+ C l–

space-filling model expanded model

Figure 6. Models of the NaCl lattice. The space-filling model illustrates the close packing of ionic solids while the
expanded model shows the coordination number of each ion and the orderly arrangement within the giant ionic lattice.

Ionic bonding exists between any two adjacent ions of opposite charge. Ionic bonding is
non-directional and extends indefinitely in all directions while a covalent bond is directional as one
covalent bond can only be formed between two specific atoms.

Coordination number (Background info)

The number of ions that surround another ion of the opposite charge in an ionic lattice is called the
coordination number of that central ion.

For example, in sodium chloride, one Na+ cation is surrounded by six Cl– anions and vice-versa so the
coordination number is six (see Figure 6).

Table 3. Coordination number of an ion in an ionic lattice depends on relative sizes and charges of cation and anion
compound cation radius anion radius anion radius coordination coordination
/nm /nm cation radius number of cation number of anion
ZnS 0.08 0.19 2.4 4 4
NaCl 0.10 0.18 1.8 6 6
MgO 0.07 0.14 2.0 6 6
CsCl 0.17 0.18 1.1 8 8
CaF2 0.10 0.13 1.3 8 4

You are not required to memorise the coordination numbers in Table 3.

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Coordination number depends on:

 Relative sizes – a small ion typically has a lower coordination number as there will be less space for
ions of the opposite charge to surround it;
 Relative charges – e.g. a cation with +2 charge needs twice as many anions with –1 charge, compared
to a cation with +1 charge, to gain charge neutrality.

3.2 Strength of Ionic Bonding

LO 7(e): explain, in qualitative terms, the effect of ionic charge and of ionic radius on the numerical magnitude of a lattice
energy

Lattice energy is defined as the heat evolved when 1 mole of a pure ionic solid is formed from its
constituent gaseous ions.

We can compare the strength of ionic bonding using lattice energy – the larger the magnitude of
lattice energy, the more heat is given out when the ionic bonds are formed, the stronger the ionic
bonding.

The magnitude of lattice energy depends on the charge of the ions, and their radii.

q + × q−
lattice energy 
r+ + r−
where q+ = charge on cation, q– = charge on anion
r+ = radius of cation, r– = radius of anion

The higher the charge and the smaller the radii of the ions, the larger the magnitude of lattice energy,
the stronger the ionic bonding.

3.3 Physical Properties of Ionic Compounds

LO 2(n): describe, interpret and/or predict the effect of different types of structure and bonding on the physical properties of
substances
LO 2(o): suggest the type of structure and bonding present in a substance from given information

3.3.1 High melting and boiling points

Ionic solids have high melting and boiling points as a large amount of energy is needed to overcome
the strong electrostatic attractions between oppositely charged ions.

The stronger the ionic bonding, more energy is needed to overcome the ionic bonding, the higher the
melting and boiling points.

Table 4. Small, highly charged ions bond strongly, leading to high melting points.
compound cation radius /nm anion radius /nm cation charge anion charge m.p. /C
NaCl 0.10 0.18 +1 –1 801
NaF 0.10 0.13 +1 –1 993
MgF2 0.07 0.13 +2 –1 1261
MgO 0.07 0.14 +2 –2 2852

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Exercise 3.1 (Worked Example)

Explain why magnesium oxide has a higher melting point than sodium chloride, quoting relevant
data from the Data Booklet.

Answer: Strategy:
From Data Booklet,  quote ionic radii from
Mg2+ O2─ Na+ Cl─ Data Booklet
Ionic radii/nm 0.065 0.140 0.095 0.181

Mg2+ has a smaller radius than Na+ while O2─ has a smaller radius than
Cl─.

Mg2+ and O2─ have higher charges than Na+ and Cl─, respectively.  compare ionic charges
q+ × q−
Lattice energy   quote LE formula &
r+ + r−
Lattice energy of MgO is larger in magnitude. compare magnitude of
lattice energy, strength
More energy is needed to overcome the stronger ionic bonding in MgO. of ionic bond & energy
needed

3.3.2 Good electrical conductivity

In the solid state, ionic compounds do not conduct electricity as the ions are in fixed positions and are
not free to move.

In the molten or aqueous state, ionic compounds are good electrical conductors because the ions can
act as mobile charge carriers.

Lamp unlit Lamp lights up Lamp lights up

Figure 7. Ionic compounds do not conduct electricity in the solid state but do so when molten or dissolved in aq. solution

The electrical conductivity of an aqueous solution of an ionic compound increases as its concentration
increases, because there are more ions to carry the charge.

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3.3.3 Hard and rigid but brittle

In an ionic lattice, oppositely charged ions are held in fixed positions throughout the crystal lattice by
strong ionic bonding. Moving the ions out of position requires large amounts of energy to overcome
these bonds. Ionic lattices are therefore quite hard (do not dent or deform easily) and rigid (do not
bend easily).

If a strong enough force (e.g. by cutting or knocking) is applied, it will force ions of like charges to move
next to each other. Repulsion between ions of like charges will cause the lattice to shatter. Ionic
lattices are therefore brittle (crack without deforming).

a force is
applied

Figure 8. A shearing force will shatter an ionic crystal

3.3.4 Solubility

Ionic compounds are usually soluble in water, e.g. NaCl, KBr and BaCl2. However, there are examples
of insoluble ionic compounds as well, e.g. AgCl. See Section 12 for the explanation on the solubility of
ionic compounds.

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4 FORMATION AND STRENGTH OF COVALENT BONDING

4.1 Covalent Bonding and Orbital Overlap

LO 2(c): describe covalent bonding in terms of orbital overlap (limited to s and p orbitals only), giving  and π bonds

A covalent bond is formed when two atoms share a pair of electrons which are found in the valence
orbitals of the atoms.

In order for the bond to be formed, the orbitals of the two atoms must overlap. The shared electrons
or bond pairs occupy the region between the two nuclei formed by the overlap.

There are two types of orbital overlap:

 sigma () bond is formed by 'head-on' overlap of two orbitals.

Figure 9. Examples of head-on overlaps (a)  bond formed by s-s overlap (e.g. H–H bond);
(b)  bond formed by s-p overlap (e.g. H–F bond); (c)  bond formed by p-p overlap (e.g. F–F bond)

 pi () bond is formed by 'side-on' overlap of two orbitals.

Figure 10. Side-on overlap between two p orbitals to form a  bond.

While p orbitals can overlap both head-on and side-on, s orbitals can only overlap head-on to form
sigma bonds; they are unable to overlap side-on to form pi bonds.

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Side-on overlap for a  bond is poorer than head-on overlap for a  bond, as the degree of overlap is
smaller for the former. Hence, a  bond is weaker than a  bond.

Between two atoms, there can only be one  bond as it is not possible for a second pair of orbitals to
overlap head-on as well. Also, for a  bond to form, a  bond must first be formed. Hence,

 a single bond consists of a  bond (the two atoms share one pair of electrons);

 a double bond consists of one  bond and one  bond (the two atoms share four electrons);

 a triple bond consists of one  bond and two  bonds (the two atoms share six electrons).

Exercise 4.1
(a) State the number of  bonds and  bonds present in a CO2 molecule, given the structure below.

2  bonds and 2  bonds

(b) Draw a diagram to illustrate how the atomic orbitals overlap for each of the following.

(i)  bond in the H2 molecule (ii)  bond in the CO2 molecule

1s orbital 1s orbital
of H atom of H atom

side-on overlap

head-on overlap

2p orbitals of C and O atoms

4.2 Strength of Covalent Bonding

LO 2(j): explain the terms bond energy and bond length for covalent bonds

Bond strength depends on the degree of orbital overlap between the two bonded atoms and also
how strongly the electrons in the overlap region are attracted to the nuclei of the atoms.

Bond energy is the average amount of energy required to break 1 mole of a covalent bond in the
gaseous state to form gaseous atoms.

We can compare the strength of covalent bonding using bond energies – the larger the bond energy,
the more heat is needed to break the bond, the stronger the covalent bonding.

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Bond energy, hence strength of covalent bonding, depends on:

 bond length i.e. the distance between the nuclei of the two bonded atoms

Smaller atoms form shorter and stronger bonds, as the overlap between orbitals is more
effective.

bond length

bond energy / kJ mol–1 +158 +244 +193 +151

Figure 11. Bond length and bond energy in the diatomic halogen molecules.

Exception: The F–F bond is shorter but weaker than the Cl–Cl bond. This is possibly due to the
repulsion between the lone pairs on the fluorine atoms which are in close proximity.

 bond order i.e. the number of covalent bonds between a pair of atoms

Multiple bonds are shorter and stronger than single bonds. When more electrons are being
shared, the attraction between the two positively charged nuclei and the shared electrons is
stronger.

Table 5. Multiple bonds are stronger and shorter than single bonds
bond energy bond energy
bond bond length /pm bond bond length /pm
/ kJ mol–1 / kJ mol–1
C–C 154 +350 C–O 143 +360
C=C 134 +610 C=O 123 +740
CC 121 +840 CO 113 +1080

LO 2(k) part: compare the reactivities of covalent bonds in terms of bond energy, bond length

In general, a longer bond is weaker so it is usually broken more easily and reacts more readily.
For example, the H-I bond is weaker than the H-Cl bond. Hydrogen iodide undergoes decomposition
readily; hydrogen chloride does not decompose on heating. N 2 is unreactive due to the strong NN
triple bond.

Exercise 4.2
Suggest, in terms of orbital overlap, why the bond energy of C=C bond (+610 kJ mol–1) is less than
twice the bond energy of C-C bond (+350 kJ mol–1).

Side-on overlap for a  bond is less effective than head-on overlap for a  bond. The region of
overlap is smaller, the overlap is poorer. A  bond is weaker than a  bond. Hence, the bond energy
of C=C bond is less than twice that of C-C bond.

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Bond Length, Covalent Radius and van der Waals Radius – Useful Information

Iodine exists as a diatomic molecule, I2. When we measure the distances between the nuclei of two
bonded iodine atoms in iodine solid, we obtain two different values.

Figure 12. Covalent radius and van der Waals radius of iodine

The shorter distance is between two bonded atoms in the same molecule. This is called the bond
length and half of this distance is called the covalent radius (referred to as ‘single covalent’ in the
Data Booklet).

The longer distance is between two non-bonded atoms in adjacent molecules. Half of this distance is
called the van der Waals radius. The van der Waals radius of an atom is always larger than its covalent
radius. In the Data Booklet, the radii listed for the noble gases are the van der Waals radii since they
do not form compounds.

Both covalent radii and van der Waals radii decreases across a period and increases down a group. It
is important to compare radii of the same type when comparing sizes of atoms. In Topic 1 Figure 14,
the van der Waals radii of He, Ne and Ar were plotted with the covalent radii of the other elements.
This explains why the atomic radii increase from Group 17 to Group 18.

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5 DOT-AND-CROSS DIAGRAMS

The dot-and-cross diagram is used to represent the type of bond (ionic or covalent) and the valence
electrons of the interacting atoms. The element's symbol represents the nucleus and the inner shell
electrons, while the dots and crosses represent the valence electrons.

When an ionic bond is formed, electron transfer occurs. When a covalent bond is formed, electron
sharing occurs. In many cases (though not always), the atoms lose, gain or share electrons to attain a
filled outer electron shell of eight electrons (i.e. octet or noble gas configuration ns2 np6). This is known
as the octet rule (see section 5.2.1 for exceptions to octet rule).

5.1 Dot-and-Cross Diagrams for Ionic Compounds

LO 2(b)(i): describe, including the use of ‘dot-and-cross’ diagrams: ionic bonding as in sodium chloride and magnesium oxide

Figure 13 shows the dot-and-cross diagrams for sodium chloride and magnesium chloride. Electron(s)
are transferred from the metal (sodium and magnesium) to the non-metal (chlorine). Each atom forms
an ion with an octet electronic configuration. The resulting ions combine in the correct proportions
such that the compound is electrically neutral.

Figure 13. Dot-and-cross diagrams for sodium chloride and magnesium chloride. When the cation is formed, the valence
electron(s) are lost so we do not draw any dots or crosses around the metal.

Exercise 5.1
(a) Draw the dot-and-cross diagrams for the following ionic compounds.

(i) magnesium oxide (MgO) (ii) sodium oxide (Na2O)

(b) Explain why the oxide of sodium has this formula Na2O.
[N2006/III/4(a) modified]

Each Na atom loses one valence electron to achieve octet when forming Na+ cation.

Each O atom has six valence electrons and gains two electrons (from two Na atoms) to achieve
octet when forming the O2– anion.

Accept alternative explanation in terms of charges on the ions.

The ratio of Na+ to O2– is 2:1 so that the compound is electrically neutral overall / Twice as many
Na+ is needed as O2–to gain charge neutrality.

Therefore, the formula is Na2O.

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5.2 Dot-and-Cross Diagrams for Covalent Compounds

LO 2(b)(ii): describe, including the use of ‘dot-and-cross’ diagrams: covalent bonding as in hydrogen; oxygen; nitrogen;
chlorine; hydrogen chloride; carbon dioxide; methane; ethene

Figure 14 shows the dot-and-cross diagrams for the hydrogen, oxygen and nitrogen molecules.
Between any two bonded atoms, use different electron symbols ( and  only; do not use other
symbols e.g. circles, triangles unless otherwise stated).

H2 O2 N2

Figure 14. Dot-and-cross diagrams for hydrogen, oxygen and nitrogen

The hydrogen atom has one valence electron, so it forms one bond. The oxygen atom has six valence
electrons. It needs two more electrons to attain an octet configuration so it forms two bonds. Similarly,
nitrogen has five valence electrons and forms three bonds. Both oxygen and nitrogen obey the octet
rule; each has eight electrons after sharing electrons. Hydrogen does not follow the octet rule since it
is in Period 1 and its valence shell (1s) can only accommodate two electrons.

Exercise 5.2
Draw the dot-and-cross diagrams for the following molecules.
(a) HCl (b) CO2 (c) CH4

5.2.1 Exceptions to the octet rule

The octet rule is based on empirical observations. We can use the rule to identify structures which are
likely to be stable but it cannot be used to explain the stability of substances.

While the octet rule is obeyed by nearly all the Period 2 elements (such as C, N, O, F), there are several
exceptions.

 Molecule whose central atom has fewer than 8 electrons

In beryllium chloride and boron fluoride, the central atoms (Be and B) have fewer than 8 electrons
in their valence shell. Beryllium chloride and boron fluoride are electron deficient species.
BeCl2 BF3

Figure 15. Dot-and-cross diagrams for beryllium chloride and boron fluoride

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Exercise 5.3
Draw the dot-and-cross diagrams for the following molecules.
(a) aluminium chloride, AlCl3 (b) boron hydride, BH3

 Molecule whose central atom has more than 8 electrons

In phosphorus pentachloride, PCl5, the central phosphorus atom has 10 electrons in its valence
shell. Phosphorus (in Period 3) can form more than 4 bonds by using its d orbitals to
accommodate additional electrons (i.e. one 3s + three 3p + one 3d). We say phosphorus (and
other elements from Period 3 and higher) can expand its octet by using energetically accessible
d orbitals.

PCl5

Figure 16. Dot-and-cross diagram for phosphorus pentachloride

Period 2 elements (e.g. nitrogen) have only four orbitals in their valence shells (2s, 2p x, 2py and 2pz).
Their 3d orbitals are not energetically accessible, because they are in an outer quantum shell which is
at a much higher energy level. Thus, elements in Period 2 cannot accommodate more than four pairs
of electrons in their valence shells. The number of covalent bonds formed is restricted by an overall
maximum of eight electrons, since every new bond brings another electron into the valence shell.

Exercise 5.4 (Worked Example)

(a) Oxygen and sulfur are both Group 16 elements. Oxygen forms OF2 with fluorine but not OF4 or
OF6. Sulfur forms SF2, SF4 as well as SF6. Give reasoning for this observation.

Answer:
Both oxygen and sulfur have six valence electrons so they use two valence electrons to form two bonds
(in OF2 and SF2) to attain octet.

Unlike oxygen in Period 2, sulfur in Period 3 is able to use its energetically accessible 3d orbitals to
accommodate more than 8 electrons. Hence, sulfur can use four or six valence electrons in bonding
with fluorine to form SF4 and SF6 respectively.

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(b) Draw the dot-and-cross diagrams for OF2 and SF6.

(c) State the number of electrons around the sulfur atom in SF4.
Answer: Comment: “electrons around the sulfur atom” here refers only to
There are 10 electrons around the valence electrons, whether lone pairs or bonding electrons. FYI,
sulfur atom in SF4

SF4 is

Besides phosphorus and sulfur, the chlorine atom can also expand its octet to form ClF3 and ClF5 but
not ClF4 and ClF6 because this will result in an unpaired valence electron. It is not able to form C lF7
because the Cl atom is too small to accommodate seven fluorine atoms around it.

 Molecule with unpaired electrons

In some molecules (with odd total number of electrons), the central atom (usually a Group 15 or
Group 17 element) has unpaired electrons in the valence shell. Species with unpaired electrons
are called radicals. Radicals are very reactive.
NO ClO2

Figure 17. Dot-and-cross diagrams for nitrogen monoxide and chlorine dioxide

5.3 Further Dot-and-Cross Diagrams

Some dot-and-cross diagrams are less straight forward to draw, for example, C 2H4 (ethene), and
polyatomic ions such as NH4+, SO42 and NO3.

General guidelines
1. Decide on the central atom, and the terminal atoms. The central atom is usually the one with the
lowest electronegativity (e.g. sulfur in SO 42) or the one that can form more covalent bonds
(e.g. carbon in C2H4 and nitrogen in NH4+); H forms one bond so it cannot be a central atom.

2. For polyatomic ions:

For each (–) charge, add one electron to the more electronegative atom.
E.g. oxygen is assigned the extra electrons in SO 42
For each (+) charge, remove one electron from the less electronegative atom.
E.g. the electron is removed from hydrogen, in NH4+
Draw square brackets around the ion and write its charge as a superscript outside the bracket.

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3. Make terminal atoms achieve octet by assigning single, double or triple bonds accordingly. The
number of bonds is equal to the number of electrons needed to achieve octet.
E.g. in SO42, the oxygen which is assigned the ‘extra electron’ has 7 electrons so it forms a single
bond while the oxygen with 6 valence electrons forms a double bond or 2 single bonds.
Draw in the remaining valence electrons of all atoms in pairs.

4. Check the central atom.

 Elements in Period 2 (e.g. C, N, O) can accommodate maximum 8 electrons; if there are more than
8 electrons, change a double bond to a co-ordinate (dative) bond (see section 5.4).
 Elements in Period 3 or higher (e.g. P, S, Cl) can accommodate more than 8 electrons.
 Elements in Group 2 (e.g. Be) and Group 13 (e.g. B, Al) may be electron deficient.
 Elements in Group 15 (e.g. N) and Group 17 (e.g. C l) may have unpaired electrons.

Exercise 5.5
Draw the dot-and-cross diagrams for the following molecules, ions or compounds.
(a) hydrogen peroxide, H2O2 (Worked Example) (b) barium peroxide, BaO2 (contains one cation and one
anion)

 The name ‘peroxide’ means two oxygen atoms are linked

together by a single covalent bond.
 Oxygen is in Period 2; do not place > 8 electrons around it.

(c) SO42– (Worked Example) (d) PCl4+

 S is the central atom. It is less electronegative than O.

 Two negative charges  add 1 electron each to two of the
O atoms. These O atoms form a single bond with S atom.
The O atoms with 6 valence electrons form a double bond.
 S is in Period 3 so it can accommodate > 8 electrons i.e.
expand its octet.
 Draw square brackets around the ion and write the charge
outside the bracket.

(e) Na2CO3 (Worked Example) (f) NaClO (contains one cation and one anion)

 Two negative charges  add 1 electron each to two of the

O atoms (more electronegative than than C).
 Ratio of Na+ to CO32– is 2:1 so that the compound is
electrically neutral.

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5.4 Co-ordinate Bonding (also called dative bonding)

LO 2(b)(iii): describe, including the use of ‘dot-and-cross’ diagrams: co-ordinate (dative covalent) bonding, as in formation of
the ammonium ion and in the Al2Cl6 molecule

So far, we have looked at covalent bonds in which each atom provides one electron to form the bond.
If both bonding electrons come from one atom, the bond is called co-ordinate bond or dative bond.
A co-ordinate bond, once formed, is no different from any other covalent bond.

To form a co-ordinate bond, the donor atom must have a lone pair (valence electron pair not involved
in bonding) while the acceptor atom must contain an empty orbital in its valence shell. We represent
a co-ordinate bond with an arrow from the donor atom to the acceptor atom. In dot-and-cross
diagrams, a co-ordinate bond is represented using two dots or two crosses.

Example 1: NH3BF3
When gaseous NH3 and gaseous BF3 react together, white solid NH3BF3 forms.
The nitrogen atom in NH3 has a lone pair. The boron atom in BF3 has only 6 electrons in its valence
shell and is electron deficient. It has an empty 2p orbital which can accept the lone pair from nitrogen.

Figure 18. Dot-and-cross diagrams for NH3, BF3, and NH3BF3

Example 2: Al2Cl6
Just below its melting point, aluminium chloride exists as the Al2Cl6 dimer.
In the monomer AlCl3, the aluminium atom has 6 electrons in its valence shell and is electron
deficient. It has an empty 3p orbital which can accept the lone pair from the chlorine atom of another
AlCl3 monomer.

Figure 19. Dot-and-cross diagram and structure of Al2Cl6 dimer. The co-ordinate bonds are broken above 800 oC.

Example 3: The ammonium cation, NH4+

When gaseous NH3 and gaseous HCl react together, the H–Cl bond breaks to give H+ and Cl–. The lone
pair on the nitrogen atom forms a co-ordinate bond with H+, which has an empty 1s orbital, to form
NH4+.

Figure 20. Dot-and-cross diagrams for NH3, HCl and NH4Cl

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Exercise 5.6
Draw the dot-and-cross diagrams for the following molecules, ions or compounds.
(a) NO2 (Worked Example) (b) CO

 Nitrogen and oxygen are in Period 2; do not place > 8

electrons around them. Hence, N does not form 2 N=O bonds
(N will have 9 electrons around it); change one N=O bond to
a co-ordinate bond.
 N atom has an unpaired electron; NO2 is a radical.

(c) ClF4– (d) Mg(NO3)2

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6 SHAPES OF MOLECULES AND POLYATOMIC IONS

LO 2(d): explain the shapes of, and bond angles in, molecules such as BF3 (trigonal planar); CO2 (linear); CH4 (tetrahedral);
NH3 (trigonal pyramidal); H2O (bent); SF6 (octahedral) by using the Valence Shell Electron Pair Repulsion theory
LO 2(e): predict the shapes of, and bond angles in, molecules analogous to those specified in (d)

The shapes of molecules and polyatomic ions refer to the geometrical figure that results if the nuclei of the
bonded atoms are joined by straight lines.

The shapes, as well as bond angles, of molecules and polyatomic ions are determined by the arrangement of
the electrons pairs around each atom. There are two types of electron pairs:

 An electron pair that is shared between bonded atoms is called a bond pair.
 An electron pair that is in the valence shell but not shared with another atom is called a lone pair.

6.1 Valence Shell Electron Pair Repulsion (VSEPR) Theory

The two main principles of the VSEPR theory are:

 The electron pairs (or electron groups) around the central atom of a molecule (or ion) arrange
themselves as far apart as possible so as to minimise their mutual repulsion.

 The repulsion between lone pair and lone pair > lone pair and bond pair > bond pair and bond
pair.

A lone pair is attracted by only one nucleus while a bond pair is attracted by two nuclei. The
electron cloud of a lone pair is less 'elongated' than a bond pair. A lone pair of a central atom takes
up more space around the atom. It is closer to the central atom so it repels other electron pairs
around it more than a bond pair would.

We can use the VSEPR theory to predict the shapes of, and bond angles in a molecule or ion.

1. Determine the number of electron pairs (i.e. total number of bond pairs and lone pairs) around
the central atom. This may be done by drawing the dot-and-cross diagram.
A double bond or triple bond is counted as one group of electrons.

2. Arrange the electron pairs (or electron groups) such that they are as far apart as possible (see
Table 6).

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Table 6. Arrangement of electron pairs around a central atom

number of electron
arrangement of electron pairs description
pairs

2 linear

3 trigonal planar

4 tetrahedral

5 trigonal bipyramidal

6 octahedral

Although they are important in determining the shape of a molecule or ion, lone pairs are not included
when describing the shape. The shape is named based on the positions of the atoms.

Figure 21. The shapes of CH4 (tetrahedral), NH 3 (trigonal pyramidal) and H2O (bent).

Consider CH4, NH3 and H2O. All three molecules have four electron pairs around the central atom but
only the methane molecule has a tetrahedral shape. Ammonia is trigonal pyramidal (it has 3 bond
pairs and 1 lone pair), and water has a bent shape (it has 2 bond pairs and 2 lone pairs).

The drawings in Figure 21 are examples of Lewis structures. Lines are drawn between bonded atoms
(‘–‘, ‘=’ and ‘’ to represent single, double and triple bonds respectively). An arrow  can be used to
represent a co-ordinate (dative) bond.

A lone pair on the central atom is indicated as two dots or drawn like an ‘electron cloud’. When
drawing structures to illustrate the shapes of molecules, we must include the lone pairs on the
central atom. The lone pairs of terminal atoms (if any) can be omitted since these are not considered
in the determination of the shapes.

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Table 7. The shapes of molecules and ions depends on the number of bond pairs and lone pairs. The shape is named based
on the positions of the atoms.
number of
shape and
electron bond lone examples
bond angle
pairs pairs pairs

2 2 0 linear ClBeCl , O=C=O , HCN

180

3 0
trigonal planar , , , NO3–, CO32–
120
3

2 1
, , PbCl2, NO2–, O3
bent
e.g. 118

4 0
tetrahedral , CCl4, SiCl4, NH4+, SO42–, ClO4–
109.5

4 3 1
, NF3, PH3, PCl3, PF3, ClO3–, H3O+
trigonal pyramidal
107

2 2
, H2S, OF2, SF2, SCl2
bent
104.5

5 0

, AsF5, SF5+
5
trigonal bipyramidal

4 1

see saw
Table continues next page

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number of
shape and
electron bond lone examples
bond angle
pairs pairs pairs

3 2
T-shape
See Useful Information
, BrF3, ICl3
5
on page 57
(cont’d)

2 3
linear , I3–, XeF2
180

6 0

octahedral , PCl6–, IF6+

90

6 5 1
, IF5, SF5–, SbCl52–
square pyramidal

4 2
, ICl4–, ClF4–
square planar
90

In the above examples, there is only one central atom in the molecule or ion. If there are more than
one central atom (e.g. H2SO4, H2O2, C2H4), we state the shape with respect to each central atom to be
unambiguous.

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Useful Information

In ClF3, the central atom is surrounded by five pairs of electrons (three bond pairs and two lone
pairs). There are three ways to arrange these five pairs of electrons.

Figure 22. Three different molecular arrangements of ClF3

C is the least stable as the 2 lone pairs are only 90o apart so lone pair-lone pair repulsion is the
greatest. B is less stable than A as B has more significant lone pair-bond pair repulsions. Although
the 2 lone pairs in B are 180o apart, the 3 bond pairs are perpendicular to the lone pairs, i.e. 90 o
apart, resulting in significant lone pair-bond pair repulsions. In A, there are only 2 bond pairs at
90o to the lone pairs. Hence, ClF3 molecule has a T-shape.

3. Bond angle is the angle between two bond pairs.

The second principle of the VSEPR theory – repulsion between lone pair and lone pair > lone pair
and bond pair > bond pair and bond pair is used to explain the bond angles in molecules such as
CH4, NH3 and H2O.

Although each molecule have four electron pairs around the central atom, only the CH4 molecule
has a bond angle of 109.5. NH3 and H2O contain one and two lone pairs respectively, which exert
a stronger repulsion than the bond pairs. The bond pairs in NH3 and H2O are pushed closer
together resulting in slightly smaller bond angles, 107 and 104.5 respectively (see Figure 21).

Compare SO3 and SO2. Both molecules have three groups of electron around the central atom (see
Table 7). SO3 is trigonal planar with a bond angle of 120. SO2 has one lone pair so it has a bent
shape and a bond angle of about 118.

Useful Information

Repulsion between electron pairs also depends on the electronegativity of both the central and
terminal atoms. For example, O is more electronegative than S. The bond pairs are closer to the
central atom in H2O than in H2S resulting in greater repulsion and larger angle.

F is more electronegative than H. The bond pairs are closer to the central atom in NH3 than in NF3
resulting in greater repulsion and a larger angle.

The bond pairs are closer to O than to S. The bond pairs are closer to N in NH 3 than in NF3.

Figure 23. H2O and H2S are both bent but have different bond angles.
NH3 and NF3 are both trigonal pyramidal but have different bond angles.

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Exercise 6.1
Predict the shapes and bond angles of the following.
BCl3 PCl3 (Worked Example) CS2

dot-and-cross diagram

no. of bond pairs around

3 3 2
central atom
no. of lone pairs around
0 1 0
central atom

arrangement of electron
pairs
(to minimise repulsion)

shape trigonal planar trigonal pyramidal linear

107
bond angle 120 180
(between two P─Cl bonds)

Exercise 6.2
Predict the shapes and bond angles of the following.

(a) XeF2 (Worked Example) (b) PCl5

linear, 180
 Xe is in Period 5 so it can expand its octet and accommodate
> 8 electrons around it
 2 bond pairs & 3 lone pairs around central Xe atom  linear trigonal bipyramidal, 120, 90
 Bond angle between two Xe─F bonds is 180°

(c) PCl6– (Worked Example) (d) ClF4–

octahedral, 90
 One negative charge  add 1 electron to one of the Cl atoms
(more electronegative than P atom) square planar, 90
 6 bond pairs & no lone pair around P atom  octahedral
 Four equatorial Cl atoms and the P atom form a square plane;
the other two Cl atoms are axial Cl atoms.

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(e) IF5 (bond angle not required) (g) ClO4–

square pyramidal
tetrahedral, 109.5

(g) C2H4 (Worked Example) (h) H2O2

trigonal planar around each C atom, 120

bent around each O atom, 104.5
 3 bond ‘pairs’ (or group of electrons) & no lone pair around
each central atom  trigonal planar around each C atom
 Bond angles between C─H bond and C=C bond and between
two C─H bonds are 120°

6.2 Hybridisation of Atomic Orbitals

LO 11.1(d): describe sp3 hybridisation, as in ethane molecule, sp 2 hybridisation, as in ethene and benzene molecules, and sp
hybridisation, as in ethyne molecule (Refer to Topic 12 Arenes with regards to benzene)
LO 11.1(e): explain the shapes of, and bond angles in, the ethane, ethene, benzene, and ethyne molecules in relation to σ and
π carbon-carbon bonds (Refer to Topic 12 Arenes with regards to benzene)

The hybridisation theory (Background Info)

To account for the bonding in diatomic molecules like HF, we picture the direct overlap of s and p
orbitals of isolated H and F atoms.

But how can we account for the shapes of so many molecules and polyatomic ions through the overlap
of spherical s orbitals, dumbbell-shaped p orbitals and cloverleaf-shaped d orbitals?

For example, consider the methane molecule,

CH4, which has a tetrahedral shape and a bond
angle of 109.5. Its tetrahedral shape suggests
that its C atom should 'provide' four orbitals
oriented in a tetrahedral geometry, each
containing one electron, and each orbital forms a
 bond with the 1s orbital of a H atom via head-
Figure 24. CH4 molecule and expected orientation of
on overlap (Figure 24). orbitals around the C atom (each orbital forms a 
bond with the 1s orbital of a H atom)

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Now look at an isolated ground-state carbon atom's valence shell electronic configuration (2s2 2p2),
and the shapes of its 2s and 2p orbitals:

Electron-in-box diagram
for the valence shell:

2s 2px 2py 2pz (empty) (combined as one diagram)

Figure 25. Electron-in-box diagram and shapes of valence atomic orbitals of an isolated ground-state C atom

There is a mismatch between the expected orientation (tetrahedral) of the orbitals involved in
bonding for the C atom in CH4, compared to those of an isolated C atom (perpendicular 2p orbitals);
and also in terms of the numbers of single unpaired electrons that can be used for  bonding.

Linus Pauling proposed that valence atomic orbitals of atoms in a molecule are different from those
of isolated atoms. In his hybridisation theory, atomic orbitals (s and p, and sometimes d) mix to form
new orbitals called hybrid orbitals which may then involve in  bonding. Using this theory, we can
explain how molecular shapes arise from the arrangements of hybrid orbitals. In the example of the
methane molecule, one 2s orbital and three 2p orbitals are mixed to give four sp3 hybrid orbitals which
are oriented 109.5 to each other so as to minimise repulsion with one another. All four hybrid orbitals
are identical in energy, so the four valence electrons of carbon occupy each hybrid orbital singly.

carbon atom in excited state sp3 hybridised carbon

(one of the 2s electrons is (the four valence electrons occupy each hybrid orbital
Energy promoted into the 2pz orbital) singly, allowing carbon atom to form four single bonds)

four sp3 hybrid orbitals, each hybrid orbital has

a large lobe and a small lobe
(but only the large lobe can engage in  bonding)

four sp3 hybrid orbitals drawn separately

s and three p orbitals drawn separately
Figure 26. Mixing of an s orbital and three p orbitals to form four sp3 hybrid orbitals for a carbon atom

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Each of the four C–H bonds is an s-sp3  bond, which is formed via a head-on overlap between the 1s
orbital of a H atom and one sp3 hybrid orbital of the C atom.

Figure 27. Overlapping of orbitals in methane, CH4

6.2.1 The bonding in ethane, CH 3CH3 and sp3 hybridisation of carbon

Similar to methane, both carbon atoms in ethane are sp3 hybridised. Each carbon atom in ethane
shares four electrons (one with each of three hydrogen atoms, and one with the other carbon atom),
forming four  bonds. Mutual repulsion of the electrons in the four  bonds around each carbon atom
tends to place them as far apart as possible. Hence, the shape about each carbon atom is tetrahedral
and the bond angles are 109.5.

i. mixing of atomic orbitals to form hybrid orbitals for a carbon atom ii. geometry in ethane
Figure 28a. Bonding in ethane, CH3CH3

For each carbon, the four sp3 hybrid orbitals, obtained by mixing one s orbital and three p orbitals,
are arranged in a tetrahedral geometry as shown in Figure 28b(i). The C–C bond is an sp3–sp3  bond,
formed from head-on overlap of two sp3 hybrid orbitals from adjacent C atoms. There are six C–H
bonds, each bond is s–sp3  bond, formed from a head-on overlap of the 1s atomic orbital of H and
the sp3 hybrid orbital of C.

i. arrangement of sp3 ii. overlapping of orbitals in ethane iii. ball & stick model
hybrid orbitals around
each carbon
Figure 28b. Bonding in ethane, CH3CH3

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6.2.2 The bonding in ethene, CH 2=CH2 and sp2 hybridisation of carbon

Each carbon atom shares three electrons (one with each of two hydrogen atoms, and one with the
other carbon atom), forming three  bonds. The fourth electron on each carbon atom occupies a 2p
orbital which overlaps side-on to form the  bond.

Mutual repulsion of the three groups of electrons around each carbon atom tends to place them as
far apart as possible. Hence, the shape about each carbon atom is trigonal planar and the bond angles
are 120.

Figure 29a. Bonding in ethene, CH2=CH2

Both carbon atoms in ethene, CH2=CH2, are sp2 hybridised. Mixing one s orbital and two p orbitals
gives three sp2 hybrid orbitals.

Figure 29b. Bonding in ethene, CH2=CH2

For each carbon, the three sp2 hybrid orbitals are arranged in a trigonal planar geometry as shown in
Figure 29c(i). One p orbital remains unhybridised, and this p orbital is arranged perpendicular to the
three sp2 hybrid orbitals as shown in Figure 29c(ii).

The C=C double bond consists of one sp2–sp2  bond formed by head-on overlap of two sp2 hybrid
orbitals, and one p-p  bond formed by side-on overlap of the unhybridised p orbitals.

There are four C–H bonds, each of which is an s–sp2  bond formed from head-on overlap of the 1s
atomic orbital of H and the sp2 hybrid orbital of C.

i. arrangement of sp2 hybrid ii. around each carbon, unhybridised p iii. overlapping of orbitals in ethene
orbitals around each carbon orbital is perpendicular to the hybrid
orbitals

Figure 29c. Bonding in ethene, CH2=CH2

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6.2.3 The bonding in ethyne, C2H2 and sp hybridisation of carbon

Each carbon atom shares two electrons (one with each hydrogen atom, and one with the other carbon
atom), forming two  bonds. The remaining two electrons on each carbon atom occupies a 2p orbital
each which overlaps side-on to form the two  bonds.

Mutual repulsion of the two groups of electrons around each carbon atom tends to place them as far
apart as possible. Hence, the shape about each carbon atom is linear and the bond angles are 180.

Figure 30a. Bonding in ethyne, H–CC–H

Both carbon atoms in ethyne, H–CC–H, are sp hybridised. Mixing one s orbital and one p orbital
gives two sp hybrid orbitals.

Figure 30b. Bonding in ethyne, H–CC–H

For each carbon, the two sp hybrid orbitals are arranged in a linear geometry as shown in Figure 30c(i).
Two p orbitals remain unhybridised, and these p orbitals are arranged perpendicular to the two sp
hybrid orbitals as shown in Figure 30c(ii).

The CC triple bond consists of one sp–sp  bond formed by head-on overlap of two sp hybrid orbitals,
and two p–p  bonds formed by side-on overlap of the unhybridised p orbitals.

Each C–H bond is an s–sp  bond formed from head-on overlap of the 1s atomic orbital of H and the
sp hybrid orbital of C.

i. arrangement of sp hybrid ii. arrangement of hybrid orbitals and iii. overlapping of orbitals in ethyne
orbitals around each unhybridised p orbitals around each
carbon carbon
Figure 30c. Bonding in ethyne, H–CC–H

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Table 8. Summary of the orbital hybridisation of carbon

Geometry of Type of hybrid
the carbon orbitals for A diagram to illustrate the relative orientation of hybrid
atom that carbon orbitals for that carbon atom
atom

tetrahedral The molecule is

tetrahedral around this
sp3 carbon atom, bond angle is
109.5 around this carbon
atom.

trigonal
planar The molecule is trigonal
planar around this carbon
sp2
atom, bond angle is 120
around this carbon atom.

linear
The molecule is linear
sp around this carbon atom,
or
bond angle is 180 around
this carbon atom.

6.2.4 Hybridisation and strength of covalent bond

Each type of hybrid orbital (sp3 vs. sp2 vs. sp) has different characteristics depending on what atomic
orbitals it originates from. A p orbital is more elongated as compared to a spherical s orbital. Hence, a
hybrid orbital that has more p character, i.e. p orbitals make up a larger fraction of the hybrid orbital,
tends to form a longer and weaker bond.

hybrid orbital ratio of s:p orbitals % s character % p character

sp3 1:3 25% 75%
sp2 1:2 33.3% 66.6%
sp 1:1 50% 50%

Hence the bond formed by an sp3 hybrid orbital is actually longer and weaker than a bond formed by
an sp hybrid orbital as it has a higher percentage of the characteristic of a p orbital.

Thus, the C–C single bond in ethane, H3C–CH3, which is formed by a sp3─sp3 overlap, is longer and
weaker than the C–C single bond in propyne, H–CC–CH3, which is formed by a sp─sp3 overlap.

[See N2010/I/19 and N2008/I/19]

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7 POLAR COVALENT BONDS and IONIC BONDING WITH COVALENT CHARACTER

Most chemical bonds are neither purely covalent nor purely ionic but have characteristics of both ionic
and covalent bonding.

increasing difference in electronegativity

100% ionic bonding ionic bonding with covalent character

polar covalent bond non-polar covalent bond

Figure 31. The classification of ionic and covalent bonds is on a continuum

The difference in electronegativity between two atoms can be used to predict the type of bond formed
between them.

General guidelines (not required to memorise):

Electronegativity 0 – 0.5 0.5 – 2.0 > 2.0
difference
Nature of bond non- polar ionic
polar covalent
covalent
Examples H–H H–Cl Na+ Cl–
Cl–Cl
C–H

Figure 32. The electronegativity difference suggests whether a covalent or ionic bonding forms between two atoms

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7.1 Polar covalent bonds

LO 2(f): explain and deduce bond polarity using the concept of electronegativity [quantitative treatment of electronegativity
is not required]

In the hydrogen molecule, the bonding electrons are equally shared between the two hydrogen atoms
as they have the same electronegativity. The H–H bond is a non-polar covalent bond. Other non-polar
bonds include the Cl–Cl bond and O=O bond.

Figure 33. Bonding electrons are shared equally in a

non-polar bond.

When the covalent bond is formed by two different atoms, e.g. hydrogen atom and chlorine atom,
the bonding electrons are not shared equally as the atoms have different electronegativities. The H–
Cl bond is a polar covalent bond.

The Cl atom is more electronegative than the H atom. The bonding electrons will be found, on average,
nearer to Cl than to H, resulting in a partial charge separation or dipole. Cl acquires a partial negative
charge (–) while H acquires a partial positive charge (+). The 'cross-and-arrow' symbol can also be
used to show the dipole moment or the direction in which the electrons are more strongly attracted.

If the electron-attracting strength is unequal, the

bond will be polar…

(a) (b)
Figure 34. (a) Unequal sharing of the bonding electrons in a
polar bond (b) Partial charge separation in a polar bond

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7.2 Ionic bonding with covalent character

In ideal ionic bonding, there is complete electron transfer. The nucleus of the cation and that of the
anion only attracts its own electrons. The electron cloud of each ion is spherical (see Figure 35a).

(a) ideal ionic bonding leads to (b) polarisation of anion leads to

spherical electron cloud covalent character in the ionic bonding

Figure 35. Ideal ionic bonding vs. ionic bonding with covalent character

However, in many cases, the cation tends to attract the electrons of the anion causing the electron
cloud to be polarised or distorted, resulting in covalent character in the ionic bonding (see Figure 35b).
The degree of covalent character depends on:

 polarising power of the cation

Cations that are small and highly charge have high charge densities (see section 2.2) and high
polarising power. These cations have a high tendency to distort the anion’s electron cloud, resulting
in greater covalent character in the ionic bonding.
Table 9. Relative charge/radii ratio of cations.
cation charge radius / nm relative charge/radii ratio
+
K +1 0.133 1/0.133 = 7.5
Li+ +1 0.078 1/0.078 = 12.8
2+
Ba +2 0.135 2/0.135 = 14.8
Mg2+ +2 0.065 2/0.065 = 30.8
Al3+ +3 0.050 3/0.050 = 60.0
2+
Be +2 0.031 2/0.031 = 64.5

 polarisability of the anion

Anions that are relatively large have high polarisability. Their valence electrons are further from and
less strongly attracted by the nucleus so the electron cloud is easily distorted by a cation, resulting in
greater covalent character in the ionic bonding.

The bonding in caesium fluoride is said to be predominantly ionic (with little covalent character).
Cs+ ion has a low charge density and low polarising power while F– ion has a low polarisability. The
electron cloud of F– ion is only slightly polarised by Cs+ ion.

The bonding in aluminium oxide is ionic with significant covalent character. Al3+ ion is highly polarising
due to the high charge density so it is able to distort the electron cloud of the oxide anion. In Topic 21
Chemical Periodicity, we will look at how the covalent character in the ionic bond affects the
properties of aluminium oxide. We will also look at how covalent character in ionic bond affects the
magnitude of lattice energy in Topic 5 Chemical Energetics.

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Summary of the concept of 'ionic bonding with covalent character'

compound formed from a metal and a non-metal


metal cation has high charge and small radius  high charge density  high polarising power
anion has large radius  high polarisability

cation attracts outermost electrons or electron cloud of anion
cation distorts or polarises electron cloud of anion

partial sharing of electrons, or even a high degree of that in some cases

ionic bonding with covalent character or even a covalent molecule

Exercise 7.1 (Worked Example)

Which of the bond is more polar, the bond in hydrogen chloride or in hydrogen bromide?
With the aid of diagrams, explain your answer.

Answer:

Cl is more electronegative than Br. The difference in electronegative between Cl and H is larger
than that between Br and H. Hence, the H-Cl bond is more polar (use a longer ‘arrow’ to represent
the larger dipole moment).

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8 POLARITY OF MOLECULES
LO 2(g): deduce the polarity of a molecule using bond polarity and its molecular shape (analogous to those specified in (d))

In section 7.1, we said that when two bonded atoms have different electronegativities, the covalent
bond is polar and has a dipole associated with it.

Depending on the shape of the molecule, the individual dipoles may or may not cancel each other
completely. If the overall dipole or net dipole is zero, the molecule is non-polar. Figure 36 shows
some examples of non-polar molecules.

(a) molecules such as Cl2, O2, N2 and (b) CO2 is non-polar; the two C=O (c) CCl4 is non-polar; the C–Cl bonds
CH4 are non-polar as the bonds are bonds are polar but the individual are polar but the individual dipoles
non-polar (note the C–H bond is dipoles cancel each other due to cancel each other due to the
considered non-polar) the linear shape tetrahedral shape

Figure 36. Non-polar molecules do not have polar bonds or the net dipole is zero

If the sum of all individual bond dipoles is not zero, the molecule is polar. Figure 37 shows some
examples of polar molecules.

(a) NH3 is polar as the N–H bonds (b) CHCl3 is polar; the C–Cl bonds (c) CFCl 3 is polar; the C–Cl and C–F
are polar and are polar but the individual dipoles bonds are polar but the individual
the net dipole is not zero do not cancel each other dipoles do not cancel each other

Figure 37. Polar molecules have polar bonds and the net dipole is not zero

Fluorine is more electronegativity than chlorine so the C–F bond is more polar than the C–Cl bond.
The individual dipoles in CFCl3 do not cancel each other so the net dipole is not zero.

Summary of the concepts of 'polar covalent bonds' and 'polar vs. non-polar simple covalent molecules'
a simple covalent molecule in which there's a difference in
electronegativity between bonded atoms

unequal sharing of bonding electrons in covalent bond(s)

polar covalent bond(s) in this molecule

any net dipole moment? (shape of molecule must be considered)
yes no
polar molecule non-polar molecule

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Exercise 8.1
The presence or absence of polar bonds, and the shape of the molecule determine its polarity.
Complete the flowchart by filling the boxes with ‘polar molecule’ or ‘non-polar molecule’.

Exercise 8.2
Deduce if each of the following molecules is polar or non-polar. Explain your answer with suitable
diagrams.

(a) BF3 (b) H2O

B–F bonds are polar but their dipole moments O–H bonds are polar and their dipole moments
cancel each other as BF3 is trigonal planar. There do not cancel each other as H2O is bent. There is
is no net dipole moment so BF3 is non-polar. a net dipole moment so H2O is polar.

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9 INTERMOLECULAR FORCES OF ATTRACTIONS

LO 2(h): describe the following forces of attraction (electrostatic in nature): (i) intermolecular forces, based on permanent
and induced dipoles, as in CHCl3(l); Br2(l) and the noble gases; (ii) hydrogen bonding, using ammonia and water as examples
of molecules containing –NH and –OH groups

There are three types of intermolecular forces (attractions between molecules):

 instantaneous dipole-induced dipole attractions (also called dispersion forces)
 permanent dipole-permanent dipole attractions
 hydrogen bonding

These intermolecular forces are attractions between partial charges and are electrostatic in nature.
They are generally weaker and require less thermal energy to overcome resulting in low melting
points and low boiling points.

Summary of how to determine the type of intermolecular forces of a simple covalent molecule
How to determine
what type of intermolecular forces
a simple covalent molecule has?

Has net dipole moment NO net dipole moment

=> polar => non-polar

The molecule has a lone pair on N/O/F

and
has a H attached to N/O/F
Dispersion forces
=> hydrogen bonding
and dispersion forces

The molecule does NOT have a lone pair on N/O/F

and/or
does NOT have a H attached to N/O/F
=> permanent dipole-permanent dipole interactions
and dispersion forces

9.1 Instantaneous Dipole-Induced Dipole Attractions (Dispersion Forces)

Dispersion forces exist between all molecules or between noble gas atoms. Between non-polar
molecules such as H2 and CH4 and between atoms of noble gases such as Ne and Ar, it is the only
intermolecular forces of attraction.

The electrons in a molecule are constantly moving. Fluctuations (or distortions) in electron
distribution can cause an instantaneous dipole in one molecule, which induces a dipole in a nearby
molecule. An attraction arises between the two molecules. This ‘short-lived’ and generally weak
attraction is called instantaneous dipole-induced dipole (id-id) attraction or dispersion forces (see
Figure 38).

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Figure 38. Dispersion forces arise due to fluctuations in electron densities

9.1.1 Strength of dispersion forces

The strength of dispersion forces depends on:

 the number of electrons in the molecule

The larger the number of electrons, the more polarisable the electron cloud, the stronger the
dispersion forces.

For example, the dispersion forces between H2 molecules (two electrons) is much weaker than
those between Br2 molecules (70 electrons).

 the surface area of contact between adjacent molecules

The larger the surface area of contact, the more easily induced dipoles are formed, the stronger
the dispersion forces.

The surface area of contact between molecules depends on the overall shape of the molecules.
Consider pentane and 2,2-dimethylpropane. These isomers (same molecular formula but different
structural formula) have the same number of electrons. Pentane has an elongated shape and a
larger surface area than 2,2-dimethylpropane which has a spherical shape. Hence, the dispersion
forces between pentane molecules are stronger.

Figure 39. Strength of dispersion forces depends on the surface area of contact

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LO 5(d): describe and explain the trend in volatility of the Group 17 elements in terms of instantaneous dipole-induced dipole
attraction
Exercise 9.1 (Worked Example)
Group 17 elements exist as diatomic molecules. At room temperature and pressure, F2 and Cl2 are
gases, Br2 is a liquid and I2 is a solid. Explain the trend in volatility of the Group 17 elements.

Answer: Strategy:
Group 17 elements are non-polar simple covalent  Identify the type of IMF and consider what
molecules. As the number of electrons increases, the affects the strength; in this case, the
instantaneous dipole-induced dipole attractions (or number of electrons increases from 18 in F 2
dispersion forces) between the molecules* become to 34 in C l2 to 70 in Br2 and 106 in I2.
 Compare the strength of IMF & energy
stronger. More energy is needed to overcome the
needed; *key words “between the
stronger intermolecular* dispersion forces so volatility
molecules” or “intermolecular”.
of the elements decreases.

9.2 Permanent Dipole-Permanent Dipole Attractions

Polar molecules have a permanent dipole, with an uneven electron distribution. The attraction
between the oppositely-charged ends (+ and –) of two polar molecules is called permanent dipole-
permanent dipole (pd-pd) attractions.

Figure 40. Permanent dipole-permanent dipole attractions

9.3 Hydrogen Bonding

Hydrogen bonding exists between certain polar molecules. For hydrogen bonding to occur,

 the molecule must contain a hydrogen atom bonded to a highly electronegative atom (F, O, N),
 there must be an atom (F, O, N) with a lone pair of electrons.

Hydrogen bonding exists between HF molecules, between H2O molecules and between NH3
molecules.

Take HF as an example. The bonding electrons in H–F bond are pulled strongly towards the highly
electronegative fluorine atom. The hydrogen atom (which has no inner electrons is practically left
with its nucleus with one proton) is highly electron deficient (carries a significant + charge).
The lone pairs on F, found in 2p orbitals which are small, is able to attract the electron deficient H
atom strongly. This particularly strong attraction between adjacent HF molecules is called hydrogen
bonding.

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Figure 41. Hydrogen bonding between HF molecules

When asked to draw a diagram to illustrate hydrogen bonding:

● label the dipole for the covalent bond (F–H, O–H or N–H) carrying the acceptor hydrogen atom
with '+' symbol on H and '–' symbol on the more electronegative F or O or N atom
● draw the lone pair of electrons for the fluorine, oxygen or nitrogen atom involved in the hydrogen
bonding
● Indicate the hydrogen bonding using a dotted/dashed line together with a label

Exercise 9.2
Draw diagrams to illustrate the hydrogen bonding

(a) between two H2O molecules (b) between one H2O molecule and one NH3 molecule

Also accept bonding between lone pair on N and H on H2O

9.3.1 Strength and extent of hydrogen bonding

 The electronegativity of the atom that H atom is bonded to affects the strength of the hydrogen
bonding. For example, F is more electronegative than N. The + charge on H in HF is larger than
that in NH3 hence the hydrogen bonding between HF molecules is stronger.

 The extent of hydrogen bonding depends on the number of H atom bonded to F, O or N and the
number of lone pairs available.

The hydrogen bonding in H2O is more extensive than that in HF or NH3. H2O has two lone pairs of
electrons and two electron deficient hydrogen atoms. H2O can form on average two hydrogen
bonds per molecule. On the other hand, NH3 has only one lone pair (despite having three
hydrogen atoms); HF has only one electron deficient hydrogen atom (despite having three lone
pairs). NH3 and HF can only form one hydrogen bond per molecule.

The effect of strength and extent of hydrogen bonding on boiling points are discussed in section 9.3.2.

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9.3.2 Effect of hydrogen bonding on some properties

LO 2(i): outline the importance of hydrogen bonding to the physical properties of substances, including ice and water
LO 2(l) part: describe, in simple terms, the lattice structure of a crystalline solid which is: (iv) hydrogen-bonded, as in ice

 Considerably high boiling points of NH3, H2O and HF

Figure 42 shows the boiling points of the hydrides (compound formed between hydrogen and
another element).

Figure 42. Boiling points of NH3, H2O and HF compared to CH4 and other hydrides in their respective groups

CH4, NH3, H2O and HF have the same number of electrons (hence similar dispersion forces).
However, the boiling points of NH3, H2O and HF are considerably higher than that of CH4. The
hydrogen bonding in NH3, H2O and HF are stronger than the dispersion forces in CH4.

Similarly, the boiling points of NH3, H2O and HF are also considerably higher than those of other
hydrides in their respective groups (Groups 15, 16 and 17).

 Boiling point: HF > NH3 (see Figure 42 and section 9.3.1)

F is more electronegative than N, the electronegativity difference between F and H is larger than
that between N and H, hence the + charge on H in HF is larger than that in NH3. More energy is
needed to overcome the stronger hydrogen bonding between HF molecules than that between
NH3 molecules hence HF has a higher boiling point.

 Boiling point: H2O > NH3 and H2O > HF (see Figure 42 and section 9.3.1)

H2O has two lone pairs of electrons and two electron deficient hydrogen atoms hence H2O can
form on average two hydrogen bonds per molecule. On the other hand, NH3 has only one lone
pair while HF has only one electron deficient hydrogen atom, hence NH3 and HF can only form
one hydrogen bond per molecule. More energy is needed to overcome the more extensive
hydrogen bonding in H2O than that in NH3 and HF hence H2O has a higher boiling point.

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 Intermolecular and intramolecular hydrogen bonding

Intramolecular hydrogen bonding occurs when the electron deficient H atom in a molecule is in
close proximity to the lone pairs on atoms (F, O, N) in the same molecule.

2-nitrophenol is able to form intramolecular hydrogen bonding so the intermolecular hydrogen

bonding is less extensive. Its isomer 4-nitrophenol is only able to form intermolecular hydrogen
bonding. Less energy is needed to break the less extensive intermolecular hydrogen bonding in
2-nitrophenol hence it has a lower boiling point.

2-nitrophenol 4-nitrophenol
boiling point 214 oC boiling point 290 oC

Figure 43. Intramolecular hydrogen bonding in 2-nitrophenol is not broken during boiling.

 Dimerisation of carboxylic acids in non-polar solvent

In water, ethanoic acid (CH3CO2H) forms hydrogen bonds with H2O molecules. However, in non-polar
solvent such as benzene (unable to form hydrogen bonding), the acid molecules form dimers via
hydrogen bonding. Hence, the observed Mr is 120 instead of 60 (expected value for CH3CO2H).

Figure 44. Dimer of CH3CO2H

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 Ice is less dense than liquid water

In ice, each H2O molecule is hydrogen bonded to four other molecules in a roughly tetrahedral
arrangement. This produces an open lattice, with empty spaces between the H2O molecules.
The more random arrangement of hydrogen bonding in liquid water takes up less space as the
H2O molecules are closer together.

For the same mass, the lattice structure of ice occupies a larger volume, hence the lower density.

(a) lattice structure of ice (b) tetrahedral arrangement of H2O

molecules in ice

(c) random arrangement of H 2O

molecules in liquid water

empty spaces

Figure 45. Tetrahedral arrangement in ice vs random arrangement in liquid water

 Liquid water has high surface tension (defined as the amount of force required to break the layer
of water molecules on its surface)

The hydrogen-bonded H2O molecules form an array across the surface of water, allowing objects
which you might expect to sink in water, such as pond skaters and even small coins (if you are
careful), to 'float' on water.

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10 COVALENT LATTICES AND PHYSICAL PROPERTIES

LO 2(m): describe, interpret and/or predict the effect of different types of structure and bonding on the physical properties
of substances

A lattice consists of particles that are arranged in a regular three-dimensional pattern. In sections 2
and 3, we described the metallic and ionic lattices respectively.

Covalent lattices can be giant molecular (as in graphite and diamond) or simple molecular (as in iodine
and ice). We will describe and explain the physical properties of these substances in terms of their
structure and bonding in the following sections.

10.1 Simple Molecular (or Simple Covalent) Lattices

LO 2(l) part: describe, in simple terms, the lattice structure of a crystalline solid which is: (ii) simple molecular, as in iodine

In simple molecular lattices, the particles are held by comparatively weak intermolecular forces (see
section 9).

Figure 46 shows examples of simple atomic and simple molecular lattices.

(a) simple atomic lattice of (b) simple molecular lattice of solid (c) simple molecular lattice of solid
solid argon hydrogen chloride iodine
(id-id attraction between atoms) (pd-pd attraction between molecules) (id-id attraction between molecules)

Figure 46. Lattice structures of solid Ar, solid HCl and solid I2

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10.1.1 Physical properties of substances with simple molecular lattices

Physical properties of simple molecular substances depends on the strength of the intermolecular
forces. In general, substances with simple molecular lattice structures have low melting points and
low boiling points as the weak intermolecular forces between molecules require little thermal
energy to overcome. For example, boiling water breaks the weak hydrogen bonding holding the
molecules together. The strong covalent bonds holding the hydrogen and oxygen atoms together are
not broken; the H2O molecules remain intact!

Many simple molecular compounds are soluble in organic solvents like propanone (CH3COCH3),
tetrachloromethane (CCl4) and benzene (C6H6). Some (e.g. ethanol, ethanoic acid, glucose) are soluble
in water due to their ability to form hydrogen bonds with water. See section 12 for more discussions
on solubility.

Simple molecular substances are unable to conduct electricity as there are no mobile charge carriers.
However, some simple covalent substances are able to react with water to give aqueous ions. This
allows the resulting solution to conduct electricity, for example: HCl(g) + H2O(l)  Cl–(aq) + H3O+(aq).

Exercise 10.1 (Worked Example)

Explain in terms of structure and bonding the following:
(a) Argon has a lower boiling point than hydrogen chloride.
Answer: Strategy:
Argon has a simple atomic structure while hydrogen  State the structures
chloride has a simple molecular structure.  Identify the type of attractions broken
Stronger permanent dipole-permanent dipole attractions during boiling; keywords “between HCl
molecules”, “between Ar atoms”
(and dispersion forces) exist between polar HC l
 Compare the strength of relevant
molecules*.
attractions (pd-pd vs dispersion forces;
Less energy is needed to overcome the weaker dispersion
HCl & Ar have comparable dispersion
forces between argon atoms* so it has a lower boiling forces due to the same no. of electrons)
point. & energy needed

(b) Hydrogen iodide has a higher boiling point than hydrogen bromide.
Answer: Strategy:
Both hydrogen iodide and hydrogen bromide are polar  State the structures
simple covalent molecules.  Identify the type of attractions broken
Permanent dipole-permanent dipole attractions and during boiling; keywords “between
molecules” or “intermolecular”
dispersion forces exist between the molecules.
 Compare the strength of relevant
HI molecules have more electrons so more energy is
attractions (in this case dispersion
needed to overcome the stronger dispersion forces
forces; pd-pd attraction is “irrelevant”
between the molecules. Hence, HI has a higher boiling as H─Br bond is more polar than H─I
point than HBr. bond so pd-pd between HBr molecules is
stronger which would result in a higher,
rather than a lower, boiling point for
HBr) & energy needed.

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10.2 Giant Molecular (or Giant Covalent) Lattices

LO 2(l) part: describe, in simple terms, the lattice structure of a crystalline solid which is: (iii) giant molecular, as in graphite;
diamond

Giant molecular lattices consist of three-dimensional arrays of atoms, held together by strong covalent
bonds. Figure 47 shows examples of giant molecular lattices.

In diamond (figure 47a), each (sp3 hybridised) C atom is covalently bonded to four other C atoms, in a
tetrahedral arrangement.

In silicon(IV) oxide (also known as quartz), each Si atom is covalently bonded to four O atoms, and each O
atom is bonded to two Si atoms. The formula SiO2 is an empirical formula. (Refer to figure 47b)

(a) diamond lattice (b) silicon(IV) oxide lattice

Figure 47. Lattice structures of diamond and silicon(IV) oxide

Diamond and graphite are allotropes of carbon – different forms of carbon, in which the atoms are
arranged in different ways.

In graphite, each (sp2 hybridised) C atom is covalently bonded to three other C atoms, forming a two-
dimensional layer of hexagonal carbon rings. Each C atom in graphite has a 2p orbital containing one
electron (not used in forming the C–C  bonds). Within each layer, the 2p orbitals side-on overlap with
each other to form a delocalised  bonding system (similar to the delocalisation of  electrons in
benzene, refer to Topic 12 Arenes!). Between the layers of carbon atoms, there is (significant)
dispersion forces due to the large surface area. (Refer to figure 48)

strong covalent
bond between C
atoms

weak dispersion
forces between
layers
(a) Within each layer: each C atom has a 2p (b) Each 2D layer consists of
orbital (containing one electron) which can covalently bonded C atoms
overlap with one another arranged hexagonally

Figure 48. Structure of graphite

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10.2.1 Properties of substances with giant molecular lattices

Unlike simple covalent compounds, substances with giant molecular lattice have very high melting
points and very high boiling points as a lot of energy is needed to break the strong covalent bonds
between the atoms.

Table 10. The structure and bonding, and some physical properties of diamond, graphite and quartz
Property Diamond Graphite Quartz
also silicon(IV) oxide
structure and bonding giant molecular giant molecular giant molecular

each C atom is covalently within each layer each Si atom is covalently

bonded to four other C each C atom is covalently bonded to four O atoms,
atoms, in a tetrahedral bonded to three other C and each O atom is bonded
arrangement. atoms, forming a 2D layer to two Si atoms.
of hexagonal carbon rings.
Si : O ratio = 1 : 2
Overlap of 2p orbitals (of
each C atom) give rise to
delocalised  bonding
system.

between layers
dispersion forces hold 2D
layers together
melting point / oC 3550 3730 1610
boiling point / oC 4827 - 2230
electrical conductivity poor good along the layers -
hardness very hard soft and slippery hard
solubility in solvents insoluble insoluble insoluble

Diamond is unable to conduct electricity as there are no mobile charge carriers. All the valence
electrons are held between the atoms and are not free to move. Graphite is a good conductor of
electricity (and heat) as the delocalised electrons are free to move along the layers – graphite is used
in batteries and electrolysis. The delocalised electrons are unable to jump from one layer to the next
so graphite does not conduct electricity in the direction at right angles to the layers.

Diamonds are very hard (the hardest natural substance known), strong and non-malleable because
of the rigid structure, held together by strong covalent bonds – diamonds are used for cutting tools
and oil rig drills. Graphite is soft (over 500 times softer than diamond) and slippery as the layers can
slide over each other due to the dispersion forces between them – graphite is used as a lubricant and
in pencils.

Both diamond and graphite are insoluble in water and organic solvents. Attractions between the
solvent molecules and carbon atoms are not strong enough to overcome the strong covalent bonds
between the carbon atoms.

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11 PHYSICAL PERIODICITY
LO 5(c) part: interpret the variation in melting point across a Period in terms of structure and bonding in the elements
(metallic, giant molecular, or simple molecular)

Figure 49 shows the variation in melting point for the period 3 elements, sodium to argon.
melting point (in C)

P4 molecule

S8 molecule

Figure 50. Structure of phosphorus and sulfur

Figure 49. Variation in m.p. for period 3 elements

Na, Mg and Al have giant metallic structures and relatively high melting points due to the strong
metallic bonding between cations and the sea of delocalised valence electrons.

From Na to Al, melting point increases as more energy is needed to overcome the stronger metallic
bonding due to
 the increase in number of valence electrons contributed per atom
 and the increase in charge density of the cation (due to increasing charge and decreasing
ionic radius/cationic size).

Table 11. Factors affecting strength of metallic bonding in Na, Mg and Al (refer also to section 2.2)
Na Mg Al
No. of valence e contributed per atom 1 2 3
Charge of cation +1 +2 +3
Ionic radius of cation / nm 0.095 0.065 0.050

Si has a giant molecular structure and a very high melting point as a lot of energy is needed to
overcome the many strong covalent bonds between the Si atoms during melting.

Non-polar P4, S8, and Cl2 have simple molecular structures. Ar has simple atomic structure. Little
energy is needed to overcome the weak dispersion forces between the molecules or between argon
atoms hence the low melting points.

The number of electrons* and hence strength of dispersion forces decreases from S8 to P4 to Cl2 to
Ar. Hence, energy needed to overcome the dispersion forces during melting and the resulting melting
point decreases in the same order.
*from Data Booklet, no. of electrons in S8 (128) > P4 (60) > Cl2 (34) > Ar (18)

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LO 5(c) part: interpret the variation in electrical conductivity across a Period in terms of structure and bonding in the elements
(metallic, giant molecular, or simple molecular)

Figure 51 shows the variation in electrical conductivity for the period 3 elements, sodium to argon.

electrical
conductivity

Figure 51. Variation in electrical conductivity for period 3 elements

Na, Mg and Al have giant metallic structures with strong metallic bonding between cations and the
sea of delocalised valence electrons. Metals are good electrical conductors because the delocalised
electrons are able to act as mobile charge carriers.

From Na to Al, the number of valence electrons contributed per atom increases. Therefore, electrical
conductivity increases.

Si has a giant molecular structure with covalent bonds between atoms. As a metalloid (an element
with properties of metals and non-metals), it is a semiconductor.

P4, S8, and Cl2 have simple molecular structures. Ar has simple atomic structure. In P4, S8 and Cl2, the
valence electrons are held strongly in covalent bonds. There are no mobile charge carriers in these
molecules as well as in argon atoms so they do not conduct electricity.

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Exercise 11.1
Using the data provided below, describe the various forces responsible for keeping the particles
together in the element or compound. Account for the melting point of each substance in terms of
its structure and bonding.

substance formula melting point / C

neon Ne –248
argon Ar –189
water H2O 0
sodium fluoride NaF 993
graphite C 3948

Graphite has a giant molecular structure which consists of layers of carbon rings.
The carbon atoms in the rings are held by strong covalent bonds while the layers are held by weaker
dispersion forces.
A lot of energy* is needed to break the strong covalent bonds so graphite has a very high melting
point.

NaF has a giant ionic lattice structure.

A lot of energy* (but less than that for graphite) is needed to overcome the strong ionic bonding
between Na+ and F– ions so NaF has a high melting point.

Water has a simple molecular structure. Argon and Neon have simple atomic structures.
The H and O atoms in each H2O molecule are held by covalent bonds# while the H2 O molecules are
held together by hydrogen bonding.
Ne and Ar exist as individual atoms with dispersion forces between the atoms.

More energy* (but less than that for NaF) is needed to overcome the stronger hydrogen bonding
between water molecules than the weaker dispersion forces between argon atoms. Hence, water
has a higher melting point than argon.

Argon has more electrons than neon so more energy* is needed to overcome the stronger
dispersion forces between argon atoms than that between neon atoms. Hence, argon has a higher
melting point than neon.

Note: comparison of strength of attraction (and specify type) broken during melting are necessary

*energy comparisons are necessary when comparing melting point

#
covalent bonds in water are not broken during melting

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12 SOLUBILITY OF A SUBSTANCE IN A GIVEN SOLVENT

LO 2(m): describe, interpret and/or predict the effect of different types of structure and bonding on the physical properties
of substances

When a solute dissolves in a solvent, the interactions between the solute particles (solute-solute
interaction) and between the solvent particles (solvent-solvent interaction) must be overcome. The
solute particles and solvent particles then need to form favourable solute-solvent interactions with
each other such that the particles are able to mix freely with each other.

In terms of energy changes, a solute is soluble in a solvent if

the energy released from solute-solvent interactions is greater than or comparable to the energy
needed to overcome solute-solute interactions and solvent-solvent interactions.

Hence, when explaining the solubility (or miscibility) of two substances, it is helpful to:
 identify the type of interactions holding solute particles together,
 identify the type of interactions holding solvent particles together,
 identify the type of interaction that can occur between the solute and the solvent particles,
 compare the strength of the new interactions (solute-solvent) with the existing interactions
(solute-solute and solvent-solvent)

Table 12. Tips on how to identify types of solute-solvent interactions

Types of chemical bonding How to identify?
Ion-dipole interaction Between a cation and a partial negatively charged atom on a polar molecule
Between an anion and a partial positively charged atom on a polar molecule

Hydrogen bonding Between one molecule that has a lone pair on N/O/F and another molecule with a H on N/O/F

Permanent dipole-permanent Between two polar molecules that cannot form hydrogen bonding
dipole interaction
Permanent dipole-induced Between a polar molecule and a non-polar molecule
dipole interaction
Instantaneous dipole-induced Between two non-polar molecules/atoms
dipole interaction But also occurs between
 two polar molecules
(also called dispersion forces)  a polar molecule and a non-polar molecule

Exercise 12.1 (Worked Example)

Identify the type of solute-solvent interaction present in the following:
solute solvent solute-solvent interaction
(a) NaCl (s) H2O (l) NaCl(s) is ionic; H2O is a polar molecule  ion-dipole interaction
ionic polar between Na+ and H2O; ion-dipole interaction between Cl− and H2O
(b) Br2 (l) CCl4 (l) Both molecules are non-polar  dispersion forces
non-polar non-polar
(c) CH2Cl2 (l) Both molecules are polar
polar  permanent dipole-permanent dipole interactions
(l)lar
(d) ICl (l) CH3(CH2)4CH3 (l) ICl (l) is a polar molecule; hydrocarbons are considered non-polar
polar non-polar  permanent dipole-induced dipole interactions
(e) CH3CH2OH (l) H2O (l) polar Both molecules are able to form hydrogen bonding
polar  hydrogen bonding

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12.1 Solubility of substances in water

Water molecules are held together by hydrogen bonding. Depending on the solute, the interactions
formed by water and a solute include:
 hydrogen bonding with polar molecules such as ethanol (CH3CH2OH), propanone (CH3COCH3)
 permanent dipole-induced dipole interactions with non-polar molecules such as iodine,
hexane (CH3(CH2)4CH3)
 ion-dipole attractions with cations or anions (from ionic solids)

Example 1: Ethanol dissolves in water

The energy released when forming hydrogen bonds between ethanol and water molecules is
comparable to the energy needed to overcome the existing hydrogen bonding between ethanol
molecules and the existing hydrogen bonding between water molecules.

(a) between ethanol molecules (b) between water molecules (c) between ethanol and
water molecules
Figure 52. Diagrams to illustrate hydrogen bonding

Example 2: Hexane, CH3(CH2)4CH3, is insoluble in water

The energy released when forming weak permanent dipole-induced dipole interactions between
polar water and non-polar hexane molecules is insufficient to overcome the dispersion forces
between hexane molecules and the stronger hydrogen bonding between water molecules.

Example 3: Sodium chloride, NaCl, dissolves in water

Sodium chloride is an ionic compound. Both Na+ and Cl– ions are able to form
ion-dipole attractions with water molecules. The ion-dipole attractions are relatively strong and very
extensive. The energy released when forming ion-dipole interactions between Na+ and H2O and
between Cl– and H2O is comparable to the energy required to overcome the hydrogen bonding
between water molecules and ionic bonding between Na+ and Cl– ions in NaCl.

(a) between Na+ and H2O (b) between Cl– and H2O

Figure 53. Diagrams to illustrate ion-dipole interactions

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Figure 54 illustrates the 'microscopic' processes that occur when sodium chloride dissolves in water.

aqueous Na+
(hydrated Na+)

ion-dipole attractions
between the ion and the
solid NaCl polar water molecules

aqueous Cl–
(hydrated Cl–)

Figure 54. Water molecules form ion-dipole attractions with ions on the crystal's surface, forming solvated aqueous ions

The energy released from ion-dipole interactions depends on the charge densities of the ions (see
Topic 5 Chemical Energetics). Ions with lower charge densities (e.g. Ag +, Cl) form weaker ion-dipole
interactions so less energy is released. This explains why some ionic compounds e.g. silver chloride
are insoluble in water.

Exercise 12.2 (Worked Example)

Propanone (CH3COCH3) and water are miscible. Explain this with a suitable diagram to show the
interactions formed between propanone and water.
Answer: Strategy:
For your info, dot-and-cross
diagram of propanone:

CH3COCH3 forms hydrogen bonding with water.  identify the solute-solvent

The energy released is able to compensate the energy interactions
needed to overcome the weaker permanent dipole-  compare strength of solute-solvent
permanent dipole interactions between CH3COCH3 interactions to solute-solute and
molecules, and the hydrogen bonding between water solvent-solvent interactions
molecules.

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12.2 Solubility of substances in organic solvents

Organic solvents can be non-polar (e.g. hexane, benzene (C6H6), tetrachloromethane (CCl4)) or polar
(e.g. propanone, ethanol). The interactions formed between the solvent and the solute depends on
the specific substances involved.

Exercise 12.3 (Worked Example)

Explain why solid iodine is soluble in an organic solvent such as CCl4 but insoluble in water.

Answer:
Both I2 and CCl4 are non-polar simple molecules. The energy released when forming dispersion
forces between I2 and CCl4 molecules is comparable to the energy needed to overcome existing
dispersion forces between I2 molecules and between CCl4 molecules. Hence, I2 is soluble in CCl4.

Water exists as polar simple molecules. The energy released when forming permanent dipole-
induced dipole interactions between polar water and non-polar I2 molecules is insufficient to
overcome the dispersion forces between I2 molecules and the stronger hydrogen bonding between
water molecules. Hence, I2 is insoluble in water.

LOOKING AHEAD
The study of chemical bonding, the structure of elements and compounds, as well as the
interactions present explains their physical properties. These ideas will be pertinent when discussing
the properties of aqueous and gaseous systems, as well as the concept of chemical changes or
reactions. In preparation for the coming topics, consider the following questions:
● How does chemical bonding influence the movement of gaseous particles?
● How does chemical bonding influence chemical changes?
● How is energy related to chemical bonding?
● How can we measure the strength of a chemical bond?

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03 The Gaseous State

GUIDING QUESTIONS
 What is a mole? Why is it important in Chemistry?
 What is an ideal gas? What conditions are needed for a gas to behave ideally?
 What is the relationship between pressure, volume, temperature and amount of a gas?
 How do the individual components of a gas mixture contribute to the pressure of the mixture?

LEARNING OUTCOMES
Students should be able to:
3(a) state the basic assumptions of the kinetic theory as applied to an ideal gas
3(b) explain qualitatively in terms of intermolecular forces and molecular size:
(i) the conditions necessary for a gas to approach ideal behaviour
(ii) the limitations of ideality at very high pressures and very low temperatures
3(c) state and use the general gas equation PV = nRT in calculations, including the determination of Mr
3(d) use Dalton’s Law to determine partial pressures of gases in a mixture
6(a) define the terms relative atomic, isotopic, molecular and formula mass (Refer to Topic 1 Atomic Structure &
Physical Periodicity for relative atomic and isotopic masses)
6(b) define the term mole in terms of Avogadro’s constant

REFERENCES
1. Peter Cann, Peter Hughes, Chemistry, 1st Edition, Hodder Education, Chapter 4
2. Silberberg, Chemistry: The Molecular Nature of Matter and Change, 3rd Edition, McGraw-Hill,
Chapter 5
3. Burrows, Holman, Parsons, Pilling, Price, Chemistry: Introducing inorganic, organic and physical
chemistry
4. http://www.chemguide.co.uk/physical/ktmenu.html#top

LOOKING BACK
In the gaseous state, the particles are far apart as compared to solid and liquid states and are in
constant random motion. An element or compound that exists as a gas at room temperature generally
have weak interactions between its particles. You should keep in mind how the structure and bonding
of a substance impact on its physical properties such as melting and boiling points.

Early experiments on the macroscopic properties of gases led to an understanding of the laws that
govern the macroscopic properties of gases and the development of the mole concept. In preparation
for this chapter, you should recall the basics of mole concept that you have learnt previously (e.g. what
is 1 mole of particles?).

You may watch the lecture recording via https://youtu.be/2TI-b-9nXAo. You may click on the time stamp
to skip to the relevant sub-sections.

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1 GASES

1.1 Development of Mole Concept through Gas Experiments (Background info)

Some of the earliest scientific investigations concerning matter

were performed by scientists trying to understand the physical
and chemical properties of gases. It was these studies (~1650–
1800 AD) that helped establish chemistry as a scientific
discipline. The experiments of scientists such as Robert Boyle
(1627 - 1691), Jacques Charles (1746-1823), and Gay-Lussac
(1778-1850) led to our understanding of laws that govern the
macroscopic properties of gases and we will learn these gas
laws in Section 3.

Joseph Louis Gay-Lussac was a French chemist who studied

how different volumes of gases combined during chemical
reactions to make products. He determined that when
different gases reacted, they would always do so in small whole
number ratios (e.g., two volumes of hydrogen would react with
one volume of oxygen in forming water) – the “Law of
Combining Volumes of Gases”. This was one of the greatest
Figure 1. Some apparatus used by Robert Boyle advancements of its time and helped form the basis for later
atomic theory and how chemical reactions occur.
Amadeo Avogadro, an Italian physics professor, hypothesised the Avogadro’s Law to explain
Gay-Lussac's data.

Avogadro's Law: Equal volumes of all gases, under the same temperature and pressure, contain the
same number of particles (atoms or molecules).

LO 6(b): define the term mole in terms of Avogadro’s constant

One mole contains exactly 6.02 × 1023 (or Avogadro constant, L) elementary entities. (notation: , unit: mol)

LO 6(a): define the terms relative atomic, isotopic, molecular and formula mass
average mass of one molecule of a substance
Relative molecular mass, Mr: 1
x the mass of one atom of 12 C
12

Note:
 Due to the presence of isotopes, the word “average” is necessary in definition of Mr
 Mr = sum of Ar of all the atoms in the molecular formula
 Mr has no units as it is a ratio of two masses
Exam tip
You are not required to remember the history of the development of mole concept for the
examinations. However, you will need to define the important terms used in mole concept (those
given in boxes above). The use of these terms in calculation will be covered in Topic 4: “Reactions
and Stoichiometry”.

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1.2 Units of Pressure

Pressure is defined as force exerted per unit area. Gas pressure is a

gauge of the frequency and force of collisions between gas particles
and the walls of the container that hold them. It is measured in a
number of different units. One of the units is the millimetre of
mercury, mmHg, which originates from measuring atmospheric
pressure (760 mmHg) with a mercury barometer.

The SI units of pressure is the pascal, Pa, defined as 1 newton, N,

per square metre. This is a very common unit used in the A-level
syllabus.
1 Pa = 1 N m–2

It is a much smaller unit of pressure than the standard atmosphere

(atm) and the bar, which are approximated to the following values
Figure 2. A mercury barometer at sea level
for calculations:

1 atm = 101,325 Pa

1 bar = 100,000 Pa

1.3 Measuring standards for gas samples

Because the physical properties of a gas sample can vary greatly depending on several factors, we
often have to specify the conditions under which the measurements were made.

Molar volume, Vm, of any gas is the volume occupied by 1 mole of the gas at a specified temperature
and pressure. The common conditions used for gas measurements and molar volumes are
summarised in the table below.

Table 1. Molar volume and measurement conditions for gas samples

Measurement conditions used
Pressure Temperature Molar volume (Vm)
Standard temperature and
1 bar (100,000 Pa) 273 K (0 °C) 22.7 dm3 mol–1
pressure (s.t.p.)
Room temperature and
1 atm (101,325 Pa) 293 K (20 °C) 24 dm3 mol–1
pressure (r.t.p.)

You do not need to memorise the conditions and molar volumes for s.t.p. and r.t.p as they are listed
on the first page of the Data Booklet!

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2 THE SIMPLE GAS LAWS AND IDEAL GAS LAW

Because most gases are difficult to observe directly, they are described through the use of four
macroscopic properties.
 Pressure (P)
 Volume (V)
 Temperature (T)
 Number of moles of gas (n)
Simple gas laws are formulated to describe the relationship between pairs of the properties and hold
to good approximations for all gases.

2.1 Simple Gas Laws

The simple gas laws describe the relationships between pairs of the above variables, when the other
two variables are held constant.

In the early 1660s, the English scientist Robert Boyle found that at constant temperature, the volume
of a fixed mass of gas (i.e. for n is constant) is inversely proportional to its pressure. The mathematical
and graphical relationships of Boyle’s Law are given below:

Mathematical relationship Graphical representation

For n is constant and T is constant,
P P
1
V∝
P
or
1
P∝
V
0 V 0 1/V

Later, in 1787, the French physicist Jacques Charles found that at constant pressure, the volume of a
fixed mass of gas is directly proportional to its absolute temperature (measured in K). The
mathematical and graphical relationships of Charles’ Law are given below:

Mathematical relationship Graphical representation

For n is constant and P is
V V
constant,

V∝ T

0 –273 T/°C
T/K
Note: this value is only 0
when temperature T is The x-intercept shifts to
in Kelvin –273 °C (≡ 0 K). The shape of
the graph remains the same.

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In 1811, Amadeo Avogadro proposed that at constant temperature and pressure, the volume of a gas
is directly proportional to the number of molecules (or number of moles of gas) present. The
mathematical and graphical relationships of Avogadro’s Law are given below:

Mathematical relationship Graphical representation

For T is constant and P is constant,
V
V∝ n

0
n

Take note that at constant temperature and volume, the pressure of a gas is also directly proportional
to the number of moles present.

Exercise 2.1
Which of the simple gas laws is at work in each of the following examples?
(i) The bubbles exhaled by a scuba diver grow in size as the bubbles approach the surface of the ocean.
(ii) On collision, airbags in cars inflate rapidly. A sensor triggers the ignition of sodium nitride according to the
following equation: 2NaN3(s)  2Na(s) + 3N2(g)
(iii) The print head of a bubble jet printer contains 64 or 128 tiny nozzles. The tip of the nozzle is filled
with ink which is then heated by an electronic heater. This vaporizes the ink and a bubble of vapor
ink is then published on the paper. This bubble when published acts as a dot, of a letter or image.

Review your answers here: (timestamp 16:52)

2.2 The Ideal Gas Equation

LO 3(c): state and use the general gas equation PV = nRT in calculations, including the determination of M r

nT
By combining the three relationships given above, we get P ∝
V
We can replace the proportionality sign by incorporating a proportionality constant known as the
molar gas constant (R):

nT
Rearrange
P = R( ) PV = nRT
V

This equation is known as the ideal gas equation. It expresses the relationship among the four
variables P, V, T and n for an ideal gas. An ideal gas is one which follows this equation exactly, under
all conditions of pressure, volume and temperature. Refer to Section 4 for more information on the
assumptions of the kinetic theory as applied to an ideal gas.
Using the ideal gas equation in calculations

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We can use the ideal gas equation to determine the value of any one of the four variables given the
other three.

When using R = 8.31 J K−1 mol−1 (Data Booklet), P, V, n and T must be in SI units:
 P must be in Pa ( N m−2)
 V must be in m3
 n must be in moles
 T must be in K

Table 2. Table showing possible units of the four measurable variables when substituted in the ideal gas equation
Variable Symbol SI units Other Units Conversions
Pressure P Pa (pascal) or N m−2 atm , bar 1 atm = 101325 Pa
1 bar = 100000 Pa
Volume V m3 cm3 ; dm3 1 cm3 = 1  106 m3
1 dm3 = 1000 cm3 = 1  103 m3
Temperature T K (kelvin) −nil− Absolute temperature (in K)
= temperature (in °C) + 273
0 K = −273 oC (absolute zero)
Amount n mol −nil−

Exercise 2.2 (Worked Example)

On the surface of Venus, the temperature is 470 °C and the pressure is 1.00 atm. What is the volume occupied by 1.00
mol of an ideal gas under these conditions?

Working and solution:

Use PV = nRT and convert all variables to SI units (Pressure from atm to Pa, Temperature from °C to K).
V = (1.00)(8.31)(470+273)/ 101325 = 0.0609 m3
(You may also review the explanation via timestamp 25:47)

2.3 Using the Ideal Gas Equation to determine Mr

mass 𝑚
n =( )=
molar mass Mr

𝑚
∴ PV = ( ) RT
Mr

Exercise 2.3
In a syringe experiment, 0.10 g of a gas is found to occupy 83.1 cm 3 measured at standard temperature and
pressure. What is the relative molecular mass of the gas?

Review your answers here: (timestamp 27:31)

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Exercise 2.4
A sample of m g of an organic compound is vaporised in a gas syringe and occupies V cm3 at T K and
P bar. What is the relative molecular mass of the compound, Mr? (N00/III/6)

m × 22700 × T m × 22700 × (T + 273)

A Mr = B Mr =
P × V × 273 P × V × 273

m × 22700 × 273 × P m × 22700 × 273 × P

C Mr = D Mr =
V×T V × (T + 273)

Review your answers here: (timestamp 30:30)

2.4 Combined Gas Equation

The combined gas equation is useful for changes to gas systems where the amount of the gas, n, is
kept constant.

Since n and R are constants,

PV PV
= nR ⟹ = constant
T T

P1V1 P2 V 2
= constant =
T1 T2

P1V1 P2V2
=
T1 T2

where P1, V1 and T1 relate to the gas in its initial condition, and P2, V2 and T2 relate to the gas in its final
condition. Temperature values must only be in K for the expression to be valid.

The combined gas equation can be further reduced to:

P1V1 = P2V2 if temperature is constant

P1 / T1 = P2 / T2 if volume is constant and
V1 / T1 = V2 / T2 if pressure is constant

Useful tip:

 Because these relationships do not make use of the gas constant R, it is possible to use any units
of pressure or volume, as long as they are consistently used for initial and final values.

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Exercise 2.5 (Worked Example)

An air bubble rises from the bottom of the sea, where the temperature is 6.0 °C and pressure is
8.4 atm, to the water surface. The water surface has a temperature of 24.0 °C at 1.0 atm. Calculate the
volume of the bubble in cm3, to 2 decimal places, if its initial volume is 0.030 cm3.

Working and solution:

The variables mentioned in the question stem are summarised below:

T1 = 273 + 6.0 = 279 K P1 = (8.4  101325) Pa V1 = (0.030  10–6 ) m3

T2 = 273 + 24.0 = 297 K P2 = (1.0  101325) Pa V2 = ?

Since the air bubble contains a fixed amount of gas,

P1V1 P2V2
=
T1 T2

(8.4  101325)  (0.030  10–6)  297

V2 = = 0.27 cm3
(1.0  101325)  279

(Note: As the conversion to SI units for pressure and volume term involves multiplying a constant, once you
are experienced enough, it need not be written out in your working as it’ll be cancelled off).

(You may also review the explanation via timestamp 40:59)

Exercise 2.6

A 400 cm3 mixture of petrol vapour and air is taken into the cylinder of a car engine at 200 °C and a pressure
of 100 kPa. The piston compresses this gaseous mixture to 50.0 cm3.
Find the pressure of the compressed gas if temperature is constant. [Assume that the gases do not react]

Review your answers here: (timestamp 44:19)

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2.5 Graphical Relationships for Ideal Gases

The graphical relationships for simple gas laws are introduced in section 2.1. In this section, we will
attempt to predict the graphical relationship between other variables, based on manipulation of the
ideal gas equation PV = nRT. Figure out which of the four variables are constants, and rearrange this
equation in the form 𝑦 = 𝑚𝑥 + 𝑐.

Exercise 2.7 (Worked Example)

Watch the video review here: (timestamp 46:41)

Situation 1
For a fixed amount of gas kept at a constant temperature, sketch a graph of
(i) PV against P (Worked Example) and
(ii) PV against V.

PV PV

(i) (ii)

0 P 0 V

Since n and T are both constant,

PV = nRT = constant
⟹ PV = k, which is a constant. Hence a horizontal line is obtained as PV remains constant even if P
changes.

Situation 2 (Extension of Boyle’s Law)

For a fixed amount of gas at two different temperatures (T1 and T2), sketch on the same axes, a graph
of P against V for
(i) T1 (Worked Example)
(ii) T2 (T2 > T1) P
(i)

T1
0 V
1
PV = nRT  P = (nRT)( )
𝑉
1
(nRT) is constant for a fixed amount of a gas at one temperature, hence 𝑃 ∝
𝑉
The graph of P against V would be like the asymptote graph shown above.
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Interpreting graphs
Each of the following graphs represents plots for an ideal gas at two different conditions. In each case,
you should be able to identify the variable with the higher value by using either of the following two
strategies:

1. Consider for a given value of a variable (taken to be the x-axis variable for consistency) by drawing
a vertical line. Then compare how the other variable would change under the two different
conditions given by looking at where the line you've drawn cuts the graphs.
2. (This works best for straight line graphs) Rearrange PV = nRT to fit the variable given by the y- and
x-axes. Check how the changing variable affects the steepness of the gradient.

Which temperature is higher, T1 or T2? Rearrange PV = nRT and make P the subject of the
equation, we will get P = (nRT)(1/V).
P
T2 Therefore, plotting P against 1/V will give us a
straight line that passes through the origin with
gradient = nRT.:
T1
Since the graph with T2 is a steeper line than that of
T1, that means nRT2 > nRT1. This is only possible if
1/V T2 > T1. Hence T2 has a higher temperature than T 1.
0
T
1
Exercise 2.8

Review your answers here: (timestamp 54:38)

(a) Which pressure is higher, P1 or P2? (Worked Strategy:

Example) Rearrange PV = nRT and make V the subject
of the equation, we will get V = (nR/P)T.
V
P2
Therefore, plotting V against T will give us a
straight line that passes through the origin
P1 with gradient = nR/P.

Since the graph with P2 is a steeper line

0 T/K than that of P1, that means nR/P2 > nR/P1.
This is only possible if P2 < P1. Hence P1 has
a higher pressure than P2.
(b) Which temperature is higher, T1 or T2?

PV

T1

T2

0 P

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Exercise 2.9

Review your answers here: (timestamp 56:51)

Which graph correctly describes the behaviour of a fixed mass of an ideal gas?

A B
constant T

PV/T PV

0 P 0 V

C D
constant T

PV/T P

0 0
V PV

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3 GAS MIXTURES AND PARTIAL PRESSURES

LO 3(d) use Dalton’s Law to determine the partial pressures of gases in a mixture

If a mixture of non-reacting gases is confined in a container, each gas occupies the volume (V) of the
container and exerts its own pressure (P) on the walls of the container as if it alone were present. This
observation is known as Dalton’s law of partial pressures, and the pressure exerted by a particular
gas in a mixture is referred to as its partial pressure.

If we let Ptotal be the total pressure of a gas mixture, we can write Dalton’s law of partial pressures as:
Ptotal = Pa + Pb + Pc + ⋯
where Pa , Pb , Pc... are the partial pressures of the individual gases a, b, c... respectively.

Since T and V are constant, the partial pressure of each component is directly dependent on (and
proportional to) the amount of each gas in the mixture. So, for gases a, b, c, etc…

𝑅𝑇 𝑅𝑇 𝑅𝑇
Pa = na ( ) Pb = nb ( ) Pc = nc ( ) … and so on
𝑉 𝑉 𝑉

Combining these into the expression for Ptotal , we get:

RT RT RT
Ptotal = na ( ) + nb ( ) + nc ( ) + ⋯
V V V
RT
= (na + nb + nc + ⋯ ) ( )
V
RT
= ntotal ( )
V

Dividing the expression for Pa by that for Ptotal , and rearranging:

na
Pa = ( )P
ntotal total

na
where ( ) is called the mole fraction, sometimes represented by the Greek letter chi, χ, or:
ntotal

Pa = 𝜒a Ptotal

Thus, in a gas mixture, the partial pressure of any individual gas is directly proportional to its mole
fraction in the mixture.

Figure 3. Illustration of Dalton’s Law of Partial Pressures

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Exercise 3.1 (Worked Example)

Two moles of oxygen and one mole of nitrogen are contained in a cylinder with a volume of
10.0 dm3 at 298 K. What is the total pressure? What is the partial pressure of oxygen?

Working and solution:

As oxygen and nitrogen do not react under the given conditions, the total pressure will simply be dependent
on the total number of moles of gas. The ideal gas equation can be used to calculate the total pressure.

totalRT (2+1)(8.31)(298)
Ptotal = = = 742914 Pa = 743 kPa
V 10.0  10–3

O 2 2
PO2 =  Ptotal =  742914 = 495 kPa
total 3

(You may also review the explanation via timestamp 1:01:37)

Exercise 3.2

Flask Q contains 1.00 dm3 of helium at a pressure of 2.00 kPa and flask R contains 2.00 dm3 of neon at a
pressure of 3.00 kPa. If the flasks are connected at constant temperature, what is the final pressure of the
system?

Review your answers here: (timestamp 1:03:17)

Exercise 3.3

A 12.5 dm3 scuba diving tank is filled with a heliox mixture containing 24.2 g of He and 4.32 g of O 2 at 298 K.
Calculate the total pressure and the partial pressures of helium and oxygen in the mixture.

Review your answers here: (timestamp 1:07:23)

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4 ASSUMPTIONS ABOUT IDEAL GASES

LO 3(a): state the basic assumptions of the kinetic theory as applied to an ideal gas

The kinetic theory of gases is a model used to describe the microscopic behaviour of gas particles and
their interactions. This theory was developed in reference to ideal gases (refer to section 2.2), though
it can be applied reasonably well to real gases. The following assumptions are about ideal gases:

1. The size of the gas particles is so small compared to the space between them that we can
assume that the particles themselves have negligible volume. In other words, the gas particles
have negligible volume compared to the volume of the container.
2. The intermolecular forces of attraction between gas particles are negligible.
3. Collisions between gas particles, and their collisions with the walls of the container, are
perfectly elastic; i.e. there is no net loss or gain of kinetic energy during collision.

Exam tip
In the A-level examinations, you may be asked to recall the assumptions of the Kinetic Molecular
Theory as applied to ideal gases. Assumptions 1 and 2 are the most important ones, particularly for
the discussion on how real gases deviate from ideal behaviour.

If you are required to state more than 2 assumptions, assumption 3 can be included.

Exercise 4.1 (Worked Example)

Argon exists in the atmosphere as a monoatomic inert gas.
(a) Using the Data Booklet, calculate the volume of an argon atom, indicating the units clearly. [Given:
volume of a sphere is 4⁄3 πr3 , where r is its radius]
(b) Calculate the total combined volume of one mole of argon atoms.
(c) If the gas volume of 1 mole of argon is 24 dm 3 at room temperature and pressure, calculate the
percentage of the total volume occupied by the argon atoms themselves.
(d) Based on your answer in (c), comment on whether it is justified to assume that argon at room
conditions behaves ideally. State the relevant assumption applied to an ideal gas.

Working and solutions:

(a) Check data booklet for atomic radius of Ar (convert nm to m)
Volume of a sphere = 4⁄3 π(0.190 x 10–9)3 = 2.87 x 10−29 m3

(b) One mole of atoms contains Avogadro’s number of particles.

Total volume of one mole of argon atoms = 2.87 x 10−29 x 6.02 x 1023
= 1.73 x 10−5 m3
(c) Molar volume at rtp = 24 dm3 = 24 x 10–3 m3
% of total volume occupied by the argon atoms at rtp = 1.73 x 10−5 m3/24 x 10–3 x 100%
= 0.0721%
(d) Yes. The assumption is that the gas particles have negligible volume compared to the volume of
the container.

(You may also review the explanation via timestamp 1:14:13)

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4.1 Conditions for real gases to behave ideally

LO 3(b)(i): explain qualitatively in terms of intermolecular forces and molecular size: the conditions necessary for a gas to
approach ideal behaviour

 At low pressures, the gaseous molecules are relatively far apart. The volume of the molecules
themselves is negligible compared to the volume of the container. Thus, real gas molecules at low
pressure can be approximated to have negligible volume. Also, intermolecular forces are negligible
as the particles are far apart. Hence their behaviour at low pressures would approach that of ideal
gases.

 At high temperatures, gas particles have enough kinetic energy to overcome intermolecular
forces, which can thus be considered insignificant. As such, the behavior of real gases approach
ideal gas behavior at high temperatures.

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5 REAL GASES AND DEVIATION FROM IDEAL BEHAVIOUR

LO 3(b)(ii): explain qualitatively in terms of intermolecular forces and molecular size: the limitations of ideality at very high
pressures and very low temperatures

Based on the reasons given in Section 4.1, real gases would therefore deviate from ideal behaviour at
high pressures and low temperatures.

Under these conditions, the following two assumptions about ideal gases are no longer valid, namely:
1) The gas particles have negligible volume compared to the volume of the container; and
2) The intermolecular forces of attraction between gas particles are negligible.

Figure 4 shows a plot of PV/RT against pressure for some real gases compared with that of an ideal
gas. For 1 mol of an ideal gas, the ratio PV/RT is equal to 1 at any pressure. In general, deviations from
ideal behaviour become greater at higher pressures.

1.0

𝑃𝑉𝑚
𝑅𝑇

Figure 4. Effect of pressure on the behaviour of several real gases at 300 K

Figure 4 also shows how different gases deviate differently from ideal behaviour. Molecules with
stronger intermolecular forces will violate assumption 2 and show greater deviation. For example, CO 2
has a larger electron cloud and hence stronger dispersion forces than N2, hence CO2 deviates more
from ideal behaviour.

For molecules with similar electron cloud size, e.g. NH3 (Mr = 17.0) versus CH4 (Mr = 16.0), other
intermolecular forces besides dispersion forces need to be considered. NH3, with stronger hydrogen
bonding, should deviate more from ideal behaviour than CH4, with only intermolecular dispersion
forces.

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Interesting to note
Liquefaction is a key property of real gases that is not predicted by the kinetic molecular theory of gases, as
it requires the action of intermolecular forces (which the theory assumes to be negligible) in order to occur.
In other words, ideal gases never condense into liquids!

Figure 5 shows how one mol of nitrogen behaves as a result of changing the temperature. The
deviation is greatest at low temperatures.

Ideal gas
1.0

𝑃𝑉𝑚
𝑅𝑇

Figure 5. Effect of temperature on the behaviour of nitrogen gas

Conclusion: Real gases do not obey the ideal gas law, especially at high pressures and/or low
temperatures.

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5.1 Explaining deviations at high pressures

 The gas particles can no longer be considered to have negligible volume compared to the
volume of the container.

At high pressures, the volume of the container decreases. The molecules are pushed closely together
and take up a significant portion of the container volume, resulting in less space in which the
molecules can move. Thus, it is no longer valid to assume that its volume is negligible compared to
the container volume, and so the gas deviates from ideal behaviour. (In fact, the total volume occupied
by a real gas is actually greater than the volume predicted by the ideal gas equation.)

Also, since the gas particles are close together, they tend to interact with one another, hence
intermolecular attractions are not negligible.

a) Low pressure b) High pressure

Figure 6. Illustration of effect of non-zero particle size at low and high pressures

5.2 Explaining deviations at low temperatures

 The intermolecular forces between gas particles become significant.

As temperature is lowered, the kinetic energy of the gas particles decreases, causing them to move
more slowly and intermolecular forces to become more significant. This also causes collisions to
become inelastic (such that assumption 3 is no longer valid either). Eventually, it reaches a point where
the particles can no longer overcome the intermolecular forces, at which point real gases liquefy
(condense to form a liquid) when cooled to below its boiling point.

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Did you notice?

Increasing the pressure on a real gas has opposite effects on the value of the product P × V.
It increases the observed V, while decreasing the observed P. This effect is summarized in Figure 7
below:
 where the value of PV deviates below that of ideal gas, the effect of intermolecular forces
dominates. As pressure increases, the gas molecules are closer together, resulting in stronger
intermolecular forces, decreasing the observed P. The stronger the intermolecular forces
present, the greater the extent of deviation.
 At higher pressures, where the value of PV deviates above that of ideal gas, the gas particles can
no longer be considered to have negligible volume compared to the volume of the container,
increasing the observed V.

As the pressure increases, the strength of the intermolecular forces increases at a greater rate than
the increase in the volume, hence the PV value decreases leading to the minimum point seen in the
graph of PV against pressure applied for some gases.

At high pressures,
the gas particles can
no longer be
𝑃𝑉
PV
𝑚 considered to have
𝑅𝑇 negligible volume
compared to the
volume of the
container. The
Ideal gas observed PV value is
At very low pressures above that of an ideal
(i.e. nearing the y-axis gas.
where P = 0), real
gases tend to
approach ideal
behaviour. P

Intermolecular forces
between gas particles cause
the observed (PV) value of a
real gas to be below that of
an ideal gas.

Figure 7. Understanding the shape of a non-ideal gas curve

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Exercise 5.1 (Worked Example)

Interpreting real gas behaviour from a plot PV/RT versus P

The following curves represent the behaviour for equal amounts of three real gases and an ideal gas at a fixed
temperature. Among the options given, what could the possible identities of real gases X, Y and Z be?

X Y Z
A NH3 N2 H2
B H2 NH3 N2
C N2 H2 NH3
D H2 N2 NH3

Working and solution:

 The question mentions that 'equal amounts' of all gases are plotted − we therefore expect n to be the
same, and thus their PV/T (which is = nR) values should also be the same when behaving ideally.
 Line Z has the greatest deviation below the ideal line and should represent the gas that has the strongest
intermolecular forces, i.e. NH3 (hydrogen bonding).
 Between the two remaining options, N2 should show greater deviation (line Y) than H2 (line X) as it has
larger electron cloud (stronger dispersion forces)
 Option D

(You may also review the explanation via timestamp 1:30:13)

Exercise 5.2

The value of PV is plotted against P for two gases, an ideal gas and a non-ideal gas, where P is the pressure
and V is the volume of the gas.

PV
ideal gas

non-ideal gas

P
Which gas shows the greatest deviation from ideality?

A ammonia C methane
B ethene D nitrogen
[N2010/I/7]

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6 DISTRIBUTION OF MOLECULAR SPEEDS

The average kinetic energy of the gas particles is directly proportional to the absolute temperature.
So at a particular temperature, all types of gaseous particles have the same average kinetic energy.

Although collectively the molecules in a gas sample have the same average kinetic energy, the
individual molecules are moving at different speeds. There exists a distribution of speeds among the
particles in a sample of gas. At a given temperature, heavier gases travel slower while lighter gases
travel faster (recall: KE = ½mv2). Figure 8 shows how the speed distribution varies with the molar mass
of the gas for different gas samples at the same temperature.

Figure 8. Variation of speed distribution with molar mass at a given T

For a gas sample at different temperatures as shown in Figure 9, the speed distribution of the
molecules shifts toward higher speeds and becomes less sharply peaked as the temperature of the
gas sample is increased. Even at low temperatures, a small number of molecules have high speed and
kinetic energy. This number of molecules increases with temperature, while the number of molecules
with low speed and kinetic energy becomes smaller but does not vanish.

300
Fraction of molecules

500 K

0
Molecular speed (m s–1)

Figure 9. Variation of speed distribution with T for a given gas sample

The above speed distributions are referred to as Maxwell-Boltzmann distribution curves, or simply,
the Boltzmann distribution curve.

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Note the following about Maxwell-Boltzmann distribution curves:

1. The examples above use speed on the horizontal axis. However, since kinetic energy of a molecule
is proportional to the square of its speed, the graph would have the same shape if kinetic energy
were used on the x-axis instead.

2. Common labels for the vertical axis include number of (gas) particles (or molecules), proportion
of particles, or fraction of particles.

3. The area under the curve generally represents the total number of particles in the sample. So for
a fixed amount of sample at different temperatures, the area should remain the same even as the
curve shifts.

4. The peak of each curve represents the most probable speed (or most probable kinetic energy,
depending on the x-axis label). As the temperature increases, the peak decreases in height and
shifts to the right as the distribution of molecular speeds becomes more spread out.

5. All curves start at the origin (0,0) because in a gas sample there are no particles with zero speed
(or zero kinetic energy). In other words, all gas particles must be moving.
[The only exception is at 0 K, absolute zero, which is the theoretical lowest possible temperature,
one at which all particles have zero kinetic energy and particle motion stops.]

6. The curves do not show a maximum speed (or kinetic energy) value and run asymptotically along
the x-axis – i.e. the curves do not intersect the x-axis again as there is theoretically no limit to the
amount of speed (or energy) a particle can have.

LOOKING AHEAD

In this topic, you have learnt to describe the behaviour of a gas in macroscopic terms of pressure,
volume, temperature and number of moles (ideal gas equation). This will set the foundation for
your learning in subsequent topics so keep in mind the following questions:

1. How to calculate partial pressures of gaseous species in reactions? (This will be especially useful
for Topic 7 Chemical Equilibria)

2. How do you use the principles of mole concept in stoichiometric calculations involving reacting
masses, volumes of gases and concentrations of solutions? (Topic 4 Reactions and
Stoichiometry)

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PLANNING FOR AN EXPERIMENT THAT INVOLVES GAS COLLECTION

The volume of a gas produced in a reaction can be measured through a variety of experiments to determine
concentration, percentage purity, rate of reaction etc.

Common reactions which can produce a gas are:

 Acid + metal  H2
 Acid + carbonate  CO2
 Catalysed decomposition of H2O2  O2
 H2O2 + oxidising agent  O2
 Decomposition of solids (e.g. Group 2 carbonate  CO2)

 You may be required to suggest the mass and/or volume of chemicals to react. These can be calculated
based on your chosen capacity of your gas collection container (e.g. gas syringe, burette). Volume of
container must be reflected in diagram or written clearly in the procedure.

 The total volume of the reaction mixture should not exceed the capacity of your chosen reaction flask e.g. a 250
cm3 conical flask.

 Ensure your proposed setup is a closed system (no loss of gas) and the chemicals are separated, ready to mix.

 The method of gas collection depends mainly on the solubility of the gas in water.
 Graduated gas syringe: suitable for all gases. Typical capacity of gas syringe: 50 cm3, 100 cm3. The syringe
must be graduated (draw markings in your diagram, or label 'graduated gas syringe').
 Downward-displacement of water in an inverted burette (50 cm3) or measuring cylinder
(50 cm3, 100 cm3 ): suitable for gases that are sparingly soluble in water, e.g. H2, O2. A burette is more precise
for measuring small volumes.

Sources of error:
 This method of collection is only appropriate for gases that have low solubility in water, e.g. H 2, O2.

 When a gas is collected over water, some water in the burette will vapourise and gets mixed with the
gas collected. The water vapour will exert its own pressure as well. Hence, the total pressure of the
gas in the burette is due to both the partial pressure of the gas collected and the partial pressure of
the water vapour.

 Pressure is the same at all points on the same horizontal level within a liquid. Since the water column
will also exert its own pressure, in (a) taking the water level as reference, Patm = Pgas + Pwater vapour +
Pwater column. As the water level inside the inverted burette changes, the pressure of the gas will also
change. This limitation has an impact on the accuracy of the volume of gas measured.

Pgas < Patm Pgas

Pgas = Patm Pgas > Patm
Patm Patm Pgas Pgas
Patm

(a) (b) (c)

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Set-up

A) Set–up with suspended test-tube and gas syringe

One reactant is added into the test-tube (or

delivery
small vial) and lowered into the flask. The other
tube
reactant is added directly into the flask. Care
stopper must be taken to ensure the two reactant do
100 cm3 frictionless not come into contact at this stage. To start the
conical flask gas syringe reaction, the flask is shaken/swirled to mix the
string
two reactants. Gas produced is collected
weighing bottle without loss.
HCl(aq) containing baking soda

B) Set-up with dropping funnel and downward displacement of water

The liquid reactant (e.g. aqueous acid) is

50 cm3 graduated dropping placed into the dropping funnel with the tap
funnel with HCl(aq) closed. The other reactant (e.g. Na2CO3 solid)
100 cm3 measuring is placed into the reaction flask. To start the
cylinder reaction, the tap is opened to release the
liquid reactant and closed when the desired
volume of liquid is added. Gas produced is
collected without loss. There will however be
a volume of air displaced into the measuring
trough
cylinder by the liquid reactant when the liquid
conical flask
baking soda with side-arm water
is added. This needs to be subtracted from the
total volume of gases collected.

Generic Procedure for (A)

1. Using an electronic balance, weigh accurately about (mass) of (solid reactant) in a weighing bottle.

2. Using a measuring cylinder, transfer (volume) of (aqueous reactant) into a 250 cm3 conical flask.

3. Carefully lower the weighing bottle containing (solid reactant) into the conical flask, ensuring the reactants do
not mix. Insert the stopper to ensure a closed set-up.

4. Set up the apparatus as shown in the diagram (A).

5. Record the initial reading, x cm3, on the gas syringe.

6. Shake the conical flask to topple the weighing bottle, and continue swirling the conical flask to thoroughly mix
the reactants.

7. When the volume reading has remained constant for a period of time, record the final reading,
y cm3, on the gas syringe (or if it’s for a kinetics experiment, “record volume of gas at appropriate time
intervals”). The volume of gas collected is (y  x) cm3.

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Generic Procedure for (B)

1. Using an electronic balance, weigh accurately about (mass) of (solid reactant) in a weighing bottle. Transfer the
solid into a conical flask with side-arm. Reweigh the weighing bottle to account for any residual solid.

2. Set up the apparatus as shown in the diagram (B).

3. Fill a 50.0 cm3 graduated dropping funnel with (aqueous reactant).

4. Record the initial reading, x cm3, on the (measuring cylinder/burette).

5. Take note of the initial reading on the graduated dropping funnel. Open the tap of the dropping funnel to add
the (aqueous reactant) to the solid. When (volume) of (aqueous reactant) has been added, close the tap. Swirl
the flask to thoroughly mix the reactants. (Note: There will be a corresponding volume of air displaced by the
added liquid)

6. When bubbling through the (measuring cylinder/burette) has stopped, record the final reading, y cm3, on the
(measuring cylinder/burette). The volume of gas collected is (y  x  Vdisplaced air) cm3.

Note:
 It may sometimes be necessary to allow the set-up to equilibrate to room conditions, for example, if the reaction
is highly exothermic. However, in a kinetics experiment where the volume of gas needs to be read at appropriate
time intervals, it would not be possible to allow the set-up to equilibrate to room conditions (Refer to planning
section in Topic 6 Reaction Kinetics.)

 If the reaction produces effervescence, it is possible to tell the reaction has stopped when no more effervescence
is observed.

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PLANNING FOR AN EXPERIMENT THAT INVOLVES HEATING OR DRYING TO CONSTANT MASS

(GRAVIMETRY)

Gravimetry (or gravimetric analysis) refers to the quantitative determination of an analyte (i.e. the substance being
analysed) based on the mass of a solid.

It may involve heating hydrated salts (e.g. Na2CO3∙10H2O), or heating to decompose a solid (e.g. MgCO 3) or mixing
two solutions to form a precipitate (e.g. BaSO 4 or AgCl), followed by filtering, drying, and weighing of the precipitate.

The principle of heating (or drying) to constant mass is applicable in this method.

Generic Procedure for Heating to Constant Mass

Using an electronic balance, weigh accurately _ (mass) _ g of __(solid)__ in a dry empty crucible (or boiling tube).
Record mass of empty crucible, mass of crucible and solid, and mass of solid collected.
1. Heat the crucible and its contents gently first for 1 min then strongly for about 5 min.
2. Allow the crucible and its contents to cool on a wire gauze.
3. Re–weigh the crucible with its contents.
4. Repeat heating, cooling and re–weighing until there is no further change in mass.

Heating to constant mass ensures that the solid is completely decomposed (or in the case of heating hydrated salts,
water of crystallization has been completely driven off). The mass lost (or mass of residue) can then be used for
stoichiometric calculations.

Why must the crucible (or boiling tube) be dry?

Any water present will contribute to the mass lost determined, leading to inaccurate calculations.

Why do we need to allow the crucible and contents to cool after every heating?
This is to prevent fluctuations of the mass readings on the electronic balance. Hot objects generate convection
currents in the air that causes the readings to fluctuate.

Heating Techniques

 Safety: Eye protection must be worn for all heating experiments.

How to arrange the crucible on Where to place the Bunsen

clay triangle burner to heat strongly using
on tripod stand hottest part of the flame

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 A common experimental set-up for heating:

 A boiling tube may also be used for heating solids.

 Use a dry crucible (or boiling tube) for heating.

 Heat gently at first to prevent ‘spitting’ of solid.

 Gradually increase the heat to maximum and then heat strongly.

 Do not overheat as the residue of some solid may decompose or vessel may crack.

 Heat the solid evenly and thoroughly (e.g. spread out the solid in the crucible instead of a heap, gently agitate
the solid by tapping the boiling tube on the wire gauze).

 Place the vessel on the heat-proof mat to cool before weighing.

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04 Reactions and Stoichiometry

GUIDING QUESTIONS
• What is the significance of a balanced equation?
• How can the amount of reactants and products in a chemical reaction be determined?
• What are acids and bases?
• What models can be used to classify substances as acids and bases?

LEARNING OUTCOMES
Students should be able to:
[the term relative formula mass or Mr will be used for ionic compounds]
6(a) define the terms relative atomic, isotopic, molecular and formula mass (Refer to Topic 1
Atomic Structure and Physical Periodicity for relative atomic and relative isotopic mass)
6(d) define the terms empirical and molecular formula
6(e) calculate empirical and molecular formulae using combustion data or composition by mass
6(f) write and/or construct balanced equations
6(g) 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]
6(h) deduce stoichiometric relationships from calculations such as those in (g)
4(a) show understanding of, and apply the Arrhenius theory of acids and bases
4(b) show understanding of, and apply the Brnsted-Lowry theory of acids and bases, including the
concept of conjugate acids and conjugate bases (Refer to Topic 14 Acid-Base Equilibria for
concept of conjugate acids and conjugate bases).
4(c) show understanding of, and apply the Lewis theory of acids and bases (including non-aqueous
system e.g. reaction between BF3 and NH3)
12(a) describe and explain redox processes in terms of electron transfer and/or of changes in
oxidation number (oxidation state)
12(h) construct redox equations using the relevant half-equations
13(g) describe and explain the use of Fe3+/Fe2+, MnO4–/Mn2+ and Cr2O72−/Cr3+ as examples of redox
systems

REFERENCES
1. Peter Cann and Peter Hughes (2015), Chemistry, Hodder Education, Chapters 1 & 7
2. Martin S. Silberberg (2009), Chemistry: The Molecular Nature of Matter and Change, 5th Edition,
McGraw Hill, Chapters 3 & 4

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LOOKING BACK
Chemistry is about the study of matter, its interactions and transformations. In the previous three
topics, we have learnt about matter in the submicroscopic level: the atom and its electronic structure.
Atoms interact and give rise to different types of bonding. We observe these interactions in our daily
life at a macroscopic level, via the physical properties of elements, compounds and gases. In Topic 3
The Gaseous State, we have also learnt the concept of the mole. We shall now look at chemical
transformations i.e. reactions, which involve the reorganisation or transfer of valence electrons
among the reactants. In all reactions, matter and energy must be conserved. In this topic, we will apply
the mole concept and key ideas of conservation of matter in the quantitative treatment of reactions
– stoichiometry.

1 FORMULAE OF COMPOUNDS
LO 6(a): define the terms relative atomic, isotopic, molecular and formula mass

1.1 Relative Masses of Compounds

In Topic 1 Atomic Structure, we learnt the definition of the relative mass of an atom and an isotope.

mass of one atom of an isotope of an element

Relative isotopic mass =
1
x the mass of one atom of 12 C
12

average mass of one atom of an element

Relative atomic mass, Ar =
1
x the mass of one atom of 12 C
12

The definitions may be extended to relative masses of molecules and ionic compounds as follows:

average mass of one molecule of a substance

Relative molecular mass, Mr =
1
x the mass of one atom of 12 C
12

average mass of one formula unit of a substance

Relative formula mass =
1
x the mass of one atom of 12 C
12

Note:
 Due to the presence of isotopes in elements, the word “average”
is necessary in the definitions.
 Mr = sum of Ar of all the atoms in the molecular formula
 All the above relative masses have no units, as they are ratios of
two masses.
 Relative formula mass is used for ionic compounds.

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Exercise 1.1

Calculate the relative molecular / formula mass of the following substances, giving your answer to
1 decimal place.
(a) Zn3(PO4)2 (b) H2C2O4 (c) C6H12O6 (d) CuSO4.5H2O

[Given Ar of H: 1.0; C: 12.0; O: 16.0; P: 31.0; S: 32.1; Cu: 63.5; Zn: 65.4]

1.2 Percentage Composition by Mass

From the formula of a compound and the relative atomic masses of the elements in it, the percentage
composition by mass of each element in the compound can be calculated.

Exercise 1.2 (Worked example)

Which one of the following compounds, both used as fertilisers, contains the higher percentage
by mass of phosphorus: Ca5(PO4)3F or (NH4)2HPO4?

Mr of Ca5(PO4)3F = 5(40.1) + 3(31.0 + 4(16.0)) + 19.0 = 504.5

3(31.0)
 Percentage by mass of P =  100% = 18.4%
504.5
Mr of (NH4)2HPO4 = 2(14.0 + 4(1.0)) + 1.0 + 31.0 + 4(16.0) = 132.0
31.0
Percentage by mass of P =  100% = 23.5%
132.0
(NH4)2HPO4 contains higher percentage by mass of P.

Exercise 1.3 (Worked example)

1. The molecular formula of chlorophyll is C55H72MgN4O5. Calculate the percentage by mass of

magnesium present in chlorophyll.

Mr of chlorophyll = 55(12.0) + 72(1.0) + 24.3 + 4(14.0) + 5(16.0) = 892.3

24.3
Percentage by mass of Mg = × 100% = 2.72% (3 sf)
892.3

2. Haemoglobin, the oxygen-carrying protein in red blood cells, has four iron atoms per molecule
and contains 0.34% iron by mass. Calculate the molar mass of haemoglobin.
Let Mr of haemoglobin be m,
0.34
m = 4(55.8)
100
m = 6.56 × 104 g mol–1

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1.3 Empirical and Molecular Formulae

LO 6(d): define the terms empirical and molecular formula

1.3.1 Definitions

The empirical formula of a compound is the simplest formula which shows the ratio of the atoms of
the different elements in the compound.

The molecular formula of a compound is the formula which shows the actual number of atoms of each
element in one molecule of the compound.

For example,

compound empirical formula molecular formula

ethanoic acid CH2O C2H4O2
ethene CH2 C2H4

1.3.2 Derivation of Formulae using Composition by Mass

Exercise 1.4 (Worked example)

1. Caproic acid (Mr = 116) occurs in goat's milk and has the following composition by mass:
C, 62.1%; H, 10.3%; O, 27.6%. Determine the empirical formula and molecular formula of
caproic acid.

C H O
mass in 100 g / g 62.1 10.3 27.6
no. of moles 62.1 / 12.0 = 5.175 10.3 / 1.0 = 10.3 27.6 / 16.0 =1.725
mole ratio 5.175 / 1.725 = 3 10.3 / 1.725 = 6 1.725 / 1.725 = 1

Empirical formula of caproic acid is C3H6O.

Let molecular formula of caproic acid be (C3H6O)n.

n(3(12.0) + 6(1.0) + 16.0) =116
n = 116 / 58 = 2
Molecular formula of caproic acid is C6H12O2.

2. A 0.4764 g sample of an oxide of iron was completely reduced by a stream of carbon monoxide
to produce 0.3450 g of pure iron as the only iron-containing product. Find the empirical
formula of the oxide.

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Thinking process: Since iron was the only iron-containing product formed, the mass of iron
present in the oxide must have been 0.3450 g. The mass of oxygen present in the oxide can
hence be found.

Fe O
mass / g 0.3450 0.4764 − 0.3450 = 0.1314
no. of moles 0.3450 / 55.8 0.1314 / 16.0
= 6.183  10−3 = 8.213  10−3
mole ratio 6.183  10−3 / 6.183  10−3 = 1 8.213  10−3 / 6.183  10−3 = 1.33
simplest ratio 3 4

Empirical formula of the oxide is Fe3O4.

Exercise 1.5

1. The formula of a complex salt Z is NH4[Cr(SCN)x(NH3)y] and analysis produced the following
composition by mass: Cr, 15.5%; S, 38.1%; N, 29.2%. Calculate the values of x and y in the
formula for Z.

2. On strong heating, 100 g of CaSO4•nH2O is dehydrated and a constant mass of 79.09 g of

anhydrous salt is obtained. Calculate n.

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1.3.3 Derivation of Formulae using Combustion Data

LO 6(e) : calculate empirical and molecular formulae using combustion data or composition by mass

Organic compounds, on complete combustion with oxygen, form CO2 and H2O. By measuring and
calculating the amount of the reactants used (i.e. the compound and oxygen) and products formed
(CO2 and H2O) in a combustion experiment, the empirical and molecular formula of the organic
compound can be obtained.

Exercise 1.6 (Worked example)

Complete combustion of a hydrocarbon (a compound that contains hydrogen and carbon only) gave
0.352 g of carbon dioxide and 0.072 g of water. Calculate the empirical formula and its molecular
formula, given that it has a molar mass of 104 g mol−1.

(Thinking process: Since the reactants of this reaction are the hydrocarbon and oxygen only,
the carbon present in CO2 and the hydrogen present in H2O must have come from the
hydrocarbon. Hence, the mass of carbon present in the hydrocarbon is equal to the mass of
carbon present in CO2, while the mass of hydrogen atoms present in the hydrocarbon is
equal to the mass of hydrogen atoms present in H2O. This is an application of Law of
Conservation of Matter – Refer to Section 2.1.)

12.0
Mass of C in 0.352 g of CO2 =  0.352 = 0.096 g
44.0
2(1.0)
Mass of H in 0.072 g of H2O =  0.072 = 0.008 g
18.0
C H
mass / g 0.096 0.008
no. of moles 0.096 / 12.0 = 0.008 0.008 / 1 = 0.008
mole ratio 1 1

Empirical formula of the hydrocarbon is CH.

Let the molecular formula of the hydrocarbon be (CH)n.
n(12.0 + 1.0) = 104  n = 104 /13.0 = 8
Molecular formula of the hydrocarbon is C8H8.

Exercise 1.7

X is an organic iron compound containing only Fe, C and H. When a 0.944 g sample of X was
subjected to complete combustion, 2.23 g of CO2 and 0.457 g of H2O were formed.
What is the empirical formula of X?

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2 REACTIONS AND STOICHIOMETRY

Stoichiometry refers to the study of the quantitative aspects of chemical formulae and reactions. It
involves both the determination of chemical formulae as well as calculations using balanced chemical
equations based on the central idea of the mole.

2.1 Law of Conservation of Matter (Background info)

A chemical equation represents what happens during a chemical reaction. The law of conservation of
matter is the fundamental principle governing the balancing of chemical equations.

When balancing chemical equations, we have to ensure that every atom of every element is accounted
for since they are not destroyed or created, but rearranged. There must be the same number of atoms
of each element on the right-hand side as there are on the left-hand side.

Exercise 2.1
Write balanced chemical equations for the following reactions.

1. lead + silver nitrate → lead nitrate + silver (Worked example)

Pb + 2AgNO3 → Pb(NO3)2 + 2Ag

2. iron(II) chloride + chlorine → iron(III) chloride

Similarly, when substances chemically react to form products, the sum of the masses of all the
products is always found to be equal to the sum of the masses of the reactants.

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Exercise 2.2 (Worked example)

A mixture of CuSO4•5H2O and MgSO4•7H2O is heated until a mixture of the anhydrous salt is
obtained. If 5.00 g of the mixture gives 3.00 g of the anhydrous salts, what is the percentage by
mass of CuSO4•5H2O in the mixture?

(Thinking process: The hydrated CuSO4•5H2O and MgSO4•7H2O are heated to give CuSO4
and MgSO4 respectively. 1 mol of each of the hydrated salt should give 1 mol of the
corresponding anhydrous salt. By relating the no. of moles of each anhydrous salt left to
their total mass, the initial mass of CuSO4•5H2O can be found.)

Let mass of CuSO4•5H2O present in the mixture be x g.

Mass of MgSO4•7H2O = (5.00 − x) g
x x
η CuSO4 .5H2O = mol  η CuSO4 = mol
249.6 249.6
5.00− x 5.00− x
ηMgSO4 .7H2O = mol  ηMgSO4 = mol
246.4 246.4
 x 
Mass of CuSO4 left =  159.6 g
 249.6 
 5.00 − x 
Mass of MgSO4 left =   120.4 g
 246.4 
 x   5.00 − x 
 159.6 +   120.4 = 3.00
 249.6   246.4 
 x = 3.69
Percentage by mass of CuSO4.5H2O in the mixture = 3.693  100% = 73.8 %
5.00

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LAW OF CONSERVATION OF MASS (Background info)

The Law of Conservation of Mass can be shown by the following experiment:

The following set-up is first done with lead(II) nitrate solution in the test tube and potassium iodide
solution in the conical flask. The entire apparatus is then weighed.

Figure 1. Experiment set-up to illustrate the Law of Conservation of Mass

When the conical flask is shaken to mix the contents, a precipitation reaction occurs (Refer to Section
2.2) forming yellow solid lead(II) iodide. On re-weighing the conical flask with its content, the mass
should be the same as its initial mass.

2.2 Limiting Reactants and Percentage Yield (Background info)

A balanced equation shows the mole ratios in which reactants react to give products, and the mole
ratios in which the products are formed. It indicates that fixed proportions of reactants will react to
give fixed proportions of products. It does not, however, represent the actual amount or proportion
in which the reactants are present in a mixture. Hence, you should first determine whether there is a
reactant in excess.

For example,
H2(g) + ½O2(g) → H2O(g)

The mole ratio (1 : ½ : 1), as shown by the stoichiometric coefficients in the balanced equation, tells
us that 1 mole of H2 must react with ½ mole of O2 to give 1 mole of H2O.

If 1 mole of H2 is mixed with 1 mole of O2, then ½ mole of O2 must remain unreacted at the end of
complete reaction. Reactants present in excess are not all consumed at the end of complete reaction.
H2, on the other hand, is the limiting reactant. Limiting reactants are completely consumed in the
reaction and limits how much products can form.

Many reactions do not, however, go to completion and there may also be a loss of product in practice
(e.g. after purification or separation). Hence, the actual yield is usually less than 100% of the
theoretical yield that is calculated based on the limiting reactant.

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Actual mass (or amount) of product formed

Percentage yield= x 100%
Theoretical mass (or amount) of product

2.3 Types of Reactions (Background info)

In Chemistry, there are several different types of chemical reactions and more than one way of
classifying them. From this section onwards, we will classify the reactions into the following reaction
types:

(a) Precipitation reaction

Precipitation reactions are reactions which involve the formation of an insoluble solid which
is known as a precipitate, from the reaction of two solutions. The precipitate and the
supernatant liquid can be separated by filtration or decanting. In calculations involving
precipitation reaction, the mass of the solid will be obtained to find out the number of moles
of the solid product formed.

Examples of precipitation reactions:

NaCl(aq) + AgNO3(aq) → AgCl(s) + NaNO3(aq)
Na2SO4(aq) + Ba(NO3)2(aq) → BaSO4(s) + 2NaNO3(aq)
(b) Thermal decomposition
Thermal decomposition is a chemical reaction caused by heat. In such reactions, a compound
breaks down into two or more substances.

Examples of thermal decomposition:

2Mg(NO3)2(s) → 2MgO(s) + 4NO2(g) + O2(g)
2HCl(g) → H2(g) + Cl2(g)

(c) Acid-base reaction – Refer to Section 3

(d) Redox reactions – Refer to Section 4

Most of the reactions you learn at A-level fall into one or more categories. Remember that no
classification is perfect and so it would be highly possible to find some reactions that do not fit nicely
into any category.

In the following sections, we will see calculations involving the use of:
(i) reacting masses (from formulae and equations)
(ii) volumes of gases (e.g. in the burning of hydrocarbons)
(iii) volumes and concentrations of solutions
However, it would be a good practice to try to identify the type of reactions taking place in each of
the exercises given.

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2.4 Calculation using Reacting Masses and Moles

LO 6(g)part: perform calculations, including use of the mole concept, involving: (iv) reacting masses (from formulae and
equations)

Exercise 2.3 (Worked example)

1. Solid aluminium sulfide reacts with water to give aluminium hydroxide and hydrogen sulfide
gas. Write a balanced equation for this reaction. What is the maximum mass of H2S that can
form when 158 g of aluminium sulfide reacts with 131 g of water? Calculate the number of
moles of the excess reagent remaining at the end of reaction.

Al2S3(s) + 6H2O(l) → 2Al(OH)3(s) + 3H2S(g)

158
ηAl2S3 = = 1.051 mol
2(27.0)+ 3(32.1)

131
ηH2O = = 7.278 mol
18.0
No. of moles of H2O required to react with 1.051 mol of Al2S3 = 1.051  6 = 6.306 mol
Al2S3 is the limiting reagent.
ηH2S formed = 1.051  3 = 3.153 mol

Maximum mass of H2S that can form = 3.153  (2(1.0) + 32.1) = 108 g (3.s.f)
No. of moles of excess H2O = 7.278 − 6.306 = 0.972 mol

2. When 41.5 g of tungsten(VI) oxide (WO3) was reacted with excess hydrogen gas, metallic
tungsten and 9.50 cm3 of water was produced. Find the mass of tungsten obtained and its
percentage yield, given that the density of water is 1.00 g cm−3.

WO3(s) + 3H2(g) → W(s) + 3H2O(l)

Amount of H2O formed = 9.50  1.00 / 18.0 = 0.5278 mol
Actual amount of tungsten obtained = 0.5278 / 3 = 0.1759 mol
Actual mass of tungsten obtained = 0.1759  184 = 32.37 g = 32.4 g (3 sf)
41.5
η WO3 = = 0.1789 mol = Theoretical amount of tungsten formed
184 + 3(16.0)

Theoretical mass of tungsten formed

OR
= 0.1789 × 184 = 32.92 g 0.1759
Percentage yield =  100% = 98.3 %
Percentage yield 0.1789

= 32.37/32.92 × 100% = 98.3%

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Exercise 2.4

When 18.5 g of methane and 43.0 g of chlorine gas undergo a substitution reaction that has an
80.0% yield, what mass of chloromethane (CH3Cl) is obtained (the other product is HCl)?

2.5 Calculation using Volumes of Gases

LO 6(g)part: perform calculations, including use of the mole concept, involving: (v) volumes of gases (e.g. in the burning of
hydrocarbons)

In Topic 3 The Gaseous State, we learnt about the Avogadro’s Law.

Avogadro's Law: Equal volumes of all gases, under the same temperature and pressure, contain the
same number of particles (atoms or molecules).

Hence, for gases in a balanced equation, volume ratio = mole ratio

For example, for a given equation: 2CO(g) + O2(g) → 2CO2(g)

The balanced equation tells us that 20 cm of carbon monoxide will react with 10 cm3 of oxygen to
3

give 20 cm3 of carbon dioxide.

Note that the ratio of volumes 20 cm3 : 10 cm3 : 20 cm3 is the same as the mole ratio 2:1:2 indicated
by the stoichiometric coefficients in the balanced equation.

The molar volume, Vm, of any gas is the volume occupied by 1 mole of the gas at a specified
temperature and pressure. Thus,
Volume of a gas, V = n  Vm
where n is the amount (in moles) of the gas

Table 1. Temperature, pressure and molar volume at s.t.p. and r.t.p.

condition temperature pressure molar volume
standard temperature and pressure, s.t.p. 273 K (0 oC) 1 bar (100 kPa) 22.7 dm3 mol-1
room temperature and pressure (room
293 K (20 oC) 1 atm (101 kPa) 24 dm3 mol-1
conditions), r.t.p.

Note: Volumes of gases are dependent on temperature and pressure. Hence these conditions must be
specified.
The units for volume are cm3, dm3 and m3; 1 dm3 (1 litre) = 1000 cm3; 1 m3 = 106 cm3

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Exercise 2.5 (Worked example)

1. A mixture of 10 cm3 of methane, CH4, and 10 cm3 of ethane, C2H6, was sparked with an excess
of oxygen. After cooling to room temperature, the residual gas was passed through aqueous
potassium hydroxide. What volume of gas was absorbed by the alkali?

CH4 + 2O2 → CO2 + 2H2O

C2H6 + 7/2O2 → 2CO2 + 3H2O
Volume of CO2 produced from complete combustion of 10 cm3 of methane = 10 cm3
Volume of CO2 produced from complete combustion of 10 cm3 of ethane
= 10  2 = 20 cm3
Total volume of CO2 absorbed by the alkali = 10 + 20 = 30 cm3

2. When 100 cm3 of a gaseous hydrocarbon W is burnt in 500 cm3 of oxygen, 50 cm3 of oxygen
is left unreacted while 300 cm3 of carbon dioxide and 300 cm3 of steam are formed. All gases
are measured at 150oC and 1 atm. Deduce the balanced equation for the reaction and hence
derive the molecular formula of W.

 y y
CxHy(g) +  x +  O2 (g) → xCO2(g) + H2O(g)
 4 2
initial vol. / cm3 100 500 – –
final vol. / cm3 0 50 300 300
100 450 300 300
reacted reacted produced produced
mole ratio 1 4.5 3 3

x = 3/1 = 3
y/2 = 3/1 = 3  y = 6
Balanced equation: C3H6 + 9/2O2 → 3CO2 + 3H2O
Molecular formula of W is C3H6.
3. 10 cm3 of a gaseous hydrocarbon was exploded with an excess of oxygen. A contraction of
20 cm3 in volume occurs after the combustion. On passing the gaseous products through
aqueous sodium hydroxide, a further contraction of 30 cm3 occurs. Deduce the formula of
the hydrocarbon. (All volumes were measured at r.t.p.)

Let a be the initial volume of oxygen, and a’ be the final volume of oxygen remaining in
cm3
 y y
CxHy(g) +  x +  O2(g) → xCO2(g) + H2O(l)
 4 2
initial vol. / cm3 10 a – –
final vol. / cm3 0 a' 30 –
10 a−a' 30
–
reacted reacted produced

Mole ratio of CxHy : CO2 = 1 : x = 10 : 30  x = 30/10 = 3

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Total initial volume − total final volume = 20 cm3

(10 + a) − (a' + 30) = 20
a − a' = 40
 y
Based on vol ratio, volume O2 reacted = 10  3 +  = a − a' = 40
 4 
y=4
Molecular formula of the hydrocarbon is C3H4.

Exercise 2.6

1. In an experiment, 20 cm3 of a gaseous organic compound was sparked with excess oxygen.
80 cm3 of carbon dioxide and 80 cm3 of water vapour were obtained. All gases are measured
at the same temperature and pressure. Which of the following molecular formula fit the
data?
1 CH3CH2CH2CH3
2 CH3CH2CH2CHO
3 CH3CH2CH2CO2H

2. What volume of oxygen is required for the complete combustion of a mixture containing
5 cm3 of methane and 10 cm3 of ethene?

3. When 20 cm3 of a gaseous hydrocarbon Y was exploded with 150 cm3 of oxygen, the residual
gases occupied 130 cm3. After shaking the products with excess aqueous sodium hydroxide,
the final volume was 90 cm3. Deduce the molecular formula of Y. (All volumes were measured
at room conditions.)

4. 20 cm3 of a gaseous hydrocarbon was mixed with 150 cm3 of oxygen so that the hydrocarbon
was completely burnt. The volume of gas remaining at the end of combustion was 100 cm 3.
After passing over potassium hydroxide, this volume was reduced to 20 cm 3. All gases were
measured at 20 oC and the same pressure. What is the formula of the hydrocarbon?

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2.6 Calculations using Concentrations

LO 6(g)part: perform calculations, including use of the mole concept, involving: (vi) volumes and concentrations of solutions

When a solute is dissolved in a solvent, a solution is formed.

If the solvent is water, an aqueous solution is formed.

The concentration of a solution shows the amount of solute dissolved in a given volume of solution.

Notation for concentration of solute X in a solution in terms of mol dm−3: [ X ]

A standard solution is a solution whose concentration is accurately known.

amount of X (in mol)

Concentration of X (mol dm −3 ), [X] =
volume of solution,V (in dm 3 )

No. of moles of solute, n

= concentration of solute (mol dm–3) × volume (dm3)
mass of X (g)
=
molar mass of X (g mol−1 )

Note: 1 dm3 = 1000 cm3 = 10−3 m3 ; 1 cm3 = 10−3 dm3 = 10−6 m3

Dilution
When a solution is diluted (by adding more solvent), the concentration of the solution decreases but
the number of moles of the solute in the diluted solution remains unchanged.

Exercise 2.7 (Worked example)

14.3 g of hydrated sodium carbonate, Na2CO3•10H2O (Mr = 286.0) were dissolved in water and the
solution made up to 500 cm3 using a volumetric flask. What is the concentration of sodium ions in
the solution?
14.3
ηNa2CO3 •10H2O in 500 cm3 = = 0.05 mol
286.0
 ηNa+ in 500 cm3 = 0.05  2 = 0.10 mol

0.10
[Na+] = = 0.200 mol dm−3
500  10 −3

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Exercise 2.8

1. Calculate the volume, in cm3, of a solution required to provide 0.85 g of ethanoic acid
(CH3CO2H, Mr = 60.0) from a 0.30 mol dm–3 solution.

2. Agricultural biochemists often use 6-benzylaminopurine (C12H11N5) in trace amounts as a

plant growth regulator. In a typical application, 150 cm3 of a solution contains 0.030 mg of
the compound. What is the concentration of the solution?

3. A sample of concentrated nitric acid solution has a density of 1.41 g cm–3 and contains 70.0%
HNO3 by mass. What is the concentration of the solution?

Exercise 2.9 (Worked example)

1. Calculate the volume (in cm3) of 18.0 mol dm–3 sulfuric acid that is required to prepare
2.00 dm3 of a 0.300 mol dm–3 sulfuric acid solution.

ηH2SO4 = 0.300  2.00 = 0.600 mol

0.600
Volume of 18.0 mol dm−3 H2SO4 required = = 0.0333 dm3 = 33.3 cm3
18.0

2. What would be the concentration of the final mixture made by combining 385 cm3 of
0.725 mol dm–3 HCl and 525 cm3 of 0.325 mol dm–3 HCl?

 385   525 
Total η HCl in the mixture =   0.725 +   0.325 = 0.4498 mol
 1000   1000 
Total volume of mixture = 385 + 525 = 910 cm3
0.4497
[HCl] in the final mixture = −3
= 0.494 mol dm−3
910  10

Exercise 2.10

1. What is the volume of 0.0500 mol dm–3 K2Cr2O7 solution required to prepare 500 cm3 of
0.0200 mol dm–3 K2Cr2O7 solution?

2. Calculate the concentration of Na+ ions in a solution made by mixing 3.58 cm3 of
0.288 mol dm–3 sodium chloride with 500 cm3 of 6.51 × 10–3 mol dm–3 sodium sulfate.

3. What is the volume of water that must be added to 150 cm 3 of 0.0262 mol dm–3 NaOH to
obtain a 0.0100 mol dm–3 NaOH solution?

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Generic procedure for preparing a solution from a solid

1. Using an electronic balance, weigh accurately about _(mass)_ g of _(solid)_ in a weighing

bottle.
2. Transfer the solid into a 100 cm3 beaker and dissolve the solid completely in some deionised
water / (given solvent). Reweigh the weighing bottle to account for any remaining solid that
is not transferred into the beaker.
3. Transfer the solution into a 250 cm3 volumetric flask. Rinse the beaker a
few times and transfer all washings into the volumetric flask.
4. Top up to the mark with deionised water / (given solvent).
5. Stopper and shake well to obtain a homogeneous solution.

Note:
The beaker must be rinsed thoroughly (in step 3) to ensure complete transfer volumetric
of solution.flask
To
prepare a standard solution by diluting a given solution, replace steps 1 to 3 with: “Using a burette
(or pipette), place _(volume)_ cm3 of _(solution) in a 250 cm3 volumetric flask.”
Table of recordings
mass of empty weighing bottle / g
mass of weighing bottle and solid / g
mass of weighing bottle and residual solid / g
mass of solid used / g

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Preparing a series of solutions of different concentrations

To prepare a series of solutions of different concentrations, you need to mix the original solution
of known concentration (sometimes called ‘stock solution’) with the solvent or another solution.
Pipettes / burettes and volumetric flasks (100 cm3 or 250 cm3) are used for the accurate
measurement of volumes of liquids.
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑜𝑟𝑖𝑔𝑖𝑛𝑎𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑢𝑠𝑒𝑑 𝑓𝑜𝑟 𝑚𝑖𝑥𝑖𝑛𝑔
new concentration = original concentration × 𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑎𝑓𝑡𝑒𝑟 𝑚𝑖𝑥𝑖𝑛𝑔

You need to decide the range of concentrations (it depends on the purpose of the experiment),
and the total volume of each solution required. If your solution is required for a subsequent
titration procedure, then the total volume must be sufficient for at least three titrations.
For example, your desired range is from 0 to 2.00 mol dm─3 at equal intervals of 0.5 mol dm─3, and
you need 100 cm3 of each solution, you may present your plan in a table as shown:
volume of original 2.00 mol dm─3 total volume after (new)
solution 3 3
H2SO4 used / cm dilution / cm [H2SO4] / mol dm─3
1 75.00 100 1.50
2 50.00 100 1.00
3 25.00 100 0.50

Generic procedure for preparing a series of solutions by dilution

1. Using a burette / pipette, add _(volume)_ of the _(original solution)_ to a 100 cm3 (or 250 cm3)
volumetric flask.
2. Top up to the mark with _(deionised water) __ .
3. Stopper and shake well to obtain a homogeneous solution.
4. Repeat steps 1 to 3, according to the volumes stated in the table above.

In the situation where you are required to prepare a very dilute solution, say 0.010 mol dm ─3, it
would mean you measure 0.5 cm3 of stock solution to top up to 100 cm3, and this will give rise to a
large measurement error. In this case, you may consider a serial dilution method, i.e. instead of
adding water to the stock solution, you may add water to successively diluted solutions. This means
that solution 2 is prepared from solution 1, solution 3 from solution 2, and so on.
solution [H2SO4] / mol dm–3
1 2.00
2 1.00
3 1.00  10–1
4 1.00  10–2
Possible procedure:
1. Using a burette, add 50.0 cm3 of solution 1 to a 100 cm3 volumetric flask.
2. Top up to the mark with deionised water.
3. Stopper and shake well to obtain a homogeneous solution. Label this solution 2.
4. To prepare solutions 3 and 4, repeat steps 1 to 3 using 10.0 cm3 of solutions 2 and 3 respectively
instead of solution 1.

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3 ACID-BASE REACTIONS

Acids and bases are important in many chemical processes that occur around us, from industrial
processes to biological ones and from reactions in the laboratory to those in our environment.

The concept of acids and bases has broadened over time as chemists seek to propose a more
comprehensive model to classify, rationalise and predict acid-base chemistry. The current
understanding of acids and bases is primarily based on the historical contributions of chemists such
as Svante Arrhenius, Johannes Bronsted, Thomas Lowry, and Gilbert Newton Lewis.

3.1 Definitions of Acids & Bases

3.1.1 Arrhenius Theory of Acids & Bases

LO4(a): show understanding of, and apply the Arrhenius theory of acids and bases

• An acid is a substance that dissociates in water to produce H3O+(aq).

E.g. HCl(g) + H2O(l) → H3O+(aq) + Cl−(aq)

Note:
In aqueous solution, H+ (a ‘bare’ proton) does not exist on its own. Instead, it forms a coordinate bond
with a water molecule to form H3O+, called hydronium or hydroxonium ion. Chemists often use H+(aq)
and H3O+(aq) interchangeably to refer to the solvated H+ ion.

• A base is a substance that dissociates in water to produce OH−(aq).

E.g. NaOH(s) → Na+(aq) + OH−(aq)

• When an acid is added to a base, according to Arrhenius, the H+ ion reacts with the OH− ion to
produce a molecule of water, and undergoes neutralisation.

E.g. HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)

Ionic equation: H+(aq) + OH−(aq) → H2O(l)

The Na+(aq) and Cl−(aq) ions do not take part in the reaction. They are called ‘spectator ions’.

The limitation of this model is that it is restricted to aqueous solutions only. This limitation could be
addressed through the introduction of the Bronsted-Lowry acid-base model.

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3.1.2 Bronsted-Lowry Theory of Acids & Bases

LO4(b): show understanding of, and apply the Brnsted-Lowry theory of acids and bases, including the concept of
conjugate acids and conjugate bases

• An acid is defined as any species which donates a proton, H+.

An acid must thus contain H in its formula. E.g. HNO3 and H2PO4–.

• A base is defined as any species which accepts a proton, H+.

A base must contain a lone pair of electrons to bind the H+ ion. E.g. NH3, CO32–, F– and OH–.

A Bronsted-Lowry acid-base reaction involves the transfer of a proton from an acid to a base.
Bronsted-Lowry acid-base reactions do not only occur in aqueous solutions. They can also occur
between gases and non-aqueous systems. E.g. HCl(g) + NH3(g) → NH4Cl(s).

While the Bronsted-Lowry acid-base model is more inclusive than Arrhenius model, it still could not
explain why substances such as BF3 or AlCl3 which do not contain any hydrogen atom but are yet
known to behave as acids. This limitation is addressed through the introduction of the Lewis acid-base
model.

3.1.3 Lewis Theory of Acids & Bases

LO4(c): show understanding of, and apply the Lewis theory of acids and bases (including non-aqueous system e.g. reaction
between BF3 and NH3)

• An acid is a species that accepts an electron pair, e.g. BF3

• A base is a species that donates an electron pair, e.g. NH3

A Lewis acid-base reaction can be viewed as a transfer of a pair of electrons from the base to the
acid.
E.g. BF3 + NH3 → BF3•NH3

Recall in Topic 2 Chemical Bonding we learnt that BF3 and NH3 can react to form white solid NH3BF3.
This can be considered an acid-base reaction according to the Lewis model. You will encounter more
examples of Lewis acids and bases later in your A-Level course in organic chemistry.

Note:
The limitation of this theory is that it is too general. Thus, it is better to use the Bronsted-Lowry theory
whenever possible for acid-base reactions, and apply Lewis theory only if the reaction does not involve
proton transfer.

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Exercise 3.1

Identify the Bronsted acid and base in each of the following (forward) reactions:
1. HNO3(aq) + NH3(aq) → NO3–(aq) + NH4+(aq) (Worked example)
acid base
2. HNO3(aq) + H2O(l) → H3O+(aq) + NO3–(aq) (Worked example)
acid base
3. HCl(g) + NH3(g) → NH4Cl(s)

4. HNO3(l) + H2SO4(l) → H2NO3+(aq) + HSO4–(aq)

Note: H2O is amphoteric (can act as an acid or base, depending on the other substance present)

The three models of acids and bases can be used to interpret different acid-base systems. Bronsted-
Lowry and Lewis theories are often used to describe specific acid-base reactions whereas Arrhenius
theory is used to describe whether isolated substances are acids, bases or neither.

For example, in the case of nitric acid:

• Using Arrhenius model, nitric acid is an Arrhenius acid as it generates hydronium ions in the
presence of water.

• Using Bronsted-Lowry model, nitric acid can be either Bronsted-Lowry acid or base, as seen in
Exercise 3.1. It depends on what nitric acid reacts with. For instance, if it reacts with an alkali
such as aqueous sodium hydroxide, it acts as a Bronsted-Lowry acid. If nitric acid reacts with a
stronger acid such as sulfuric acid, it behaves like a Bronsted-Lowry base. (The concept of
‘strength of acid’ will be dealt with in Topic 14 Acid-Base Equilibria)

3.2 Titrations

Titration (or volumetric analysis) is a technique where a solution is gradually added from a burette to
a fixed volume of another solution, i.e. the aliquot (measured with a pipette and placed in a conical
flask), until the reactants in the two solutions have reacted completely. Titration is suitable for
reactions in which the reactants react rapidly and completely.

It is used to obtain quantitative information such as the concentration of a solution or to establish the
stoichiometry of a reaction. Usually one of the solutions used must be of an accurately known
concentration, and this is called the standard solution.

The equivalence point occurs when the reactants in the two solutions react according to the
stoichiometry of the reaction. The volume of solution added from the burette is the titre volume.

For an acid-base titration, the completion of the reaction is often found by noting the colour change
of an indicator added to the reaction flask. The point where the indicator changes colour is known as
the end point.

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Indicators for acid-base titration have distinct colours in the 'acid' and 'base' region as shown in
Table 2. At certain pH, called the working range, the indicator will change its colour.

Table 2. Some common indicators

pH working colour at end
indicators ‘acid’ region ‘base’ region
range point
methyl orange 3.1 – 4.4 red yellow orange
screened methyl
3.0 – 4.6 violet green grey
orange
bromothymol blue 6.0 – 7.6 yellow blue green
phenolphthalein 8.0 – 9.6 colourless pink pink
thymol blue 8.0 – 9.6 yellow blue green

NaOH(aq)
phenolphthalein

methyl orange

HCl(aq) Volume of NaOH added / cm3

Figure 2. Titration curve of a strong acid-strong base titration.
(Titration curves will be covered in Topic 14 Acid-Base
Equilibria.)

Generic procedure for titration

1. Pipette _(volume)_ cm3 of __(solution X)__ into a 250 cm3 conical flask.
2. Add 2 to 3 drops of __(suitable indicator)__ (for acid–base titration).
3. Fill a burette with _(known concentration in mol dm–3) (solution Y)__. Record the initial
burette reading.
4. Titrate__(solution X)__ against __(solution Y)__ until the colour of the solution changes from
__(initial colour)__ to __(colour at end-point)__. Record the final burette reading.
5. Repeat titration until two consistent titres within ±0.10 cm3 are obtained.

Table of recordings
final burette reading / cm3
initial burette reading / cm3
volume of (solution Y) used / cm3

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Note:
• For KMnO4 titrations, replace step 2 with “Add (volume) cm3 of dilute H2SO4 using a measuring
cylinder”. (To ensure that the acid is in excess. Normal laboratory concentration of H2SO4 is
1.0 mol dm–3.) {Refer to Section 4.4.1 Potassium manganate(VII) titration}
• For I2 / S2O32– titrations, remove step 2, and replace step 4 with: Titrate the I2 against
Na2S2O3(aq) until the solution changes (from brown) to pale yellow, then add 10 drops (or
1 cm3) of starch solution which gives an intense dark blue-black colour, then continue titration
until the blue-black colour just disappears. {Refer to Section 4.4.2 Iodometric titrations –
iodine / thiosulfate titration}

Choice of indicators for titrations

type of titration indicator colour change

starch solution (add
I2 – thiosulfate (in burette) 1 cm3 or 10 drops when
blue-black to colourless
solution turns pale
yellow)
Fe(II) – KMnO4 (in burette) – yellow to orange
strong acid – weak base (in burette) methyl orange red to orange
weak acid – strong base (in burette) phenolphthalein colourless to pink
weak acid – strong base (in burette) thymol blue yellow to green

Note:

• For acid-base titrations, the choice of indicators depends on the strength of the acid and
base, i.e. whether the acid/base is strong/weak. This table shows the suitable indicator for
different combinations of acid/base strengths.

• For KMnO4 titrations, refer to Section 4.4.1.

• For I2/S2O32- titrations, refer to Section 4.4.2.

• For all procedures, state clearly when titration should be stopped, i.e. from ___(colour in
conical flask at start of titration)____ to ___(‘midway’ colour of indicator)___. For example,
from strong acid-weak base (in burette), stop titration when methyl orange changes from red
to orange (not yellow).

• If the positions of the reagents are reversed, e.g. strong acid (in burette) – weak base, the
colour change is also reversed, i.e. methyl orange changes from yellow to orange (not red).

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Exercise 3.2 (Worked example)

A student was given solutions of HCl and NaOH with unknown concentrations. He carried out
titrations and found that 27.50 cm3 of the NaOH solution was required to completely react with
100 cm3 of the HCl solution. In a separate experiment, he used 18.40 cm3 of the NaOH solution to
titrate completely 50.00 cm3 of a 0.0782 mol dm–3 H2SO4. What are the concentrations of the given
HCl and NaOH solutions?

H2SO4 + 2NaOH → Na2SO4 + 2H2O

50
ηH2SO4 used in titration =  0.0782 = 0.00391 mol (note: the H2SO4 is the standard
1000 solution)
ηNaOH reacted with H2SO4 = 0.00391  2 = 0.00782 mol

0.00782
[NaOH] = = 0.425 mol dm−3
18.40 10 −3

NaOH + HCl → NaCl + H2O

27.50
ηNaOH reacted with HCl =  0.425 = 0.01169 mol
1000

η HCl in 100 cm3 = 0.01169 mol

0.01169
[HCl] = = 0.117 mol dm−3
100  10 −3

Exercise 3.3 (Worked example)

27.82 g of hydrated sodium carbonate crystals with the formula Na2CO3•nH2O were dissolved in
water and made up to 1.00 dm3 aqueous solution. 25.0 cm3 of this solution was neutralised by
48.80 cm3 of 0.100 mol dm–3 dilute HCl. Find the value of n.

2HCl + Na2CO3 → 2NaCl + CO2 + H2O

2HCl ≡ Na2CO3
48.80
In 25.0 cm3 of solution, amount of Na2CO3 = ½ × 1000 × 0.100 = 0.00244 mol
1000
In 1.00 dm3 of solution, amount of Na2CO3 = 0.00244 × 25 = 0.0976 mol
Na2CO3.nH2O ≡ Na2CO3 ≡ nH2O
27.82
106 + 18n = 0.0976 mol

n ≈ 10

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3.3 Back Titration (Application Example)

In a back titration, a known excess of one reagent A is allowed to react with an unknown amount of
B. The amount of unreacted A is then determined by titration with a reagent C of known
concentration. From the titration results, the amount of unreacted A and the amount of B can be
found by simple stoichiometric calculations.

In summary amount of unreacted A found from titration results

Total  A =  A that reacted with B +  A that reacted with C

General Steps:
1) Determine the amount of C required in the titration.
2) Using stoichiometry, find amount of A that reacted with C in the titration.
3) Note: amount of A that reacted with C in the titration
= amount of A that did not react with B earlier
4) Therefore, amount of A that reacted with B
= total amount (known excess) of A added – amount of A that did not react with B earlier
5) Knowing now the amount of A that reacted with B, using stoichiometry, the amount of B is found.

Exercise 3.4 (Worked example)

1. A sample of impure magnesium was analysed by allowing it to react with excess HCl solution.
After 1.32 g of the impure metal was treated with 100 cm3 of 0.750 mol dm–3 HCl, the
remaining solution required 50 cm3 of a 0.250 mol dm–3 aqueous sodium hydroxide for
complete neutralisation. Assuming the impurities do not react with the acid, what is the
percentage by mass of Mg in the sample?

Mg + 2HCl → MgCl2 + H2
HCl + NaOH → NaCl + H2O
50
ηNaOH used to react with remaining HCl =  0.250 = 0.0125 mol
1000
η HCl remaining after reaction with Mg = 0.0125 mol

100
Initial η HCl used =  0.750 = 0.0750 mol
1000
 η HCl reacted with Mg = 0.0750 − 0.0125 = 0.0625 mol

 η Mg present = 0.0625  2 = 0.03125 mol

Mass of Mg present = 0.03125  24.3 = 0.759 g

0.759
Percentage by mass of Mg =  100% = 57.5 %
1.32

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2. 1.60 g of a metallic oxide, MO, was dissolved in 100 cm3 of 1.0 mol dm–3 HCl. The resulting
liquid was made up to 500 cm3 with distilled water. 25.0 cm3 of this solution required
21.05 cm3 of a 0.1020 mol dm–3 sodium hydroxide for neutralisation. Calculate:
(i) the mass of the oxide that reacts with 1 mole of HCl,
(ii) the relative formula mass of the oxide and the relative atomic mass of the metal.

MO + 2HCl → MCl2 + H2O

HCl + NaOH → NaCl + H2O

21.05
ηNaOH used to react with remaining HCl =  0.1020 = 2.147 10−3 mol
1000

 η HCl in 25.0 cm3 = 2.147 10−3 mol

500
 η HCl in 500 cm3 = 2.147 10−3  = 0.04294 mol
25.0

= η HCl remaining after reaction with MO

100
Initial η HCl used =  1.0 = 0.100 mol
1000

 η HCl reacted with MO = 0.100 − 0.04294 = 0.05706 mol

1.60
(i) Mass of MO that reacted with 1 mole of HCl = = 28.0 g (3.s.f)
0.05706

28.0
(ii) Mr of MO = = 56.1 (3.s.f)
0.5

Ar of M = 56.1 − 16.0 = 40.1 ( M is calcium)

Exercise 3.5

A sample containing ammonium chloride was warmed with 100 cm3 of 1.00 mol dm–3 sodium
hydroxide. After all the ammonia had been driven off, the excess sodium hydroxide required
50.00 cm3 of 0.250 mol dm–3 sulfuric acid for neutralisation. What mass of ammonium chloride did
the sample contain?

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4 REDOX REACTIONS
LO12(a): describe and explain redox processes in terms of electron transfer and/or of changes in oxidation number
(oxidation state)

4.1 Definitions

Redox reaction: A reaction that involves reduction and oxidation simultaneously.

In ‘O’ Level, we have defined reduction and oxidation processes in terms of gain or loss of H or O. At
‘A’ Level, we shall further define these processes in terms of electron transfer and/or changes in
oxidation number (oxidation state).

Reduction: A process whereby a substance gains electrons, resulting in a decrease in oxidation

number.
e.g. Cu2+ + 2e– → Cu

Oxidation: A process whereby a substance loses electrons, resulting in an increase in oxidation

number.
e.g. Zn → Zn2+ + 2e–  Acronym: O I L R I G

Reducing agent (reductant): A substance that gives electrons to another, itself being oxidised in
the process.
e.g. Fe2+, C2O42–, I−, S2O32−

Oxidising agent (oxidant): A substance that takes in electrons from another, itself being reduced
in the process.
e.g. MnO4–, Cr2O72–, H2O2, I2

Disproportionation: A redox reaction in which the same substance is both oxidised

and reduced.
e.g. 3Cl2 + 6OH− → 5Cl− + ClO3− + 3H2O

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Oxidation number (oxidation state): The total number of electrons that an atom either gains or loses
in order to form a chemical bond with another atom.

An oxidation number is a number that is assigned to an atom in a substance. The oxidation number
could be positive, negative, or zero, and it indicates if electrons are lost or gained. In other words, the
oxidation number is a number that helps us keep track of electrons in an atom (so called its ‘electron
environment’).

The calculation of oxidation state by first principle is based on one simple assumption – a perfect ionic
model, i.e. what is the charge that an atom would have if the more electronegative element takes all
the electrons.

Two examples are used below, H2O and H2O2. The dot-and-cross diagrams of both compounds are
drawn and a boundary (represented using dotted lines) is drawn to show what happens if the more
electronegative element takes all the electrons. If the same element is bonded next to each other,
then each element ‘will take back their own’.

xx xx
H O H x
xx
x
H O O H
x
xx
x x

For the oxygen atom in H2O, after drawing the boundary, a quick count reveals 8 electrons. Originally,
oxygen has 6 electrons around it; the oxidation state of oxygen in H2O is –2.

Similarly, for H2O2, a quick count reveals 7 electrons. Therefore, the oxidation state of oxygen in H2O2
is –1.

4.2 Assigning Oxidation Number

• When writing the oxidation number (O.N.), the +/– signs must be stated before the number.
• For a covalent compound, the covalent bond is 'converted' to ionic by assigning the shared
electrons to the more electronegative atom, such that the oxidation numbers of the atoms are
therefore the 'charges' on the 'ions'.
• Here are the most important rules and exceptions to remember when assigning oxidation
numbers:

example
O.N. of Na = 0,
1. For an atom in its elemental form, oxidation number = 0
O.N. of O in O2 = 0
2. For a monoatomic ion, oxidation number = charge on the O.N. of Mg in Mg2+ = +2
ion O.N. of I in I− = –1
In MnO4−,
3. For a polyatomic ion, sum of all the oxidation numbers
(O.N. of Mn) + 4(O.N. of O) = –1
= charge on the polyatomic ion
 O.N. of Mn = +7

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4. For a neutral compound, sum of all the oxidation In Fe2O3,

numbers = 0 2(O.N. of Fe) + 3(O.N. of O) = 0
In ClF, O.N. of F = −1; O.N. of Cl= +1
5. For a compound, the more electronegative element is
In HCl, O.N. of H = +1; O.N. of Cl= −1
given the negative oxidation number.
In NaH, O.N. of H = −1

Some elements nearly always exhibit the same oxidation number in their compounds. Hence, they are
used as reference points in assigning oxidation numbers to other elements. For example,

+1, except in metal hydrides (e.g. NaH) where O.N. is –

hydrogen, H
1
oxygen, O –2, except in peroxides (e.g. H2O2) where O.N. is –1
Group 1 metals: Li, Na, K, Rb, Cs, Fr +1
Group 2 metals: Be, Mg, Ca, Sr, Ba, Ra +2
aluminium, Al +3
fluorine, F –1

For elements other than these reference elements, the oxidation number can be calculated using the
equations in rules (3) or (4), as shown above for Mn in MnO4—, and Fe in Fe2O3. Note that when
applying these equations, the oxidation number obtained is the average oxidation number because
you are assuming that all the atoms of the element has the same electron environment (i.e. the atoms
are bonded in the same way to the other atoms). This is not always be the case, as you will see in the
example below.

Using first principle, calculate the oxidation state of each carbon atom individually in the compound,
ethanol.

• CH3CH2OH

You find that because the two C atoms have are bonded to different atoms (i.e. have different
‘electron environments’), they have different oxidation numbers: the oxidation no of the first C is –3,
while that for the second C is –1. On the other hand, if you use rule (4), you obtain the oxidation no
of –2, which is the average oxidation no.

In most applications, you will use the five rules to assign the (average) oxidation number. You seldom
need to calculate the oxidation number individually from first principles, unless when dealing with
how atoms in different electron environments will react specifically in a given reaction.

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Exercise 4.1 (Worked example)

State the oxidation number of the underlined element in the following:

(i) CH3OH (ii) S8 (iii) BrF3 (iv) HNO2 (v) Ca(HCO3)2

(i) C + 3 – 1 = 0 ⇒ C = –2
(ii) 8(S) = 0 ⇒ S = 0
(iii) Br – 3 = 0 ⇒ Br = +3
(iv) 1 + N + 2(–2) = 0 ⇒ N = +3
(v) 2 + 2(1 + C + 3(–2)) = 0 ⇒ C = +4

Exercise 4.2

Identify the type of reactions represented in the following equations.

Which are the reducing and oxidising agents for the redox reactions?

(i) NO3–(aq) + 4Zn(s) + 7OH–(aq) + 6H2O(l) → 4Zn(OH)42–(aq) + NH3 (aq) (Worked example)
5 0 +2 −3
Type of reaction: redox reaction
Oxidising agent: NO3− Reducing agent: Zn

(ii) KCl(aq) + AgNO3(aq) → KNO3(aq) + AgCl(s) (Worked example)

Type of reaction: Precipitation

(iii) NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l) (Worked example)

Type of reaction: acid-base reaction / neutralisation

(iv) H2O2 (aq) + 2Fe2+ (aq) + 2H+ (aq) → 2Fe3+ (aq) + 2H2O (l)

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4.3 Balancing Redox Equations

LO12(h): construct redox equations using the relevant half-equations

In a redox reaction, there is a transfer of electrons from the reducing agent (which loses electrons and
is oxidised) to the oxidising agent (which gains electrons and is reduced).

Hence, in a balanced redox equation, the number of electrons lost by the reducing agent must be
equal to the number of electrons gained by the oxidising agent, i.e. there are no free electrons in the
overall balanced equation. Once again, the Law of Conservation of Mass applies here.

When you are balancing an ionic equation, besides balancing the atoms, you also need to balance the
charges as well.

Balancing redox equations using half equations (ion-electron method)

In the ion-electron method (also called the half-equation method), the redox equation is separated
into two half-equations - one for oxidation and one for reduction. Each of these half-reactions is
balanced separately and then combined to give the balanced redox equation.

1. Divide the unbalanced redox equation into two half-equations (an oxidation half-equation and
a reduction half-equation). If the equation is written in the molecular form, re-write it as an ionic
equation before splitting it into half-equations.
2. Balance each half-equation as follows:
• Balance the element undergoing oxidation or reduction in the reactant and product.
• Work out the oxidation number of the relevant elements.
• Add the appropriate number of electrons according to the change in oxidation numbers of
elements, taking into account the number of each element in the formula unit.
• Balance the charges on both sides of the half-equation by adding the appropriate number of
H+ (under acidic conditions) or OH− (under alkaline conditions). Under neutral conditions,
either H+ or OH− can be used.
• Balance the O (or H) atoms by adding H2O on the appropriate side.
• Check the number of H (or O) atoms on both sides – it should be balanced.
3. Multiply each balanced half-equation by an appropriate integer, if necessary, to make electrons
lost = electrons gained (i.e. total number of electrons lost by reducing agent = total number of
electrons gained by oxidising agent).
4. Add the half-equations together (electrons on both sides must cancel out each other).
5. Simplify by cancelling any extra species appearing on both sides.
6. Make a final check that the redox equation is balanced in terms of atoms and charge.

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Exercise 4.3 (Worked example)

Balance the following redox reactions.

(i) Cr2O72− + Fe2+ → Cr3+ + Fe3+ (acidic)

Reduction: Cr2O72− + 14H+ + 6e− 2Cr3+ + 7H2O

Oxidation: Fe2+ → Fe3+ + e−

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

(ii) Cl2 → Cl– + ClO3– (basic)

Reduction: Cl2 + 2e− → 2Cl−

Oxidation: Cl2 + 12OH− → 2ClO3− + 6H2O + 10e−

Overall: 3Cl2 + 6OH− → 5Cl− + ClO3− + 3H2O (basic)

This is a disproportionation reaction where the same species (C l2 in this case)

undergoes both oxidation and reduction.

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Balancing redox equations without splitting into half equations

Where it is not required to work with half equations, you may balance a redox equation without
splitting into half equations, using the same principles as in the ion-electron method.

1. Write the unbalanced redox equation with the two reactants and their corresponding products
on the same line (with some spaces on top and below for working). Balance the element
undergoing oxidation or reduction in the reactant and product.
2. Determine the number of electrons gained / lost by each element undergoing reduction /
oxidation, according to the change in oxidation number of the element, and then determine the
number of electrons gained / lost per formula unit of the two reactants, taking into account the
number of each element in the formula unit.
3. Determine the correct mole ratio of the two reactants, such that electrons lost = electrons gained
(i.e. total number of electrons lost by reducing agent = total number of electrons gained by
oxidising agent).
4. Complete the balancing of charges and O (or H) as in the ion-electron method.
5. Make a final check that the redox equation is balanced in terms of atoms and charge.

These steps are illustrated below for the example below.

Electrons lost = −1e x 2 = −2e

MnO4─ + C2O42─ → Mn2+ + 2 CO2 Step 1:

Balance the Mn and C atoms
+7 +3 +2 +4
Electrons gained = +5e

Step 2:
Determine electrons gained per formula unit

Step 3: Determine mole ratio such that electrons lost = electrons gained
2 MnO4─ + 5 C2O42─ → 2 Mn2+ + 10 CO2

Step 4: Balance charges and O / H atoms

2 MnO4─ + 5 C2O42─ + 16 H+ → 2 Mn2+ + 10 CO2 + 8 H2O

Step 5: Check atoms and charges are balanced

Exercise 4.4 (Worked example)

Review your answers here: (timestamp 3:43:03)
Balance the following redox reaction.

H2O2 + I– → I2 + H2O (acidic) 2H+ + H2O2 + 2I– → I2 + 2H2O

TcO4− + As → Tc + AsO2− (basic) 3TcO4– + 7As + 4OH– → 3Tc + 7AsO2– + 2H2O

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4.4 Redox Titrations

LO13(g): describe and explain the use of Fe3+/Fe2+, MnO4–/Mn2+ and Cr2O72−/Cr3+ as examples of redox systems

In a redox titration, a known concentration of oxidising agent is used to find an unknown

concentration of reducing agent (or vice versa). Redox titrations are also used to establish the
stoichiometry of redox reactions. The calculations involved are based on the mole concept, similar to
acid-base titrations.

Table 3. Common oxidising agents

oxidant reaction medium product
acidic Mn2+ (colourless)
MnO4− (purple)
alkaline MnO2 (dark brown solid / ppt)
Cr2O72− (orange) acidic Cr3+ (green)
I2 (brown in aqueous solution) neutral I– (colourless)
H2O2 (colourless) acidic H2O

Table 4. Common reducing agents

reductant reaction medium product
Fe2+ (pale green) acidic Fe3+ (yellow)
I– (colourless) acidic/alkaline/neutral I2 (brown in aqueous solution)

S2O32– (colourless) neutral S4O62– (colourless)

H2O2 (colourless) acidic O2
C2O42– (colourless) acidic CO2

4.4.1 Potassium Manganate(VII) titration

1. The KMnO4 solution is usually placed in the burette and added into the conical flask containing
the reductant (e.g. Fe2+ determination)

2. Typical reducing agents that can react with KMnO4 are: Fe2+, C2O42−, H2O2 and I−

3. Manganate(VII) titrations are usually carried out in acidic conditions. The acid used is sulfuric
acid (usually at 1 mol dm–3) and added into the conical flask.
Note: Nitric acid and hydrochloric acid are both not suitable as nitric acid is itself an oxidising
agent while hydrochloric acid can be oxidised by manganate(VII) ion to give chlorine.

Relevant half-equation: MnO4− + 8H+ + 5e− → Mn2+ + 4H2O

4. During the titration, the purple MnO4– turns colourless as it is reduced to Mn2+ ions (colourless
/ pale pink).

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5. When all the reductant is used up, the first extra drop of KMnO4 makes the solution in the conical
flask turn permanently pink. This sharp colour change indicates that the end-point is reached.
Hence no other indicator is required.

4.4.2 Iodometric titrations – iodine / thiosulfate titration

Iodine is often used to oxidise thiosulfate ions to tetrathionate ions, itself reduced to iodide.

Relevant equation: 2S2O32− + I2 → 2I− + S4O62−

1. The thiosulfate solution is usually placed in the burette and the brown iodine solution in the
conical flask.

2. During the titration, the thiosulfate is added from the burette into the flask and reduces brown
iodine into colourless iodide ions. The solution gradually fades to pale yellow.

3. At this point, starch indicator is added into the flask. Solution turns blue-black as starch forms
an intense blue-black complex with the remaining iodine.

4. Titration then continues till all iodine is used up. Colour change at the end-point is from
blue-black to colourless.

Points to note when conducting iodometric titration

a) The iodine solution should be titrated as soon as possible once it is prepared. Why?

Iodine is volatile and will vaporise easily at room temperature hence titration must be carried
out as soon as possible. If this is not possible, cover all flasks containing iodine.

b) Why is the starch indicator added only towards the end of titration when the iodine solution is
pale yellow, instead of right at the start?

Starch forms a blue-black water-soluble complex with iodine in which the iodine is trapped
within the starch molecules. Hence, starch should not be added at the beginning of the titration
when there is a high concentration of iodine since some iodine may remain trapped in the starch
even at the equivalence point.

c) After titration is complete, a slow return of the blue colour is observed. Why is this so? Should
we continue our titration?

This is due to atmospheric oxidation of I− back to I2.

Ignore any slow return of blue colour after the titration is done.

Iodometric back titrations are often used to analyse redox reactions involving some other oxidants
(e.g. H2O2) that can oxidise iodide to iodine. This analysis takes place in two steps:

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i. A known excess of potassium iodide solution is added to the oxidant (with unknown
concentration) in a conical flask to liberate iodine. (Note: Excess I− ensures all the oxidant is
reacted and serves to dissolve iodine in aqueous solution.)
Example: H2O2 + 2I– + 2H+ → 2H2O + I2
ii. The iodine liberated is then titrated with standard thiosulfate solution from a burette. From the
titration results, the amount of iodine liberated, and hence the amount of oxidant can be
determined.

Exercise 4.5 (Worked example)

1. 27.50 cm3 of a 0.0200 mol dm–3 solution of acidified potassium manganate(VII) was required
to oxidise a 25.0 cm3 solution of hydrogen peroxide. What was the concentration of hydrogen
peroxide and the volume of oxygen (at s.t.p.) evolved during the titration?
Reduction: MnO4− + 8H+ + 5e− → Mn2+ + 4H2O

Oxidation: H2O2 → O2 + 2H+ + 2e−

Overall: 2MnO4− + 5H2O2 + 6H+ → 2Mn2+ + 5O2 + 8H2O

27.50
ηMnO− used =  0.0200 = 5.50  10−4 mol
4
1000

ηH2O2 present = 5.50  10−4  5/2 = 1.375  10−3 mol

1.375 10 −3
[H2O2] = = 0.0550 mol dm−3
25.0 10 −3

ηO2 evolved = 1.375  10−3 mol

Volume of O2 evolved = 1.375  10−3  22.7 = 0.0312 dm3

2. A 0.1576 g of iron wire was converted into Fe2+ ions and then acidified, and titrated against
potassium dichromate(VI) solution of concentration 1.64 × 10–2 mol dm–3. Given that
27.30 cm3 of the oxidant was required, calculate the percentage purity of the iron wire.

Reduction: Cr2O72− + 14H+ + 6e− → 2Cr3+ + 7H2O

Oxidation: Fe2+ → Fe3+ + e−

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

27.30
η Cr O2 − used =  1.64 10 −2 = 4.477  10−4 mol
2 7
1000

ηFe2 + present = 4.477  10−4  6 = 2.686  10−3 mol = ηFe present in the wire

Mass of Fe in the wire = 2.686 10−3  55.8 = 0.1499 g

0.1499
Percentage purity of the iron wire =  100% = 95.1%
0.1576

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Exercise 4.6 (Worked example)

Chlorine reacts with iodine to form a compound T, ICl7. When dissolved in an excess of aqueous
potassium iodide, T liberates iodine, I2, which is the only iodine-containing product in the reaction.

ICl7 + 7I− → 4I2 + 7Cl−

T

(i) Calculate the number of moles of iodine liberated when 1.00 g of T reacts with an excess of
aqueous potassium iodide.

T ≡ 4I2
1.00
Amount of I2 liberated = 4 × 375.4 = 0.01066 mol ≈ 0.0107 mol (3sf)

(ii) What volume of 1.00 mol dm−3 sodium thiosulfate would be required to react with all the
iodine liberated in (i)?

2S2O32– + I2 → 2I– + S4O62–

2 S2O32– ≡ I2
Amount of S2O32– required = 2 × 0.01066 = 0.02132 mol
Volume of solution required = 0.02132 ÷ 1.00 = 0.2132 dm3 = 21.3 cm3 (3 sf)

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4.5 Application of Oxidation Number and Electron Transfer (Application Example)

General Strategy:

To determine the change in oxidation number of B when a known amount of A reacts with
stoichiometric amount of B in a redox reaction, the following steps can be taken:

1) Construct the half-equation for A, the reactant whose initial and final oxidation numbers are
known.
2) Calculate the number of moles of electrons lost (or gained) using amount of A. Equate this to the
number of moles of electrons gained (or lost) by the other reactant (B).
3) Determine the mole ratio of B and the electrons gained (or lost) by B. This gives the number of
moles of electrons transferred for 1 mol of B.
4) Hence determine the new oxidation number of B.

Exercise 4.7 (Worked example)

1. In an experiment, 50.0 cm3 of a 0.10 mol dm–3 solution of a metallic salt reacted exactly with
25.00 cm3 of a 0.1 mol dm–3 aqueous sodium sulfite. The half-equation for the oxidation of
sulfite is shown below.
SO32–(aq) + H2O(l) → SO42–(aq) + 2H+(aq) + 2e−
If the original oxidation number of the metal in the salt was +3, what would be the new
oxidation number of the metal?

25.00
ηSO2 − reacted =  0.1 = 0.0025 mol
3
1000

η e- lost by SO32− = 0.0025  2 = 0.0050 mol = ηe- gained by M3+

50.0
ηM3 + reacted =  0.10 = 0.0050 mol
1000

 ηM3 + : η e- gained = 0.0050 : 0.0050 = 1 : 1

Each mole of M3+ gains 1 mole of electrons.

New oxidation number of the metal = +3 −1 = +2

2. 25.0 cm3 of a solution of 0.0200 mol dm–3 potassium ethanedioate, K2C2O4, reacted with
20.0 cm3 of an acidified solution of 0.0100 mol dm–3 potassium manganate(VII).

Find the oxidation number of carbon in the product and hence suggest the identity of this
product.

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Hwa Chong Institution 2023 04 – Reactions and Stoichiometry

MnO4− + 5e− + 8H+ → Mn2+ + 4H2O

20.0
ηMnO− reacted =  0.0100 = 0.0002 mol
4
1000

η e- gained by MnO4− = 0.0002  5 = 0.0010 mol = η e- lost by C2O42−

25.0
η C O 2- reacted =  0.0200 = 0.0005 mol
2 4 1000

η C O 2- : η e- lost = 0.0005 : 0.0010 = 1 : 2

2 4

Each mole of C2O42− loses 2 moles of electrons.

There are 2 C atoms in each C2O42−

Each C loses 1 electron.

The oxidation state of C in C2O42− is +3.

Exercise 4.8

In a redox reaction, 1 mol of S2O32– is oxidised by 4 mol of Cl2. Which of the following is the sulfur-
containing product of this reaction?
S , SO2 , SO32–, SO42–, S4O62–

LOOKING AHEAD

The stoichiometry concepts learnt in this topic will be applicable in almost all future topics where
you are required to write balanced equations for all reactions, and work out quantities of reagents
to be used (e.g. in organic synthesis) etc. Our knowledge of redox reactions and acid-base reactions
will also be expanded in the extension topics of electrochemistry and acid-base equilibria.

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Hwa Chong Institution 2023 05 – Chemical Energetics: Thermochemistry & Thermodynamics

Chemical Energetics: Thermochemistry &

05 Thermodynamics
GUIDING QUESTIONS
• What are the energy changes in a chemical or physical process?
• Why do some chemical or physical processes take place spontaneously? How can we predict if a
process is spontaneous?
• How can we measure or find out the energy change in a chemical or physical process?

LEARNING OUTCOMES
Students should be able to:
7(a) explain that most chemical reactions are accompanied by energy changes, principally in the
form of heat usually associated with the breaking and forming of chemical bonds; the
reaction can be exothermic (H negative) or endothermic (H positive)
7(b) construct and interpret an energy profile diagram, in terms of the enthalpy change of the
reaction and of the activation energy (Refer to Topic 6 Reaction Kinetics)
7(c) 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) (Refer to Topic 2 Chemical Bonding)
(iii) lattice energy (H negative, i.e. gaseous ions to solid lattice)
7(d) calculate enthalpy changes from appropriate experimental results, including the use of the
relationship: heat change = mcT
7(e) explain, in qualitative terms, the effect of ionic charge and of ionic radius on the numerical
magnitude of a lattice energy (Refer to Topic 2 Chemical Bonding)
7(f) apply Hess’ Law to construct simple energy cycles, e.g. Born-Haber cycle, and carry out
calculations involving such cycles and relevant energy terms (including ionisation energy and
electron affinity), with particular reference to:
(i) determining enthalpy changes that cannot be found by direct experiment, e.g. an
enthalpy change of formation from enthalpy change of combustion
(ii) the formation of a simple ionic solid and of its aqueous solution
(iii) average bond energies
7(g) explain and use the term entropy
7(h) discuss the effects on the entropy of a chemical system by the following:
(i) change in temperature
(ii) change in phase
(iii) change in the number of particles (especially for gaseous systems)
(iv) mixing of particles
[quantitative treatment is not required]
7(i) predict whether the entropy change for a given process or reaction is positive or negative

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Hwa Chong Institution 2023 05 – Chemical Energetics: Thermochemistry & Thermodynamics

7(j) state and use the equation involving standard Gibbs free energy change of reaction, G:
G = H − TS

[the calculation of standard entropy change, S, for a reaction using standard entropies, S,
is not required]
7(k) state whether a reaction or process will be spontaneous by using the sign of G
7(l) understand the limitations in the use of G to predict the spontaneity of a reaction
7(m) predict the effect of temperature change on the spontaneity of a reaction, given standard
enthalpy and entropy changes

REFERENCES
1. Peter Cann & Peter Hughes, Cambridge international AS & A level Chemistry, Hodder Education,
Chapter 5 & 20
2. Martin S. Silberberg, Chemistry: The Molecular Nature of Matter and Change, 6th Edition,
McGraw-Hill Higher Education, Chapter 6 & 20

LOOKING BACK
In the topic of Chemical Bonding, we saw how atoms are chemically bonded to each other. Energy changes
take place when atoms combine to form different compounds. By measuring these energy changes, we can
learn about the strength of the bonding that hold atoms together. For example, we saw that lattice energy is
a measure of the strength of ionic bonding. Also, the concept of energy changes is fundamental to our
understanding of the chemical reactions or physical processes that we observe in our everyday life. For
example, the energy changes that took place during the dissolution of a solute help to explain its solubility. In
this topic, we will look at other energy changes to understand why other chemical reactions or physical
processes take place. We will also look at another factor, known as entropy change, which affects the
spontaneity of a chemical reaction or physical process.

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Hwa Chong Institution 2023 05 – Chemical Energetics: Thermochemistry & Thermodynamics

1 INTRODUCTION

1.1 Enthalpy and enthalpy changes

LO 7(a): explain that most chemical reactions are accompanied by energy changes, principally in the form of heat usually
associated with the breaking and forming of chemical bonds; the reaction can be exothermic ( H negative) or endothermic
(H positive).

The total chemical energy of a substance is called its enthalpy (or heat content). Chemical energy
consists of kinetic energy and potential energy. The potential energy, due to electrostatic attraction
between the particles, is usually the main component of the total chemical energy.

During a chemical reaction, bonds are broken and new bonds are formed. The breaking of bonds
requires energy while the formation of bonds releases energy. The energy change that occurs is called
the enthalpy change. The symbol is H and the units are J mol–1 or kJ mol–1.

1.2 Endothermic and exothermic processes

H is positive, H > 0 H is negative, H < 0

Energy
Energy
products
reactants
H > 0 H < 0
reactants
products
Energy level diagrams

The products have higher energy content than The products have lower energy content than
the reactants. the reactants.
The reaction absorbs heat from the The reaction releases heat to the surroundings.
surroundings.

The temperature of the surroundings decreases. The temperature of the surroundings increases.

The reaction is said to be endothermic. The reaction is said to be exothermic.

Table 1. Endothermic and Exothermic reactions

If the energy level of the products is lower than that of the reactants, we say the products are
energetically more stable than the reactants.

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Hwa Chong Institution 2023 05 – Chemical Energetics: Thermochemistry & Thermodynamics

1.3 Energy profile diagram

LO 7(b): construct and interpret an energy profile diagram, in terms of the enthalpy change of the reaction and of the
activation energy (see also Topic 6 Reaction Kinetics)

The activation energy of a reaction (Ea) is the minimum energy which the reacting particles must
possess in order to overcome the energy barrier before becoming products.

The enthalpy change and activation energy of a reaction can be represented in an energy profile
diagram (reaction pathway diagram) as shown in Table 2 below. An energy profile diagram is different
from the energy level diagrams in Table 1.

Endothermic Reaction, H > 0 Exothermic Reaction, H < 0

Energy Energy

Ea
Ea products
reactants
∆H > 0 ∆H < 0

reactants products

Progress of reaction Progress of reaction

Table 2. Energy profile diagrams for 1-step endothermic and exothermic reactions

1.4 Thermochemical equation

A thermochemical equation is a balanced equation that includes the enthalpy change of the reaction.

E.g. H2(g) + ½O2(g) → H2O(l) Hr = –285.9 kJ mol–1

This equation indicates that 285.9 kJ of heat is released when 1 mole of H2 gas reacts with 0.5 mole of
O2 gas to give 1 mole of liquid H2O.

The term ‘mol–1’ in the Hr units does not refer to 1 mole of H2 or 1 mole of H2O. Instead, it refers to
the whole reaction as written, in this case, when 1 mole of H2 gas reacts with 0.5 mole of O2 gas.

It is important to include state symbols to all formulae given in a thermochemical equation since a
change in state might be accompanied by an appreciable change in energy.

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Hwa Chong Institution 2023 05 – Chemical Energetics: Thermochemistry & Thermodynamics

Exercise 1.1 (Worked Example)

(a) Write down the enthalpy change of reaction for the following reactions, given that:
H2(g) + ½O2(g) → H2O(l) Hr = –285.9 kJ mol–1
(i) H2O(l) → H2(g) + ½O2(g)

Solution:
Hr = –(–285.9) = +285.9 kJ mol–1

Comments:
This equation is the reverse of the example given above. Since 285.9 kJ of heat is
released when 1 mole of H2 gas reacts with 0.5 mole of O2 gas to give 1 mole of liquid
H2O, then 285.9 kJ of heat will be absorbed when 1 mole of liquid water forms 1 mole of
H2 gas and 0.5 mole of O2 gas.

(ii) 2H2(g) + O2(g) → 2H2O(l)

Solution:
Hr = 2(–285.9) = –571.8 kJ mol–1

Comments:
The coefficients in this equation is twice that of the example given above. Since two the
no. of moles of H2 gas and O2 gas are reacting, twice the amount of heat should be
evolved.

(b) H2(g) + ½O2(g) → H2O(g) Hr = –241.8 kJ mol–1

Explain why the enthalpy change of the above reaction is less exothermic than –285.9 kJ mol–1.

Hr is less exothermic as heat is absorbed to convert liquid water to water vapour.
The difference of +44.1 kJ mol–1 represents the enthalpy change of vaporization of water.

Comments:
Compare the two equations. The difference between the two reactions is the state that water
is in at the end of the reaction. As such, the reason for the difference in the enthalpy change of
the reaction should be due to the difference in the state of water.

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Hwa Chong Institution 2023 05 – Chemical Energetics: Thermochemistry & Thermodynamics

1.5 Standard conditions and standard states

LO 7(c)(i)part: explain and use the term: standard conditions.

A set of standard conditions has been defined for thermochemistry:

Temperature 298 K (25 °C)
Pressure 1 bar (1 bar = 105 Pa)
Concentration of any solution 1.0 mol dm–3
Table 3. Standard conditions for thermochemical measurements

• A substance in its normal (most stable) physical state at 298 K and 1 bar is said to be in its
standard state. E.g. I2(s), Br2(l), C(s) (Refer to note below).

• The actual enthalpy of an element cannot be measured. Elements in their standard states under
standard conditions are assigned zero enthalpy (H = 0).

• When the enthalpy change is determined under standard conditions, it is referred to as the
standard enthalpy change and is represented by the symbol HꝊ.

Note:
C(s) refers to the graphite allotrope; graphite has a lower energy level and is energetically more stable
than diamond.
C(graphite) + O2(g) → CO2(g) HꝊr = –393 kJ mol–1
C(diamond) + O2(g) → CO2(g) HꝊr = –395 kJ mol–1

Energy / kJ mol−1 C (diamond) + O2(g)

C (graphite) + O2(g)
0
HꝊr = –395 kJ mol–1

H r = –393 kJ mol–1

CO2(g)

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Hwa Chong Institution 2023 05 – Chemical Energetics: Thermochemistry & Thermodynamics

2 ENTHALPY CHANGES OF REACTION, FORMATION, COMBUSTION & NEUTRALISATION

LO 7(c)(i)part: explain and use the terms, enthalpy change of reaction, with particular reference to: formation; combustion.

2.1 Standard enthalpy change of reaction

The enthalpy change when molar quantities of reactants as specified by the chemical equation
react to form products at 1 bar and 298 K (standard conditions).

E.g. NH3(g) + HCl(g) → NH4Cl(s) HꝊr = –176 kJ mol–1

Cu(s) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s) HꝊr = –146 kJ mol–1

2.2 Standard enthalpy change of formation

The enthalpy change when 1 mole of a substance is formed from its constituent elements in their
standard states at 298 K and 1 bar.

E.g. ½H2(g) + ½I2(s) → HI(g) HꝊf = +26.5 kJ mol–1

2C(s) + 3H2(g) + ½O2(g) → C2H5OH(l) HꝊf = –298 kJ mol–1

• From the definition, the enthalpy change of formation of elements in their standard state (at
298 K and 1 bar) is 0 kJ mol–1.

• HꝊf is a measure of the energetic stability of a substance relative to its constituent elements.

If HꝊf is positive  compound is energetically less stable than its constituent

elements
 greater likelihood for compound to decompose into its constituent
elements
If HꝊf is negative  compound is energetically more stable than its constituent
elements
 less likelihood for compound to decompose into its constituent
elements

• Enthalpy changes of formation are often theoretical. Some reactions may not take place in
practice. E.g. C2H5OH cannot be formed by just mixing C, H2 and O2. In such cases, HOf can be
calculated indirectly using Hess’ Law (Refer to Section 4).

Exercise 2.1
Write an equation to represent the standard enthalpy change of formation of CaSO4(s).
Ca(s) + 1/8 S8(s) + 2O2(g) → CaSO4(s) OR Ca(s) + S(s) + 2O2(g) → CaSO4(s)

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Hwa Chong Institution 2023 05 – Chemical Energetics: Thermochemistry & Thermodynamics

2.3 Standard enthalpy change of combustion

The heat evolved when 1 mole of a substance is completely burnt in excess oxygen at 298 K and
1 bar.

E.g. CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) HꝊc = –866 kJ mol–1

Mg(s) + ½O2(g) → MgO(s) HꝊc = –601 kJ mol–1

• The enthalpy change of combustion is always exothermic i.e. heat is always evolved in
combustion.

Exercise 2.2
What is the name of the enthalpy change represented by the equation: H2(g) + ½O2(g) → H2O(l)?

2.4 Standard enthalpy change of neutralisation

LO 7(c)(i)part: explain and use the term, enthalpy change of neutralisation

The heat evolved when 1 mole of water is formed in the neutralisation reaction between an acid and
a base, at 298 K and 1 bar.

• Neutralisation is an exothermic reaction since it involves the attraction of H+ and OH– ions to
form an O–H bond.

H+(aq) + OH–(aq) → H2O(l) HꝊneut = –57.0 kJ mol–1

• The enthalpy change of neutralisation of a strong acid with a strong base is almost the same
for all strong acids and bases (–57.0 kJ mol–1).

Reason:
Strong acids and strong bases ionise completely in dilute aqueous solution. Reaction between
them is effectively the reaction between aqueous H+ ions and OH– ions.

E.g. KOH(aq) + HNO3(aq) → KNO3(aq) + H2O(l) HꝊneut = –57.0 kJ mol–1

NaOH (aq) + HCl (aq) → NaCl(aq) + H2O(l) HꝊneut = –57.0 kJ mol–1

Effectively H+(aq) + OH–(aq) → H2O(l) HꝊ = –57.0 kJ mol–1

K+, NO3–, Na+ and Cl– ions are essentially spectator ions in the above neutralisation reactions.

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Hwa Chong Institution 2023 05 – Chemical Energetics: Thermochemistry & Thermodynamics

• The enthalpy change of neutralisation involving a weak acid or weak base is slightly less
exothermic than –57.0 kJ mol–1.

Reason:
Weak acids (or weak bases) do not ionise completely in dilute aqueous solution. During
neutralisation, energy is absorbed to ionise the un-ionised weak acid (or weak base). Thus, less
energy is released and the resulting HꝊneut is less exothermic.

E.g. CH3CO2H(aq) ⇌ CH3CO2–(aq) + H+(aq) HꝊ = +1.8 kJ mol–1

Then H+(aq) + OH–(aq) → H2O(l) HꝊ = –57.0 kJ mol–1

Overall NaOH(aq) + CH3CO2H(aq) → CH3CO2– Na+(aq) + H2O(l) HꝊneut = –55.2 kJ mol–1

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Hwa Chong Institution 2023 05 – Chemical Energetics: Thermochemistry & Thermodynamics

3 EXPERIMENTAL DETERMINATION OF ENTHALPY CHANGE

LO 7(d): calculate enthalpy changes from appropriate experimental results, including the use of the relationship: heat change
= mcT

The reaction (part of the universe that is being studied) is defined as the system. The environment of
the reaction (rest of the universe that is not part of the system) is known as the surrounding.

The enthalpy change at constant pressure appears as heat. The heat given out (or taken in) by a
reaction is transferred to the surrounding. The surrounding is often some water or a solution
containing the reactants and products.

For example, CuSO4(aq) + Zn(s) → ZnSO4(aq) + Cu(s) H = −219 kJ mol−1

The system consists of the reactants and the products. The reaction between CuSO4 and Zn takes place
in an aqueous medium. Since the reaction is exothermic (sign of H is negative), heat is released by
the reaction and is transferred to the surrounding aqueous medium.

The heat that is absorbed by the aqueous medium or solution causes the temperature of the solution
to rise. This amount of heat can be determined by measuring the temperature change.

q = heat change of solution (J)

m = mass of solution (g)
q = mcT
c = specific heat capacity of solution (J g–1 K–1)
T = change in temperature of the solution (K or oC)

The specific heat capacity, c, is defined as the amount of heat required to raise the temperature of
1 g of the substance by 1 K (or 1 oC). The unit of specific heat capacity is J g–1 K–1.

The heat capacity, C, is defined as the amount of heat required to raise the temperature of the
substance by 1 K (or 1 oC). The SI unit for heat capacity is J K–1.

If heat capacity of the solution is given instead, then the heat that is absorbed (or released) by the
solution can be calculated as follows:

q = CT C = heat capacity of solution (J K–1)

Hence by measuring the temperature change of the solution, we can determine the heat transferred
to the surrounding solution and hence the heat absorbed or released by the reaction.

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Hwa Chong Institution 2023 05 – Chemical Energetics: Thermochemistry & Thermodynamics

The enthalpy change can be calculated as follows:

Sign of H is positive. Heat is absorbed by
q
Endothermic reaction H = + the reaction. Temperature of the
n
surrounding solution decreases.

Sign of H is negative. Heat is released by

q
Exothermic reaction H = − the reaction. Temperature of the
n
surrounding solution increases.

q = heat change (heat absorbed or released)

n = no. of moles of substance according to the definition of the enthalpy change (e.g. nH2O for Hneut,
nsubstance combusted for Hc)
Note: For a thermochemical equation whose limiting reactant’s stoichiometric coefficient is not 1,
q/n must be multiplied by the limiting reactant’s stoichiometric coefficient to give that enthalpy
change of reaction defined by the thermochemical equation. See Exercise 3.3 / 3.4.

3.1 The calorimeter

For reactions involving solutions, a simple calorimeter consisting of a polystyrene cup with a lid and a
thermometer can be used to determine the heat change.

thermometer

lid

reaction polystyrene cup

mixture 250 cm3 beaker
Figure 1. A simple calorimeter
Note:
• Polystyrene is an excellent insulator so heat loss from the sides is minimised. The lid also helps
to minimise heat exchange with the surrounding air.
• The polystyrene cup is often supported in a 250 cm3 beaker or using a retort stand, to prevent
toppling under the weight of the thermometer. The insulation can be improved by nesting two
cups.
• The temperature changes are often small, so for accurate work the thermometer should have
a precision of ±0.1oC.

3.2 Assumptions in the calculations

To ensure accurate results, all the heat released (or absorbed) by the reaction must be used to raise
(or lower) the temperature of the solution. In practice, we cannot totally eliminate heat exchanges
with the surrounding air or apparatus so we make the following assumptions in our calculations.

• No heat loss to (or heat gain from) surrounding air

• Heat capacity of the calorimeter (e.g. polystyrene cup) is omitted

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Hwa Chong Institution 2023 05 – Chemical Energetics: Thermochemistry & Thermodynamics

In addition, it is more convenient to measure the volume of the solution. Hence to calculate the mass
of the solution, we assume that the density of the solution is the same as that of water (1.00 g cm–3)
since the solution is very dilute.

3.3 Reaction between two aqueous solutions

Generic Procedure for reactions involving mixing of two solutions

1. Measure _(volume)_ cm3 of __(solution X)__ into a polystyrene cup using a measuring cylinder
/ pipette / burette. Record the initial temperature of solution X with a thermometer.
2. Measure _(volume)_ cm3 of __(solution Y)__ in another measuring cylinder. Record the initial
temperature of solution Y with the thermometer.
3. Add solution Y quickly to solution X in the polystyrene cup and stir the mixture gently.
4. Record the highest / lowest temperature reached with the thermometer.
Note:
• The initial temperature to use for calculations is the weighted average (by volume) of the
initial temperatures of the two solutions.
Tsolution X  Vsolution X + Tsolution Y  Vsolution Y
Weighted average initial temperature =
Vsolution X + Vsolution Y

• The solution that kickstarts the reaction is added quickly to minimise heat loss. Hence, it
should not be measured with a burette or pipette.

Exercise 3.1 (Worked Example)

40.0 cm3 of 2.0 mol dm–3 HCl(aq) were added to 50.0 cm3 of 2.0 mol dm–3 NaOH(aq) in a polystyrene
cup. The following results were obtained.

Initial temperature of HCl (aq) / oC 22.3

Initial temperature of NaOH (aq) / oC 22.5
Highest temperature reached / oC 34.6

Calculate the enthalpy change of neutralisation.

HCl + NaOH → NaCl + H2O Hneut = ?

40 cm3 50 cm3
2.0 mol dm–3 2.0 mol dm–3
Ti = 22.3 C Ti = 22.5 C

40×22.3 +50×22.5
Average initial temperature = = 22.4 C
40+50

Comments:
This is called a weighted average, see Lecture Notes pg12 above.

Heat evolved = 90  4.18  (34.6 – 22.4) = 4589 J

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Hwa Chong Institution 2023 05 – Chemical Energetics: Thermochemistry & Thermodynamics

Comments:
In calculating the heat evolved, two assumptions are made:
1. The density of the solution is the same as that of water (1.00 g cm–3), so the mass of 90
cm3 of solution is 90 g. Take note that this assumption is used very often in doing such
calculations.
2. specific heat capacity of the solution is the same as that of water (4.18 J g–1 K–1 from Data
Booklet).

Note that the value for T in C or K is the same, T= 34.6 – 22.4 = 12.2 C or 12.2 K

HCl is limiting ( same concentration of solutions, 1:1 mole ratio, but smaller volume of HCl used)

40
n(H2O) formed = n(HCl) reacted = 1000  2.0 = 0.08 mol
−4589
Hneut = 0.08
= –57.4 kJ mol−1

Comments:
Hneut is the heat evolved when 1 mol of H2O is formed in the neutralisation reaction between an
acid and a base. In the experiment, 0.08 mol of H2O is formed. Hence to calculate Hneut here, we
divide q by n(H2O) formed. Since Hneut is exothermic (temperature increased), the – sign must be
indicated.

Exercise 3.2
25.0 cm3 of 2.0 mol dm–3 H2SO4(aq) were added to 25.0 cm3 of 2.0 mol dm–3 NaOH(aq) in a polystyrene
cup. The initial temperatures of the solutions were 30.0 oC and 29.8 oC respectively. When the
solutions were mixed, the highest temperature reached was 43.6 oC. Use the data to calculate a value
for the enthalpy change of neutralisation. [–57.3 kJ mol–1]

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Thermometric Titration

Suppose we need to determine a value for Hneut using aqueous sodium hydroxide and hydrochloric
acid but the concentration of hydrochloric acid is unknown. In this case, we are unable to determine
the limiting reactant and the amount of water formed. Hence the generic procedure for reactions
involving mixing of two solutions given earlier cannot be used.

Instead, we can use thermometric titration in which a series of temperatures is recorded after each
(small and fixed) addition of the solution from the burette until equivalence point is reached and
passed. Extrapolation on the temperature–volume graph allows us to determine both the
maximum temperature and the volume at which complete neutralisation is achieved. These results

can then be used to determine the unknown concentration as well as a value for H neut.
Temperature / C

T

Volume of Y added /cm3

Vneut

Generic Procedure for Thermometric Titration

1. Pipette _(volume)_ cm3 of __(solution X)__ into a polystyrene cup.
2. Record the temperature of the solution with a thermometer.
3. From a burette, add _(volume of each addition) cm3 of (solution Y)__ quickly to the polystyrene
cup.
4. Stir the mixture with the thermometer and record its temperature.
5. Repeat steps 3 and 4 until __(total volume) cm3__ of __(solution Y)__ has been added.

Note:
• No indicator is required.
• The total volume of solution added from the burette must be more than that required for
complete reaction, such that there are sufficient data points to obtain a best–fit line for the
downward slope of the graph.
• The actual experimental data may show gentle curves before and after the equivalence point.
Before the equivalence point, each addition of solution Y releases the same amount of heat
but it is spread over a larger volume of solution, thus resulting in a smaller temperature rise.
After the equivalence point where the reaction is complete, further addition of solution Y
that is of lower temperature cools the reaction mixture. As the temperature difference
between solution Y and the reaction mixture decreases, the temperature drop becomes
smaller.

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3.4 Reaction between a solid and aqueous solution

Generic Procedure for reactions involving adding a solid to a solution

1. Weigh accurately _(mass)_ g of __(solid X)__ in a weighing bottle using an electronic balance.
2. Measure _(volume)_ cm3 of __(solution Y)__ into a polystyrene cup using a measuring
cylinder / pipette / burette. Record the initial temperature of solution Y with a thermometer.
3. Add solid X quickly into the cup and stir the mixture gently.
4. Record the highest / lowest temperature reached with the thermometer.
5. Re–weigh the weighing bottle and the residual solid.
Note:
• The solid is added quickly to minimise heat loss.
• As the solid may not be transferred completely, the weighing bottle and the residual solid
must be re–weighed to determine the exact mass of solid added.

Exercise 3.3
50.0 cm3 of 0.10 mol dm–3 silver nitrate solution were placed in a polystyrene cup. A known mass
of zinc powder was added and the following results were obtained.

mass of weighing bottle and 4.31 Initial temperature of 21.1

Zn powder / g solution / oC
mass of weighing bottle and 3.51 Highest temperature 26.3
remaining Zn / g reached / oC
mass of Zn added / g 0.80 T / oC 5.2

Calculate the enthalpy change for the reaction Zn(s) + 2Ag+(aq) → Zn2+(aq) + 2Ag(s).

Heat evolved = 50  4.18  5.2 = 1086.8 J

0.80
n(Zn) added = 65.4 = 0.0122 mol
50
n(Ag+) present = 1000  0.10 = 0.005 mol, Ag+ is the limiting reactant

Zn + 2Ag+ → Zn2+ + 2Ag

1086.8
Hr = − × 2 = −435 kJ mol−1
0.005

Comments:

In this reaction, the reaction between Zn and Ag+ heats up the solution it is in. As such, the reaction
between Zn and Ag+ is treated as the ‘system’. The water or solution is treated as the ‘surrounding’.
When calculating mcT, mass m refers to the ‘surrounding’ which in this question is the 50 cm 3
solution i.e. 50 g assuming its density is the same as that of water. The Zn is part of the ‘system’ and
not considered in m.

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When calculating the Hr, Note that the given equation shows that 2 mol of Ag+ reacted with 1 mol
1086.8
of Zn. In doing the calculation, − = −217 kJ mol−1, this shows the amount of heat evolved
0.005
when 1 mol of Ag+ reacts. Hence −217 kJ mol−1 needs to be multiplied by 2 to give the Hr with
respect to the given equation.

Hr may also be calculated based on the number of moles of Zn that reacted.

n(Zn) reacted = 0.005  ½ = 0.0025 mol

1086.8
Hr = − 0.0025 = −435 kJ mol−1

Dividing 1086.8 J by 0.0025 mol Zn gives the Hr based on 1 mol of Zn as is given in the equation.

This reaction is exothermic (temperature increased), the – sign must be indicated for Hr

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3.5 Temperature correction

In many experiments, the temperature may not immediately reach a maximum (or minimum),
especially when the reaction is slow and heat loss to (or gain from) the surroundings becomes
significant. To account for heat loss to (or gain from) the surroundings, a series of temperatures can
be recorded before and after the mixing to give a temperature-time graph. Extrapolation is done to
the point of mixing to obtain a more accurate maximum (or minimum) temperature.

Generic Procedure to obtain Maximum/ Minimum Temperature by Extrapolation

1. Weigh accurately _(mass)_ g of __(solid X)__ in a weighing bottle using an electronic balance.
/ Measure _(volume)_ cm3 of __(solution X)__ using a measuring cylinder.
2. Measure _(volume)_ cm3 of __(solution Y)__ into a polystyrene cup using a measuring
cylinder / pipette / burette.
3. Record the temperature of solution Y every 30 seconds for 2.5 minutes using a thermometer.
4. At exactly 3.0 minutes, add solid X / solution X quickly into the cup and stir the mixture gently.
5. Continue to record the temperature every 30 seconds from 3.5 minutes to 10.0 minutes.
6. Re–weigh the weighing bottle and the residual solid (if a solid is used).

Exercise 3.4
The experiment in Exercise 3.3 was repeated using the above procedure (temperature was
monitored for 10 minutes) and the following results were obtained.
Time, t / min 0 0.5 1.0 1.5 2.0 2.5 3.5 4.0 4.5 5.0
Temperature / oC 21.1 21.1 21.1 21.1 21.1 21.1 25.4 25.8 26.3 25.9
Time, t / min 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0
Temperature / oC 25.4 25.0 24.2 24.0 23.8 23.2 22.7 22.3 21.9 21.4

Use the data and graph to calculate the enthalpy change for the reaction
Zn(s) + 2Ag+(aq) → Zn2+(aq) +2Ag(s).
29
Maximum temperature
28
if no heat loss
27
Temperature / oC

26
25
24
23
22
21
20
0 1 2 3 4 5 6 7 8 9 10
Time, t / min

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3.6 Experimental method to determine enthalpy change of combustion


The following experiment set-up can be used to determine the H c for a fuel such as ethanol. The
heat released during combustion is used to heat a known mass of water in a copper calorimeter.

thermometer
shield
Note:
lid
Both the shield and lid
water (known mass) help to reduce heat loss
copper to surroundings.
calorimeter

spirit burner that contains fuel

(weighed before and after burning)
Figure 2. Experimental set-up to determine enthalpy change of combustion of a fuel

Generic Procedure for Combustion Reactions

1. Weigh the spirit burner containing the fuel using an electronic balance.
2. Using a measuring cylinder, place 100 cm3 of water in a copper calorimeter. Record the initial
temperature of the water with a thermometer.
3. Set up the apparatus as shown in the diagram.
4. Ignite the fuel and heat up the water. Stir gently with the thermometer.
5. When a temperature rise of about __(temperature change)__ C is reached, extinguish the
flame and record the maximum temperature reached with the thermometer.
6. Allow the spirit burner to cool to room temperature. Re–weigh the spirit burner containing
the remaining fuel.

Note:
Unlike the polystyrene cup, the heat absorbed by the copper calorimeter is usually included in the
calculation of heat, q, because copper is a good conductor of heat. In some cases, the total heat
capacity of the copper can and water may be given.

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Exercise 3.5
In an experiment to determine Hc for ethanol, the following results were obtained. Calculate Hc
for ethanol. Compare the experimental value with the literature value of –1368 kJ mol–1 and
account for any difference.

Mass of water in calorimeter / g 250.00

Mass of burner and ethanol before combustion / g 16.20
Mass of burner and ethanol after combustion / g 15.67
Temperature of water before combustion / oC 29.6
Temperature of water after combustion / oC 40.0

A bomb calorimeter is used to obtain highly accurate values of Hc as heat loss is minimised.

Experimental Method using a Bomb Calorimeter

1. A known mass of the substance (whose Hc is to

be determined) is burnt in excess oxygen in a
bomb calorimeter.
2. The heat released is transferred to a known mass
of water in the calorimeter.
3. The rise in temperature of the water is then
measured.
4. Allowance is made for the heat capacity of the
bomb calorimeter and the heat evolved in burning
the iron ignition wire used to ignite the substance.
Thus Hc can be measured accurately.
Figure 3. Bomb calorimeter

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4 HESS’ LAW AND ITS APPLICATIONS

Some enthalpy changes of reaction can be determined directly by experiment (e.g. enthalpy change
of combustion using a bomb calorimeter). For reactions that are diffcult to carry out directly, we can
use Hess’ Law to determine the enthalpy changes of these reactions from other enthalpy data.

4.1 Hess’ law of constant heat summation

The enthalpy change (H) of a reaction is determined only by the initial and final states and is
independent of the reaction pathway taken.

H1
A D
pathway 1
H2 H4
pathway 2
H3
B C

By Hess’ Law, enthalpy change for pathway 1 = enthalpy change for pathway 2
H1 = H2 + H3 + H4

LO 7(f)(i)part: apply Hess’ Law to construct simple energy cycles, and carry out calculations involving such cycles and relevant
energy terms, with particular reference to: determining enthalpy changes that cannot be found by direct experiment, e.g. an
enthalpy change of formation from enthalpy change of combustion

General steps to calculate H of a reaction using Hess’ Law:

1. Write the equation representing the enthalpy change that you are required to calculate.
2. Construct a fully labelled energy cycle incorporating the enthalpy changes provided, including
state symbols.
3. Apply Hess’ Law to calculate the required enthalpy change.

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4.2 Application: Calculations using standard enthalpy change of combustion

Worked Example 4.1
Given the following enthalpy changes of combustion, calculate the standard enthalpy change of
formation of carbon monoxide.
HꝊc (carbon) = –394 kJ mol–1
HꝊc (carbon monoxide) = –283 kJ mol–1

Method 1a: Constructing an Energy Cycle

1 Start with the equation that represents HꝊf (CO).
○

2 Since HꝊc (C) and Hc (CO) are given, we can draw a cycle where C(s) on the left-hand side
○
of the equation undergoes complete combustion to form CO2(g). To do this we need to add
½ mol of O2(g). Hence ½ mol of O2 must also be added on the right-hand side of the equation.
This ½ mol of O2(g) reacts with CO(g) to form CO2(g).

HꝊf (CO)
C(s) + ½ O2(g) CO(g)
+ ½ O2(g) + ½ O2 (g)

HꝊc (C) = HꝊc (CO) =

−394 kJ mol−1 −283 kJ mol
−1

CO2(g)

By Hess’ law,
HꝊf (CO) = −394 − (−283)
= −111 kJ mol−1

Quick Check  Equations are balanced

 State symbols are correct
 Sign of H is consistent with direction of arrow

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Method 1b: Constructing an Energy Level Diagram

If H is negative (exothermic reaction), we draw the arrow pointing down and vice versa.

Energy / kJ mol−1 By Hess’ law,

HꝊf (CO) + (−283) = −394
C(s) + O2(g) HꝊf (CO) = −111 kJ mol−1
0

HꝊf (CO)

CO(g) + O2(g) −394 Quick  Equations are balanced and state symbols are
check correct
 Axis is labelled
−283
 Zero energy level is labelled if applicable
CO2(g)  Sign of H is consistent with direction of arrow

Method 2: Equation Method

C(s) + O2(g) → CO2(g) H = HꝊc (C) = −394 kJ mol–1

CO2(g) → CO(g) + ½O2 (g) H = −HꝊc (CO) = +283 kJ mol–1
C(s) + ½O2(g) → CO(g) HꝊf (CO) = −394 + 283 = −111 kJ mol–1

Exercise 4.1 (Worked Example)

Calculate the standard enthalpy change of formation of propane using the combustion data
provided.
Substance HꝊc / kJ mol–1
Graphite –394
Hydrogen –286
Propane –2220

Hf (propane)
3C(s) + 4H2(g) CH3CH2CH3(g)
+ 3O2(g) + 2O2(g) + 5O2(g)

3(−394) + 4(−286) −2220

= −2326
3CO2(g) + 4H2O(l)

By Hess’s Law, Hf (propane) = –2326 –(–2220) = –106 kJ mol–1

Comments:
In drawing an energy cycle, it might be useful to write out the chemical equations that represent
the various enthalpy changes.

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Exercise 4.2
Calculate the standard enthalpy change of formation of ethanol using the combustion data
provided. [–279 kJ mol–1]
Substance HꝊc / kJ mol–1
Graphite –394
Hydrogen –286
Ethanol –1367
2(–394) + 3(–286) – (–1367) = –279 kJ mol–1

General Formula: Hr =  m H 

c (reactants) –  n H 
c (products)

where m, n = stoichiometric coefficients of the reactants and products in the given reaction.

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4.3 Application: Calculations using standard enthalpy change of formation

Exercise 4.3 (Worked Example)
Calculate the standard enthalpy change for the reaction below using the data given.
CaCO3(s) → CaO(s) + CO2(g)

Substance HꝊf / kJ mol–1

CaCO3(s) –1207
CaO(s) –635
CO2(g) –394

CaCO3(s) CaO(s) + CO2(g)

−1207 −635 + (−394) = −1029

Ca(s) + C(s) + 3/2 O2(g)


By Hess’s Law, H r = +1207 – 1029 = +178 kJ mol–1

Exercise 4.4
Calculate the standard enthalpy of formation of solid ammonium chloride, NH4Cl(s), using the given
data.
NH3(g) + HCl(g) → NH4Cl(s) HꝊr = –176.0 kJ mol–1
HꝊf [NH3(g)] = –46.1 kJ mol–1 ; HꝊf [HCl(g)] = –92.3 kJ mol–1 [–314 kJ mol–1]

Hf (NH4Cl(s)) = −176.0 + (−46.1) +(−92.3) = –314 kJ mol–1

General Formula: Hr =  m H 

f (products) –  m H 
f (reactants)

where m, n = stoichiometric coefficients of the products and reactants in the given reaction .

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5 BOND ENERGY AND STANDARD ENTHALPY CHANGE OF ATOMISATION

5.1 Bond energy, B.E.

LO 7(c)(ii): explain and use the term, bond energy (H positive, i.e. bond breaking) (see also Topic 2 Chemical Bonding)

Bond energy is the energy required to break 1 mole of a covalent bond in the gaseous state.

E.g. H2(g) → 2H(g) B.E.(H−H) = +436 kJ mol−1

HCl(g) → H(g) + Cl(g) B.E. (H−Cl) = +431 kJ mol−1
½H2O(g) → H(g) + ½ O(g) B.E. (O−H) = +460 kJ mol−1

• Bond energies are always positive because energy is needed to pull the two atoms apart
(endothermic process) to break the covalent bond.

• Some bond energy data in the Data Booklet are average values derived from a large range of
molecules containing that particular covalent bond.
E.g. B.E. (C–Cl) = +340 kJ mol–1 (from Data Booklet)
However, average bond energy for the C–Cl bond in CCl4 = +327 kJ mol–1

5.2 Calculations using bond energy

LO 7(f)(iii) apply Hess’ Law to construct simple energy cycles and carry out calculations involving such cycles, with particular
reference to: average bond energies

• The enthalpy change of a reaction involving gaseous molecules can be calculated using bond
energy values.


Gaseous reactants H r Gaseous products

 B.E. (bonds broken) − B.E. (bonds formed)

Gaseous atoms

Hr =  B.E. (bonds broken) –  B.E. (bonds formed)

• As some bond energy data in the Data Booklet are average values, using them in calculations
can result in discrepancies when compared to values obtained by other means e.g. from
experiments or calculated from other enthalpy changes.

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Exercise 5.1 (Worked Example)

(a) Oxyacetylene torches, which operate at temperatures as high as 3300 °C, are fuelled by the
combustion of acetylene (i.e. ethyne), C2H2. The equation is given below:

2C2H2(g) + 5O2(g) → 4CO2(g) + 2H2O(g)

Use bond energy values from the Data Booklet to calculate Hr of the above reaction.


H r
2 H–CC–H + 5 O=O 4 O=C=O + 2

bonds broken bonds formed

4  C–H 4(410) 8  C=O 8(805)
2  CC 2(840) 4  O–H 4(460)
5  O=O 5(496)
5800 8280

Hr = +5800 – 8280 = –2480 kJ mol–1

Comments:
To help to visualize the types and number of bonds between the atoms, it is useful to draw
out the full structural formula of the molecules. Take note that bond breaking is endothermic
and bond forming is exothermic.

(b) Calculate another value for the Hr of this reaction using the following enthalpy changes of
formation.
Hf [C2H2(g)] = +227 kJ mol–1; Hf [CO2(g)] = –394 kJ mol–1; Hf [H2O(g)] = –242 kJ mol–1

Hr =  mHf (products) –  nHf (reactants)

= 4(−394) + 2(−242) − 2(+227)
= –2514 kJ mol–1

(c) Suggest a reason for the difference in the values of Hr, obtained in parts (a) and (b).

The bond energies given in the Data Booklet are the average bond energies of that particular
covalent bond in different types of molecules. These values may not apply to the specific
molecules in this reaction.

Exercise 5.2
Sulfur hexafluoride can be made by reacting sulfur tetrafluoride with fluorine.
SF4(g) + F2(g) → SF6(g) H = –434 kJ mol–1
By considering the bonds broken and bonds formed during the reaction, calculate a value for the
average bond energy of the S–F bond. State any assumptions you have made. [+296 kJ mol–1]

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5.3 Standard enthalpy change of atomisation

LO 7(c)(i)part: explain and use the term, enthalpy change of atomisation.

Hatom for an element is the energy required when 1 mole of gaseous atoms is formed from the
element at 298 K and 1 bar.

E.g. Na(s) → Na(g) HꝊatom = +107 kJ mol–1

½Br2(l) → Br(g) HꝊatom = +112 kJ mol–1
½H2(g) → H(g) HꝊatom = +218 kJ mol–1
What are some elements with enthalpy change of atomisation = 0 kJ mol–1?


H atom for a compound is the energy required to convert 1 mole of the compound into gaseous
atoms at 298 K and 1 bar.

E.g. CH4(g) → C(g) + 4H(g) HꝊatom = +1662 kJ mol–1

• HꝊatom values are always positive since atomisation involves breaking bonds.

• For gaseous diatomic elements, enthalpy change of atomisation and bond energy are related:
HꝊatom (X2) = ½  B.E. (X–X)

E.g. ½ Cl2(g) → Cl(g) HꝊatom = ½  B.E. (Cl−Cl) = ½(244) = +122 kJ mol–1

½ O2(g) → O(g) HꝊatom = ½  B.E. (O=O) = ½(496) = +248 kJ mol–1
½ N2(g) → N(g) HꝊatom = ½  B.E. (NN) = ½(944) = +472 kJ mol–1

LO 7(f)(iii) apply Hess’ Law to construct simple energy cycles and carry out calculations involving such cycles, with particular
reference to: average bond energies
Exercise 5.3
Phosphorus exists as P4 molecule with the following structure.

Use the following data to calculate the average bond energy of P−P bond.
Standard enthalpy change of formation of P4(g) = +58.91 kJ mol−1
Standard enthalpy change of atomisation of phosphorus = +314.4 kJ mol−1

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6 LATTICE ENERGY AND BORN-HABER CYCLE

LO 7(c)(iii)part: explain and use the term, lattice energy (H negative, i.e. gaseous ions to solid lattice)
LO 7(e): explain, in qualitative terms, the effect of ionic charge and of ionic radius on the numerical magnitude of a lattice
energy
LO 7(f): apply Hess’ Law to construct simple energy cycles, e.g. Born-Haber cycle, and carry out calculations involving such
cycles and relevant energy terms (including ionisation energy and electron affinity), with particular reference to: the
formation of a simple ionic solid

6.1 Lattice energy, L.E.

The heat evolved when 1 mole of solid ionic compound is formed from its constituent gaseous ions.

E.g. Na+(g) + Br−(g) → NaBr(s) L.E. = –742 kJ mol–1

Mg2+(g) + 2Cl −(g) → MgCl2(s) L.E. = –2326 kJ mol–1

• Lattice energy is always negative as heat is evolved in forming electrostatic forces of attraction
between oppositely charged ions (i.e. ionic bonding).

• Lattice energy is a measure of the strength of ionic bonding and the stability of the ionic
compounds. The more exothermic the lattice energy, the stronger the ionic bonding and the
more stable the ionic compound.

6.2 Factors affecting lattice energy

The magnitude of lattice energy depends on:
• the charges on the ions
• the sizes of ions or inter-ionic distance

These two factors can be combined into the following expression.

q+ and q− are the charges on the cation and anion respectively.

q+  q−
L.E. 
r+ + r−
(r+ + r−) is the inter-ionic distance between the two ions in the lattice.

Compound q+ q– r+ / nm r– / nm L.E. / kJ mol–1

NaCl +1 –1 0.095 0.181 –776
MgCl2 +2 –1 0.065 0.181 –2375
Table 4. Factors affecting lattice energy

• MgCl2 and NaCl have the same anion. Mg2+ has a higher charge and smaller ionic radius than
q+  q−
Na+. Since L.E.  , L.E. of MgCl2 is more exothermic than that of NaCl.
r+ + r−

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6.3 Born-Haber cycle

Lattice energy can be calculated using a Born-Haber cycle. A Born-Haber cycle is usually presented in
the form of an energy level diagram where the ‘zero reference line’ refers to the elements in the
standard states.

Energy/ kJ mol−1 Gaseous cation and anion

I.E. + E.A.

Gaseous atoms L.E.

Hatom
0 Elements
Hf Ionic solid

Figure 4. Outline of a Born-Haber cycle in energy level diagram format

Note: I.E. and E.A. should be represented by separate arrows. Refer to Exercise 6.1 / 6.2.

6.3.1 Ionisation Energy, I.E.

The first ionisation energy is the energy required to remove 1 mole of electrons from 1 mole of
gaseous atoms to form 1 mole of singly charged gaseous cations.

• I.E. is always positive since energy is required to remove an electron (endothermic process).

6.3.2 Electron Affinity, E.A.

The first electron affinity is the enthalpy change when 1 mole of electrons is added to 1 mole of
gaseous atoms to form 1 mole of singly charged gaseous anions.

• 1st E.A. is usually negative as the effective nuclear charge of the atom leads to an attraction of
the incoming electron. When the attraction is stronger, the energy given off is greater and hence
E.A. is more negative.

• 2nd and subsequent E.A. are always positive because energy is required to overcome the
electrostatic repulsion between the incoming electron and the anion.
E.g. O(g) + e− → O−(g) 1st E.A. = –141 kJ mol–1
O− (g) + e− → O2−(g) 2nd E.A. = +844 kJ mol–1

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Exercise 6.1 (Worked Example)

Construct a Born-Haber cycle for the formation of Na2O from its elements and calculate the lattice
energy of Na2O from the following data:

H/ kJ mol–1
Enthalpy change of formation of Na2O(s) –414
Enthalpy change of atomisation of sodium +107
First electron affinity of oxygen –141
Second electron affinity of oxygen +844

By Hess’s Law,
−414 = 2(107) + ½(496) + 2(494) −141 + 844 + L.E.
–414 = 2153 + L.E.
 L.E.(Na2O) = –2567 kJ mol–1

Comments:
Elements are placed on the ‘zero reference line’ on the energy axis. As we are drawing an energy
level diagram, the relative energy levels at each step need to correspond to their relative positions
on the energy axis. As such, if the enthalpy change of the reaction is negative (exothermic), the
arrow is drawn pointing down, and if the enthalpy change of the reaction is positive (endothermic),
the arrow is drawn pointing up.

Exercise 6.2
Construct a Born-Haber cycle for the formation of CaCl2 from its elements and calculate its lattice
energy from the following data and relevant data from the Data Booklet.
Hatom of Ca = +178 kJ mol−1; Hf of CaCl2 = −796 kJ mol−1; First E.A. of Cl = −349 kJ mol−1;
[−2260 kJ mol–1]

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6.4 Experimental versus theoretical lattice energies

• Experimental lattice energy refers to the value found from experimental results using the
Born-Haber cycle.

• Theoretical lattice energy refers to the value calculated based on a model which assumes that
the compound is completely ionic.

• There is always a difference between the two values which suggests that no compound is
completely ionic (Refer to Topic 2 Chemical Bonding for the continuum from a theoretical pure
ionic model to purely covalent compounds.)

• A small difference shows that the ionic model is a good one for the compound.

• A large difference shows that there is covalent character in the ionic compound. This is most
apparent when a cation with a high charge density distorts an anion with a large electron cloud.

Compound Theoretical L.E. / kJ mol–1 Experimental L.E. / kJ mol–1

CsCl –657 –659
MgCl2 –2326 –2375
AgF –953 –967
AgI –808 –889
Table 5. Theoretical and Experimental lattice energies of some compounds

• There is good agreement between the theoretical and experimental lattice energy for CsCl but
the discrepancy is greater for MgCl2. Mg2+ has higher charge and smaller ionic radius than Cs+.
Mg2+ thus has higher charge density and greater polarising power than Cs+. Hence Mg2+ distorts
the electron cloud of Cl− to a greater extent, resulting in greater covalent character in MgCl2.

• There is also close agreement between the theoretical and experimental lattice energy for AgF
but not for AgI. This is because I− has a larger ionic radius than F− and is hence more polarisable.
Thus Ag+ polarises the electron cloud of I− to a larger extent, resulting in greater covalent
character in AgI.

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7 STANDARD ENTHALPY CHANGES OF HYDRATION AND SOLUTION

LO 7(c)(i)part: explain and use the terms: enthalpy change of hydration; solution
LO 7(f)(ii): apply Hess’ Law to construct simple energy cycles, and carry out calculations involving such cycles and relevant
energy terms, with particular reference to: the formation of a simple ionic solid and of its aqueous solution

7.1 Standard enthalpy change of hydration

The heat evolved when 1 mole of free gaseous ions is dissolved in an infinite volume of water at
298 K and 1 bar.

E.g. Na+(g) + aq → Na+(aq) HꝊhyd = –405 kJ mol–1

Br‾(g) + aq → Br‾(aq) HꝊhyd = –337 kJ mol–1


• H hyd is always negative (regardless of anion or cation) as heat is evolved in forming ion-dipole
interactions between the ions and the polar water molecules.

Figure 5. Hydrated Na+ and Br− ions

• The magnitude of Hhyd of an ion depends on its charge density. (Refer to Topic 2 Chemical
Bonding for the definition of charge density.)

q
Hhyd 
r

The higher the charge density of the ion, the stronger the ion-dipole interaction and Hhyd will
be more exothermic.
E.g. Na+(g) + aq → Na+(aq) HꝊhyd = –405 kJ mol–1 ; Na+ = 0.095 nm
Mg2+(g) + aq → Mg2+(aq) HꝊhyd = –1920 kJ mol–1 ; Mg2+ = 0.065 nm

7.2 Standard enthalpy change of solution, Hsol

The enthalpy change when 1 mole of solute is completely dissolved in an infinite volume of solvent
at 298 K and 1 bar.

E.g. NaCl(s) → Na+(aq) + Cl‾(aq) HꝊsol = +3.88 kJ mol–1

MgCl2(s) → Mg2+(aq) + 2Cl‾(aq) HꝊsol = –160 kJ mol–1

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• The solute is usually an ionic compound while the solvent is usually water.
• HꝊsol can be either positive or negative.
If HꝊsol is highly positive  salt is likely insoluble
If HꝊsol is negative  salt is likely soluble

Note: There are salts with positive HꝊsol and are soluble e.g. NaCl, KCl, NH4NO3 due to positive
entropy change (Refer to Section 8).

7.3 Relationship between lattice energy, enthalpy changes of hydration and enthalpy change of
solution

• The dissolution of an ionic solid MX(s) can be divided into 2 processes:

1) Breaking up the solid ionic lattice to form isolated gaseous ions.

Process is endothermic (overcoming ionic bonding) and the enthalpy change is ‘–LE’.

MX(s) → M+(g) + X–(g) H = –LE

2) Hydration of the gaseous ions.

Process is exothermic (forming ion-dipole interactions between ion and water).

M+(g) + X–(g) + aq → M+(aq) + X–(aq) H = Hhyd(M+) + Hhyd(X–)

Overall MX(s) → M+(aq) + X–(aq) HꝊsol = – L.E. + sum of HꝊhyd

If | L.E. | > | HꝊhyd |  HꝊsol > 0 (endothermic) – Refer to diagram below

If | L.E. | < | HꝊhyd |  HꝊsol < 0 (exothermic) – try drawing the energy level diagram

Energy / kJ mol−1
Gaseous ions M+(g) + X−(g)

Hhyd(cation)
+
L.E. Aqueous ions M+(aq) + X−(aq) Hhyd(anion)

Hsoln
Ionic solid MX(s)

Figure 6. Energy level diagram to determine enthalpy change of solution of an ionic solid

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Exercise 7.1 (Worked Example)

(a) By means of an appropriate energy cycle, calculate the enthalpy change of hydration of the
chloride ion using the data provided.

Enthalpy change of solution of NaCl(s) +5 kJ mol–1

Enthalpy change of hydration of Na+(aq) –390 kJ mol–1
Lattice energy of NaCl(s) –776 kJ mol–1

Hsol = +5 + –
NaCl(s) Na (aq) + Cl (aq)

+ –
L.E. = –776 Hhyd(Na ) + Hhyd(Cl )
+ – –
Na (g) + Cl (g) = –390 + Hhyd(Cl )
By Hess’s Law,
–776 + 5 = –390 + Hhyd (Cl–)
Hhyd (Cl–) = –381 kJ mol–1

(b) The enthalpy change of hydration of iodide ion was found to be −296 kJ mol−1. Comment on
the difference between this value and the value found in (a).
𝑞
 Hhyd  
𝑟
I− has the same charge but a larger ionic radius than Cl–.
So the ion-dipole attractions between I− ion and the water molecules are weaker.
Hence, Hhyd of I− is less exothermic than that of Cl–.

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8 ENTROPY AND GIBBS FREE ENERGY CHANGE

8.1 Spontaneous processes (Background info)

From our experience, there are processes that take place on its own. For example, if we ignite a
mixture of hydrogen and oxygen, they combine rapidly to form water. An iron nail rusts slowly when
left to stand. All of these chemical reactions can be described as spontaneous. There are also physical
processes which are spontaneous. For example, when a drop of dye is placed in a beaker of water,
diffusion takes place resulting in a uniformly coloured solution.

A spontaneous process is one that takes place naturally in the direction stated. In other words, the
change occurs without a need for continuous input of energy from outside the system.

It is useful to predict if a reaction will occur spontaneously when reactants are brought together under
a certain set of conditions. When we think of spontaneous process, many of the examples we have
seen, such as combustion, are exothermic processes.

However, there are endothermic reactions which are also spontaneous.

For example, N2O5(s) → 2NO2(g) + ½O2(g) H = +109.5 kJ mol–1

Many soluble salts (e.g. NaCl, KCl, NH4NO3) dissolve endothermically and spontaneously.

For example, KCl(s) → KCl(aq) H = +25.7 kJ mol–1

Hence, the sign of H by itself does not predict if a reaction is spontaneous.

If we examine the two examples above, they have one major feature in common: the chemical species
(atoms, molecules, or ions) have more freedom of motion after the change. The particles have a wider
range of energy of motion (kinetic energy) which means the energy has become more dispersed or
distributed.

When solid N2O5 changes to gaseous NO2 and O2, the motion of the molecules in the solid state is
restricted while the gaseous particles have more freedom of motion. Thus the energy of motion is
more distributed after the change.

Similarly, dissolving a salt separates the ions in the crystalline solid. The ions in the aqueous state have
greater freedom of motion (or are more disordered) and their energy of motion is more distributed.

Hence, a change in the freedom of motion of particles in a system, that is, the distribution of their
energy of motion, is one key factor affecting the direction of a spontaneous process. This factor is
known as entropy change.

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8.2 Entropy and entropy changes

LO 7(g): explain and use the term entropy

Entropy ‘S’ is a measure of the randomness or disorder in a system, reflected in the number of ways
that the energy of a system can be distributed through the motion of its particles. Units: J mol–1 K–1.

For the same amount of a substance, entropy of solid < liquid << gas.

In a solid, the particles are relatively fixed and possess the least kinetic energy.
There are few ways that the energy of particles is distributed.

In a gas, the particles are able to move freely and possess a wide range of kinetic
energy. There are many ways that the energy of the particles is distributed.

Figure 7. Arrangement of particles in solid and gaseous state

Many chemical reactions or physical processes are accompanied by a change in entropy, S.
• If a reaction or process results in more ways to disperse or distribute the energy, entropy
increases (S > 0).
• If a reaction or process results in less ways to disperse or distribute the energy, entropy
decreases (S < 0).

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8.3 Predicting the sign of S for some processes

LO 7(h): discuss the effects on the entropy of a chemical system by the following: (i) change in temperature, (ii) change in
phase, (iii) change in the number of particles (especially for gaseous systems), (iv) mixing of particles
[quantitative treatment is not required]
LO 7(i): predict whether the entropy change for a given process or reaction is positive or negative

(1) Change in temperature

As temperature increases, the average kinetic energy of the particles and the range of energies
increase as shown in the Maxwell-Boltzmann distribution curves below. (Refer to Topic 3 The Gaseous
State for explanation on the shape of the curves.) There are more ways to disperse the energy among
the particles. Hence, entropy increases (S increases, S is positive).

Fraction of T1
particles

T2 > T1

0 kinetic energy
Figure 8. Maxwell–Boltzmann distribution curve

(2) Change in phase

Figure 9. Change in entropy during phase change

• The particles in the solid state vibrate about their fixed positions. The energy is thus the least
dispersed and the solid has the lowest entropy.

• When temperature increases, entropy increases gradually as the kinetic energy of the particles
increases.

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• When the solid melts, the particles move more freely in the liquid state and become more
disordered. Hence there is an abrupt increase in entropy (S > 0) as there are more ways to
distribute the particles and their energy in the liquid state.

• Likewise, as the liquid is heated, its entropy increases as the particles gain kinetic energy. During
vaporisation, the liquid converts to a gas where the particles are able to move even more
freely. Hence there is a large increase in entropy (S >> 0) as there are more ways to distribute
the particles and their energy in the gaseous state.

(3) Change in the number of particles (especially gaseous particles)

• When a chemical reaction results in an increase in the number of gas particles, there is a large
increase in entropy. This is because the particles in gas are the most disordered so the number
of ways that the particles and the energy can be distributed increase greatly.

For example, many decomposition reactions result in an increase in the number of gas particles,
hence an increase in entropy.

N2O(g) → N2(g) + ½O2(g) no. of gas particles increase by 0.5 mol, S > 0
2NaN3(s) → 2Na(s) + 3N2(g) no. of gas particles increase by 3 mol, S > 0

• If there is no change in the number of gas particles, entropy may increase or decrease but S
will be relatively small numerically. For example,

N2(g) + O2(g) → 2NO(g) S  0

(4) Mixing of particles

• Consider the mixing of equimolar H2 gas and N2 gas at constant pressure as shown below.
Before mixing, each gas has the same volume and pressure. After the barrier is removed, each
gas expands to occupy the whole container and hence the volume of each gas doubles. The
partial pressure of each gas is reduced by half but total pressure remains constant.

H2 N2 Gases mixed
Figure 10. Mixing of 2 gases at constant pressure

As the volume available for each gas (H2 and N2) is increased, there are more ways to distribute
the particles and hence their energy. Thus, entropy increases (S > 0).

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Note:
When a gas expands, the volume available for distribution of the particles increases. Entropy
increases as there are more ways that the particles and the energy can be distributed.

Figure 11. Expansion of gas

• When gases are mixed at constant volume, i.e. the volume available to distribute each gas
particle is the same. Hence the entropy does not change (S = 0).

Figure 12. Mixing of 2 gases at constant volume

• When liquids with similar polarities (e.g. benzene and hexane) are mixed together, entropy
increases. This is because total volume increases and hence there are more ways to distribute
the particles and hence their energy.

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(5) Dissolution of an ionic solid

Two entropy terms operate when an ionic solid is dissolved in water:

• Entropy increases because the ions in the solid are free to move in solution.
• Entropy decreases because water molecules that were originally free to move become
restricted in motion as they arrange themselves around the ions.

If the first factor is more significant, the overall entropy change is positive.

E.g. NaCl(s) + aq → Na+(aq) + Cl–(aq) S > 0

Figure 13. Entropy change during dissolution of an ionic solid

In Topic 2 Chemical Bonding, we saw that dissolution of a compound depends on the energy change.
In addition to enthalpy change, the entropy change also plays a part when predicting the solubility of
a compound.

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Exercise 8.1
Predict whether S is positive or negative in each of the following processes.

Process Sign of S Explanation

(a) N2(g) + 3H2(g) → 2NH3(g) – Number of gas molecules decreases.
The number of ways that the particles and the
energy can be distributed decrease.
Hence, there is a decrease in entropy.

(b) H2O(l) → H2O(g) + When a liquid vaporizes into a gas, the particles in
the gaseous state move more freely and are in a
more disordered state than in the liquid state.
There is an increase in number of ways that the
particles and the energy can be distributed.
Hence, there is an increase in entropy.

(c) CaCO3(s) → CaO(s) + CO2(g) + Number of gas molecules increases.

The number of ways that the particles and the
energy can be distributed increase.
Hence, there is an increase in entropy.

(d) 1 mol of Cl2(g) at 298K is heated + As temperature increases, the average kinetic
to 373K energy of the particles and the range of energies
increase.
There are more ways to disperse the energy among
the particles.
Hence, entropy increases.

(e) Na+(g) + Cl–(g) → NaCl(s) – Gaseous ions are converted into an ionic solid
where are the ions are more ordered.
The number of ways that the particles and the
energy can be distributed decrease.
Hence, there is a decrease in entropy.

(f) Ar at 2 atm → Ar at 1 atm + When pressure is decreased, the volume available

for the gas is increased.
There are more ways that the particles and the
energy can be distributed.
Hence, entropy increases.

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8.4 Gibbs free energy change

LO 7(j): state and use the equation involving standard Gibbs free energy change of reaction, G: G = H − TS [the
calculation of standard entropy change, S, for a reaction using standard entropies, S, is not required]
LO 7(k): state whether a reaction or process will be spontaneous by using the sign of G

The Gibbs free energy change of reaction is given by:

G = H – TS

Units of G and H : kJ mol–1 or J mol–1

Units of S : kJ mol–1 K–1 or J mol–1 K–1 Josiah Willard Gibbs (1839 – 1903),
Units of T :K the father of chemical thermodynamics

The standard Gibbs free energy change of reaction, GꝊ, is the Gibbs free energy change needed to
convert reactants into products at 1 bar and at constant temperature (usually at 298 K).

We can use the sign of G to predict if a reaction is spontaneous.

G < 0 G = 0 G > 0
The reaction takes place The system is at equilibrium. The reaction cannot take place
spontaneously. There is no net reaction in spontaneously.
the forward or backward It is spontaneous in the reverse
direction. direction.

The reaction is said to be E.g. G = 0 during melting The reaction is said to be

exergonic. and boiling at the melting endergonic.
point and boiling point
respectively
Table 6. Sign of G and spontaneity of reaction

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8.4.1 Calculations using G = H − TS

Exercise 8.2 (Worked Example) Calculating G from H and S

Chemical Reaction H / kJ mol–1 S/ J mol–1 K–1

2Fe(s) + 3/2O2(g) → Fe2O3(s) –825 –272

Calculate the standard Gibbs free energy change for the rusting of iron.

−272
G = H – TS = –825 – 298( 1000 ) = –744 kJ mol–1

Comments:
The energy units of H and TS must be made compatible (i.e. standardise to kJ mol–1 or J mol–1).

means that the temperature is at 298 K.
Since G < 0, the rusting of iron is spontaneous at room temperature which is consistent with
our observation/daily experience.

Exercise 8.3

Chemical Reaction H / kJ mol–1 S/ J mol–1 K–1

2NaHCO3(s) → Na2CO3(s) + H2O(g) + CO2(g) +130 +335

Calculate the standard Gibbs free energy change for the decomposition of one mole of sodium
hydrogen carbonate. [+15.1 kJ mol–1]

Exercise 8.4 Calculating S for phase change

Given the enthalpy change of fusion of ice (conversion of solid ice to liquid water) is 6.0 kJ mol–1,
calculate the entropy change which accompanies the melting of ice.

Exercise 8.5

Given the enthalpy change of vaporisation of water is 44.0 kJ mol–1, calculate the entropy change
which accompanies the boiling of water. [+118 J mol–1 K–1]
Comment on the difference in magnitude of Svaporisation with Sfusion for water.

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8.4.2 Calculations of Gr from Gf

Like enthalpy change (H), Gibbs free energy change (G) is a state function. This means that the
value that it takes only depends on the state of the substance, and not how it was brought to that
state. The ‘state’ is specified by variables such as temperature and pressure. Hence G of a reaction
can be calculated in a similar way as H in Section 4 (Hess’ law). Likewise, S is a state function and
S of a reaction can also be calculated a similar way.

Exercise 8.6
7
Calculate GꝊ for the reaction C2H6(g) + O2(g) → 2CO2(g) + 3H2O(l) using the data below.
2
GꝊf (C2H6(g)) = −32.9 kJ mol−1; GꝊf (CO2(g)) = −394.4 kJ mol−1; GꝊf (H2O(l)) = −237.2 kJ mol−1;

8.4.3 Temperature dependence of G

The term [–TS] in the equation G = H – TS indicates that G is temperature-dependent.

We can assume that H and S remain roughly constant regardless of temperature and use them to
calculate G at other temperatures. This assumption is valid as shown in the following example
involving the reaction between hydrogen gas and chlorine gas at 298 K and 500 K.

T /K H /kJ mol–1 S /J mol–1 K–1 TS /kJ mol–1 G /kJ mol–1

H2(g) + Cl2(g) → 2HCl(g) 298 –184.6 +20.0 +6.0 –190.6
H2(g) + Cl2(g) → 2HCl(g) 500 –185.6 +17.5 +8.8 –194.4

If we were to assume that H and S do not change with temperature, we can use the values of H
and S at 298 K to calculate a value for G at 500 K as shown:

G500K  H298K – 500 x S298K

= –184.6 – 500 x 20.0 = –194.6 kJ mol–1
1000

This approximate value of G (–194.6 kJ mol–1) is close to the actual value (–194.4 kJ mol–1) obtained
by using values of H and S at 500 K.

The assumption that H and S remain roughly constant is not valid if there is a change in phase of
one of the reactants or products as the temperature is increased. Under these conditions, both H
and S change significantly. For example, consider the synthesis of hydrogen iodide at 298 K and
500 K.
T/K H/ kJ mol–1 S/ J mol–1 K–1 TS/ kJ mol–1 G/ kJ mol–1
H2(g) + I2(s) → 2HI(g) 298 +53.0 +166 +49.5 +3.5
H2(g) + I2(g) → 2HI(g) 500 –11.0 +18 +9.0 –20.0

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As a result of the phase change in I2 (from solid to gaseous), G changes from being slightly positive
at 298 K to being very negative at 500 K. This means that the synthesis of HI is not spontaneous at
room temperature but it becomes spontaneous if the temperature is raised above the boiling point of
I2.

Exercise 8.7 (Worked Example) Calculating the temperature at which a reaction becomes
spontaneous.

The standard enthalpy change of formation, HꝊf , and the standard Gibbs free energy change of
formation, GꝊf , of CO(g) and of CO2(g) are as follows.

CO(g) CO2(g)
HꝊf / kJ mol –1
–110.5 –393.5
GꝊf / kJ mol–1 –137.2 –394.4

(a) Calculate the standard entropy change of formation, SꝊf , in J mol−1 K−1, of CO(g) and of
CO2(g). [+89.6 J mol-1 K-1; +3.02 J mol-1 K-1]
G = H – TS  S = (H – G) / T

C(s) + ½O2(g) → CO(g)

−110.5−(−137.2)
Sf = = +0.0896 kJ mol–1 K–1
298

C(s) + O2(g) → CO2(g)

−393.5−(−394.4)
Sf = 298
= +0.00302 kJ mol–1 K–1

(b) Using the HꝊf values given and your answers in (a), show that the reaction:
C(s) + CO2(g) → 2CO(g) is not spontaneous at 298 K and calculate the minimum temperature
at which reaction becomes spontaneous.
C(s) + CO2(g) → 2CO(g)

Hr =  mHf (products) –  nHf (reactants)

Hr = 2(–110.5) – (–393.5) = +172.5 kJ mol–1
Sr =  mSf (products) –  nSf (reactants)

S r = 2(+0.0896) – (+0.00302) = +0.1762 kJ mol–1 K–1


At 298 K, G r = +172.5 – 298(+0.1762) = +120 kJ mol–1 > 0
Hence, reaction is not spontaneous.

To be spontaneous, G < 0  H − TS < 0

TS > H
T > H /S
T > 172.5 / 0.1762
T > 979 K

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Exercise 8.8

The standard enthalpy and entropy changes for the thermal decomposition of sodium
hydrogencarbonate are given below:

Chemical Reaction HꝊ /kJ mol–1 SꝊ /J mol–1K–1

2NaHCO(s) → Na2CO3(s) + H2O(g) + CO2(g) +130 +335

Calculate the temperature at which the decomposition becomes spontaneous. [388 K]

8.4.4 Effect of Temperature on spontaneity of a reaction

LO 7(m): predict the effect of temperature change on the spontaneity of a reaction, given standard enthalpy and entropy
changes

For a reaction to be spontaneous, G should be negative. The sign of G depends on the signs and
magnitudes of H and S, as well as temperature. We observe that most exothermic reactions are
spontaneous as the enthalpy contribution to G is much more than the entropy contribution. Hence
a highly negative H is likely to make G negative. However, the temperature of a reaction influences
the magnitude of the term TS and hence the spontaneity of many reactions depends on the
temperature. We can use the equation G = H − TS to predict the sign of G when temperature is
varied (assuming H and S do not change with temperature).

There are four possibilities:

If H is and S is G (= H − TS) is Reaction is

negative positive always negative spontaneous at all temperatures

positive negative always positive not spontaneous at all temperatures

spontaneous at low temperatures

negative negative negative if H > TS
(reaction is enthalpy driven)
spontaneous at high temperatures
positive positive negative if H < TS
(reaction is entropy driven)
Table 7. Effect of Temperature on spontaneity of a reaction

(1) H negative and S positive

−TS is always negative hence G < 0 for all temperatures. These reactions are always spontaneous,
so a continuous input of energy from outside the system is not needed for such reactions.

(2) H positive and S negative

−TS is always positive hence G > 0 for all temperatures. Reactions of this type are not spontaneous
and energy must be continuously supplied for the process to take place.

(3) H and S both negative

At low temperatures, TS < H, so G < 0. These exothermic reactions are spontaneous at low
temperatures.

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Hwa Chong Institution 2023 05 – Chemical Energetics: Thermochemistry & Thermodynamics

(4) H and S both positive

At high temperatures, TS > H, so G < 0. These endothermic reactions, which may not be
spontaneous at room temperature, become spontaneous if the temperature is sufficiently raised.

For example, at 25 C, Gvap(H2O) = Hvap(H2O) − TSvap(H2O) = 44.0 – 298(118/1000) = +8.84 kJ mol−1
> 0. This means that boiling of water is not spontaneous at room temperature which is consistent with
our observation. When temperature is raised to 100 C, G = 0 which means liquid water and steam
are in equilibrium. At temperature above 100 C, G < 0 and hence the boiling of water is
spontaneous.

Water boils (Gvap = 0)

Water exists predominantly Water exists predominantly
as a liquid (Gvap > 0) as a gas (Gvap < 0)
Temperature /C
25 C 100 C
Figure 14. Effect of temperature on spontaneity of boiling of water

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Hwa Chong Institution 2023 05 – Chemical Energetics: Thermochemistry & Thermodynamics

Exercise 8.9
For each of the following reactions, explain whether the reaction is spontaneous at all temperatures,
at low temperature, at high temperature or not spontaneous at all temperatures. Predict how G will
change with increasing temperature.
Explain whether the reaction is
Predict how G will
spontaneous at all temperatures, at low
Reaction change with increasing
temperature, at high temperature or not
temperature.
spontaneous at all temperatures.
Example
S is positive since there is an increase in When temperature
number of moles of gas. Hence there are increases, TS becomes
more ways to distribute the particles and more positive.
their energies. G = H − TS
2N2O(g) + O2(g) → 4NO(g)
G = H − TS Hence G becomes more
H = +197.1 kJ mol−1
G is negative when TS > H, i.e. when negative.
temperature is high.
The reaction is spontaneous when
temperature is high.

2H2O2(l) → 2H2O(l) + O2(g)

H = −196 kJ mol−1

3O2(g) → 2O3(g)
H = +286 kJ mol−1

2SO2(g) + O2(g) → 2SO3(g)

H = −198 kJ mol−1

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Hwa Chong Institution 2023 05 – Chemical Energetics: Thermochemistry & Thermodynamics

8.5 Limitation in the use of G to predict spontaneity of a reaction

LO 7(l): understand the limitations in the use of G to predict the spontaneity of a reaction

8.5.1 Non-standard condition

G can only be used to predict spontaneity of a reaction under standard conditions. Under non-


standard conditions, G must be calculated.

8.5.2 Kinetics consideration

It is important to keep in mind that just because a reaction is spontaneous does not mean that it will
occur at an observable rate.

While the Gibbs free energy change can be used to determine the spontaneity of a reaction, it does
not take into account the kinetics of the reaction, that is, the rate at which the reaction takes place.
The reacting species may have to overcome a large energy barrier (Ea) before reaction can occur.

Some reactions are thermodynamically (or energetically) favourable (G is negative) but kinetically
not favourable (occur very slowly). Such reactions are spontaneous but slow, for example rusting.
Another example is the conversion of diamond into graphite.

C(diamond) → C(graphite)

With respect to graphite, diamond is thermodynamically less stable (G < 0). However, due to the high
activation energy for the reaction, diamond does not turn into graphite overnight. We say that
diamond is kinetically stable.

LOOKING AHEAD
We have seen in this topic that energy is the key consideration for any transformation to take place –
energy (and/or matter) tends to be dispersed during a chemical or physical change. However, not all
transformations take place at considerable rate (as mentioned in Section 9.4) and transformation from
reactants to products may not occur to completion. In the next two topics, we will be looking at some
characteristics of chemical and physical change, such as the rate of change (reaction kinetics) as well
as the extent of change (chemical equilibrium). We will revisit the concept of Gibbs free energy change
and learn how the value of G can allow us to predict the extent of change (chemical equilibrium).

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Hwa Chong Institution 2023 05 – Chemical Energetics: Thermochemistry & Thermodynamics

Summary of enthalpy terms

Enthalpy change Definition Examples Sign

Enthalpy change of
formation

Enthalpy change of
combustion

Enthalpy change of
neutralisation

Bond energy

Enthalpy change of
atomisation

Lattice energy

Ionisation energy

Electron affinity

Enthalpy change of
hydration

Enthalpy change of
solution

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Hwa Chong Institution 2023 06 – Reaction Kinetics

06 Reaction Kinetics
GUIDING QUESTIONS:
• What do we mean by rate of reaction? How could we measure it?
• What are the factors affecting rate? Why?
• How can we determine and express the relationship between rate and
concentration mathematically? How are the other factors affecting rate featured in
this equation?
• What can we infer about the mechanism of a reaction from the order of reaction?
Why do many reactions not occur in a single step?
• What are the general types of catalysts? How are they similar and how do their modes of action differ?

LEARNING OUTCOMES
Students should be able to:
8(a) explain and use the terms: rate of reaction; rate equation; order of reaction; rate constant; half-life
of a reaction; rate-determining step; activation energy; catalysis
8(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 multi-step processes with a rate-determining step, for which m and n are 0, 1 or 2),
including:
(i) deducing the order of a reaction by the initial rates method
(ii) justifying, 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
(v) calculating an initial rate using concentration data
[integrated forms of rate equations are not required]
8(c) (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
8(d) calculate a rate constant using the initial rates method
8(e) devise a suitable experimental technique for studying the rate of a reaction, from given information
8(f) explain qualitatively, in terms of frequency of collisions, the effect of concentration changes on the
rate of a reaction
8(g) show understanding, including reference to the Boltzmann distribution, of what is meant by the term
activation energy
7(b) construct and interpret an energy profile diagram, in terms of the enthalpy change of the reaction
and of the activation energy
8(h) explain qualitatively, in terms of both the Boltzmann distribution and of collision frequency, the
effect of temperature change on a rate constant (and hence, on the rate) of a reaction
8(i) (i) explain that, in the presence of a catalyst, a reaction has a different mechanism, i.e. one of
lower activation energy, giving a larger rate constant
(ii) interpret this catalytic effect on a rate constant in terms of the Boltzmann distribution

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Hwa Chong Institution 2023 06 – Reaction Kinetics

8(j) 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 (refer to Topic
10 Alkanes under catalytic converter)
(iii) the catalytic role of atmospheric oxides of nitrogen in the oxidation of atmospheric sulfur
dioxide
(iv) catalytic role of Fe2+ in the I–/S2O82– reaction
8(k) describe enzymes as biological catalysts which may have specific activity
8(l) explain the relationship between substrate concentration and the rate of an enzyme-catalysed
reaction in biochemical systems

REFERENCES
1. Cann & Hughes, Chemistry for Advanced Level, Chapters 8 & 21.
2. Martin S. Silberberg, Chemistry The Molecular Nature of Matter and Change, 6th Ed., Chapter 16
3. Petrucci & Harwiidm General Chemistry – Principles and Modern Applications, 6th Ed., Chapter 15

LOOKING BACK
Topic 5 Chemical Energetics looked at energy changes of reactions, in terms of enthalpy, entropy and
Gibbs’ free energy. While the sign of △G may indicate the direction of chemical change, it gives no
information on how fast a reaction occurs. A thermodynamically spontaneous reaction (where △G is
negative) may be so slow that no significant reaction could be observed. The study of the rates of
chemical reactions is called kinetics. The rate of reaction depends on a number of factors, each of
which can be studied separately, and can only be determined by experiment.

1 INTRODUCTION

Rates of reaction are studied for two reasons:

• To discover the best conditions to make the reaction go as quickly or as slowly as possible.
Some reactions need to be fast, for example, those which occur inside your body when you take
a pain reliever; while some reactions should be as slow as possible, like the rusting of iron in
machinery and motor vehicles.

• To gather information about the mechanism, that is, how the reaction actually takes place.
Reaction mechanisms are particularly important when studying organic reactions.

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Hwa Chong Institution 2023 06 – Reaction Kinetics

2 THE RATE OF A REACTION

2.1 Rate of reaction

LO8(a)part: explain and use the terms: rate of reaction

The rate of a reaction is defined as the change in concentration of a reactant or a product per unit
time.

Mathematically,

d [product] d [reactant]
rate = or rate = −
dt dt

Since [reactant] decreases during a reaction,

d[reactant]/dt is negative. The negative sign is
added to give a positive value to rate.

Units of rate: mol dm−3 s−1 (or other units of time, e.g. mol dm−3 min−1)

Consider the reaction: H2 + I2 → 2HI

For every mole of H2 that is consumed, one mole of I2 is also consumed and 2 moles of HI are formed.
Hence, the change in concentrations of H2 and I2 are the same, but the change in concentration of HI
is two times faster.

d[H2 ] d[I ] 1 d[HI]

We express the rate as: rate = − =− 2 =
dt dt 2 dt

When there are different coefficients in the chemical equation, we commonly define the rate in terms
of the substance with a coefficient of 1.

Exercise 2.1 (worked example)

For the reaction, BrO3−(aq) + 5Br−(aq) + 6H+(aq) → 3Br2(aq) + 3H2O(l), which of the following
relationships are correct?

d [Br2 ] d [H2O]
1 =
dt dt
d [Br2 ] d [BrO3− ]
2 =− 3
dt dt
d [Br − ] d [H+ ]
3 −5 = −6
dt dt

A 1, 2 and 3 are correct

B 1 and 2 only are correct
C 2 and 3 only are correct
D 1 only is correct

For every mole of BrO3−(aq) consumed, 5 moles of Br−(aq) and 6 moles of H+(aq) are consumed,
while 3 moles of Br2(aq) is produced. Hence we can see that the rate of consumption of H+(aq) is
the highest, followed by rate of consumption of Br−(aq), then rate of production of Br2(aq). The rate
of consumption of BrO3−(aq) is the slowest.

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Hwa Chong Institution 2023 06 – Reaction Kinetics

𝑑[𝐵𝑟𝑂3 − ] 1 𝑑[𝐵𝑟 − ] 1 𝑑[𝐻 + ] 1 𝑑[𝐵𝑟2 ]

We express the rate as: rate = − =− =− = based on
𝑑𝑡 5 𝑑𝑡 6 𝑑𝑡 3 𝑑𝑡
the coefficients of the aqueous species present. Hence only options 1 and 2 are correct.

2.2 Instantaneous, Initial and Average Rates

Since the rate of a reaction is defined as the change in concentration of a reactant or a product per
unit time, we can obtain the rate of a reaction from the gradient of the tangent of a concentration-
time graph.

Figure 1 shows the concentration-time graphs for the decomposition of dinitrogen tetraoxide into its
monomers: N2O4 (g) → 2NO2 (g).

The rate of a reaction at a specified time t is called the instantaneous rate of reaction. It can be
determined from the gradient of the tangent at time t, as shown in Figure 1.

When t = 0, the rate is called the initial rate of reaction, which is the rate at the start of a reaction.
It can be determined from the gradient of the tangent at t = 0.

The average rate of reaction is the change in concentration of a reactant or a product over a specified
time interval.

A negative gradient indicates a decrease in concentration while a positive gradient indicates an

increase in concentration. In Figure 1, the [N2O4]-time graph has a negative gradient since N2O4 is the
reactant, while the [NO2]-time graph has a positive gradient since NO2 is the product.

The steeper the gradient, the faster the rate of

reaction. When gradient is zero, there is no
change in concentration. This means rate of
reaction is zero, i.e. the reaction has stopped.

By comparing the gradients of the tangents at

time t, we can see that the rate of change in
concentration of NO2 is twice as fast as the rate
of change in concentration of N2O4.

The rate of reaction at time t can be expressed

as: rate = − d[N2O4 ] = 1 d[NO2 ]

dt 2 dt

Figure 1. Concentration-time graphs for the reaction, N2O4 (g) → 2NO2 (g)

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 Hwa Chong Institution 2023 06 – Reaction Kinetics

Exercise 2.2 [source of data: N2000/1/3] (worked example)

The following data and graph were obtained for the reaction, CH3Br + OH− → CH3OH + Br−.
time t /min 0 40 80 120 160 200 240
–3
[CH3Br] /mol dm 0.0100 0.0079 0.0062 0.0049 0.0038 0.0030 0.0024

[CH3Br] 0.0100
/ mol dm–3
0.0090

0.0080

0.0070

0.0060

0.0050

0.0040

0.0030

0.0020
0 20 40 60 80 100 120 140 160 180 200 220 240 t / min

(a) Determine the initial rate of the above reaction.

Note that the units of rate follows the unit of time on the x-axis in the concentration-time graph.

The initial rate is the rate of reaction at t = 0. Draw a tangent at t = 0 min to find the gradient. Note
that although the gradient is negative, the rate of a reaction is always expressed as a positive number.

0.0100 − 0.0024
initial rate = − = 5.43  10–5 mol dm–3 min–1
0 − 140

A range of answers is accepted to accommodate errors. [Range: 4.80 to 6.00  10–5 mol dm–3 min–1]

(b) Determine the instantaneous rate of the above reaction at t = 120 min.

Draw a tangent at t = 120 min to find the instantaneous rate at 120 min.

0.0076 − 0.0032
rate at 120 min = − = 3.03 10–5 mol dm–3 min–1
30 − 175

[Range: 2.50 to 3.10  10–5 mol dm–3 min–1]

(c) Determine the average rate of the above reaction for the first 120 min.

overall change in [CH3 Br] 0.0049 − 0.0100

average rate = =− = 4.25  10–5 mol dm–3 min–1
overall time taken 120

(You draw a straight line from the first point to the last point and find the gradient of this line)
You can also view the video explanation via this link.

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Hwa Chong Institution 2023 06 – Reaction Kinetics

Refer to the diagram below for the graphs you are expected to draw in each case.

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Hwa Chong Institution 2023 06 – Reaction Kinetics

3 RATE EQUATION, ORDER OF REACTION AND RATE CONSTANT

LO8(a)part: explain and use the terms: rate equation; order of reaction; rate constant

3.1 Rate equation, order of reaction and rate constant

The stoichiometric equation cannot be used to predict how concentration of reactants affects the rate
of a reaction. Instead, we obtain this data experimentally and summarise it in the form of a rate
equation, or rate law.

Consider the reaction: a A + b B → products

The rate equation for this reaction is given by: rate = k [A]m [B]n

where m and n are the orders of reaction with respect to [A] and [B] respectively
and k is the rate constant

The rate equation is an experimentally determined equation that relates the rate of reaction
to the concentrations of the reactants raised to appropriate powers.

The order of reaction with respect to a reactant is the power on its concentration term in the
rate equation. The order of reaction must be determined experimentally.

The overall (or total) order of reaction is the sum of the individual orders.

The rate constant, k, is the proportionality constant in the experimentally-determined rate

equation. It is a constant at a given temperature.

The stoichiometric coefficients in the chemical equation are not necessarily related to the values of
the orders of reaction in the rate equation. This is illustrated by the data in the table below.

Reaction Rate Equation

CH3Br(aq) + OH−(aq) → CH3OH(aq) + Br−(aq) Rate = k[CH3Br][OH−]
BrO3−(aq) + 5Br−(aq) + 6H+(aq) → 3Br2 + H2O Rate = k[BrO3−][Br−][H+]2
CHCl3(g) + Cl2(g) → CCl4(g) + HCl(g) Rate = k[CHCl3][Cl2]1/2

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Hwa Chong Institution 2023 06 – Reaction Kinetics

3.2 Understanding order of reaction

The order of reaction with respect to a reactant, A, tells us how the concentration of that reactant
affects the reaction rate.

Consider the reaction: a A + b B → products

If the rate of reaction is

• independent of the concentration of A, i.e. changes in [A] do not change the rate of reaction,
then: rate ∝ [A]0 and order of reaction is zero order with respect to [A],

• directly proportional to [A], i.e. when [A] doubles, rate doubles, then: rate ∝ [A]1 and order of
reaction is first order with respect to [A],

• directly proportional to [A]2, i.e. when [A] doubles, rate quadruples (increases 4 times),
then: rate ∝ [A]2 and order of reaction is second order with respect to [A].

The order of reaction are usually positive integers (0, 1, 2…) although they can also be fractional or
even negative.

For the reaction between nitrogen monoxide and hydrogen gas,

2NO(g) + 2H2(g) → N2(g) + 2H2O(g)

the rate equation was found experimentally to be: rate = k[NO]2[H2]

The reaction is thus second order with respect to [NO] and first order with respect to [H2]. The overall
order is third order ( 2 + 1 = 3). Note that the power ‘1’ after [H2] may be omitted in the rate
equation.

Exercise 3.1 (worked example)

For the reaction between hydrogen peroxide and acidified iodide ions,

H2O2(aq) + 3I⁻(aq) + 2H+(aq) → I3⁻(aq) + 2H2O(l)

the orders of reaction with respect to [H2O2], [I⁻] and [H+] were found to be 1, 1 and 0 respectively.

(a) Write the rate equation for the reaction.

rate = k[H2O2]1[I⁻]1[H+]0 or rate = k[H2O2][I⁻]

The power ‘1’ may be omitted in the rate equation. Any term raised to the power of zero is equal
to 1, so the term [H+]0 could be omitted altogether.

(b) State the overall order of reaction. 2

overall order of reaction = 1 + 1 = 2

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Hwa Chong Institution 2023 06 – Reaction Kinetics

3.3 Understanding the rate constant

Besides concentration of reactants, temperature and presence of catalysts also affect the rate of a
reaction. These factors are included in the rate constant, k.

The Arrhenius equation shows how the rate constant, k, is affected by temperature and activation
energy:
k = Ae−Ea/RT

where, A = pre-exponential factor

Ea = activation energy of the reaction (refer to Section 6.2)
R = molar gas constant
T = absolute temperature

From the Arrhenius equation, we can see that the rate constant, k
• increases with increase in temperature,
• increases with decrease in activation energy (due to presence of catalyst),
• is unaffected by changes in concentration (since there is no concentration term).
Consider again the rate equation, rate = k[A]m[B]n, we can see that the larger the rate constant, the
faster is the rate of reaction.

The units for rate constant, k, depend on the overall order of the reaction.

For example, if the overall order is second order, the units for k can be deduced as follows:

mol dm −3 s −1
units of k = −3 2
= mol–1 dm3 s–1 (or other units of time, e.g. mol–1 dm3 min–1)
(mol dm )

Exercise 3.2
What are the units of the rate constant k for the following? Use ‘second’ as the units for time.

(a) Overall first order reaction: (worked example)

𝑚𝑜𝑙 𝑑𝑚−3 𝑠 −1
Overall first order reaction: units of k = = s–1
𝑚𝑜𝑙 𝑑𝑚−3

(b) Overall third order reaction:

𝑚𝑜𝑙 𝑑𝑚−3 𝑠 −1
Overall third order reaction: units of k = = mol–2 dm6 s–1
(𝑚𝑜𝑙 𝑑𝑚−3 )3

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4 DETERMINING THE RATE EQUATION

To determine the rate equation, experiments are conducted to obtain data so that suitable graphs can
be plotted to determine the orders of reaction with respect to each reactant. Alternatively, the initial
rates method can also be used to determine the orders of reaction.

4.1 Determining order of reaction from graphs

Several graphs can be plotted to determine the order of reaction:

• concentration-time graph
• rate-concentration graph
• rate-time graph

4.1.1 Concentration-time graphs and half-life

LO8(b)part: construct and use rate equations of the form rate = k [A]m [B]n (limited to simple cases of single-step reactions and of multi-
step processes with a rate-determining step, for which m and n are 0, 1 or 2), including: (ii) justifying, for zero- and first-order reactions,
the order of reaction from concentration-time graphs
LO8(a)part: explain and use the terms: half-life of a reaction

For a particular reactant R that may affect the reaction rate, we express it as: rate = k[R]m

How do we tell the order of reaction, m, with respect to [R] from a concentration-time graph?

Figure 2 shows three possible concentration-time graphs.

[R] / mol dm–3 [R] / mol dm–3 [R] / mol dm–3

(a) (b) (c)

Figure 2

When studying concentration-time graphs, look at the shape of the graphs and when necessary the
half-life. It is also useful to remember that the gradient represents the rate of reaction (Section 2.2).

The half-life, t½, of a reaction is the time taken for the concentration of a reactant to decrease
to half its initial value.

• If the graph is a straight line with a constant gradient (Figure 2a), this means that rate is constant
when [R] decreases during the course of reaction. i.e. rate is independent of [R]. Hence, the
reaction is zero order with respect to [R].

• If the graph is a curve with constant half-life* (Figure 2b), the reaction is first order with respect
to [R]. In addition, as [R] decreases, rate decreases proportionally (see Section 4.1.2 Figure 4b).

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Hwa Chong Institution 2023 06 – Reaction Kinetics

• If the graph is curve and half-lives are not constant (but become longer), the order of reaction
with respect to [R] is not first order (Figure 2c). In this case, to confirm the order of reaction, we
can determine the gradient (hence rate) of the concentration-time graph at various times and plot
a rate-concentration graph (Section 4.1.2).

* What does constant half-life mean?

To show that half-life is constant, we find any two half-lives (usually the first and the second half-lives)
and compare their values. If the two half-lives are the same, we say the reaction has a constant half-
life. We can obtain half-lives from either a [reactant]-time graph (Figure 3a) or a [product]-time graph
(Figure 3b).

[R] / mol dm−3 [P] / mol dm−3

[R]
1.00
0 0.995

[P]f
0.796
0.75

¾0.597
[P]f
½ 0.50
[R]0
½0.398
[P]f
¼ [R]
0.250
0.199

0.00 0
0 5 10 15 20 0 0 12.5 25 37.5 50
st
1 t½ nd
2 t½ time / min time / min
1st t½ 2nd t½
(a) (b)
Figure 3

• [R]0 is the initial concentration • [P]f is the final concentration of product, P, when the
of reactant, R, at t = 0 min. reaction is complete. This is obtained via stoichiometric
• The first half-life is the time calculations from the amount of reactants used.
taken for [R] to decrease from • The first half-life is the time taken for [P] to increase
[R]0 to ½[R]0. from zero to ½[P]f i.e. to produce the first 50% of the
• The second half-life is the time product.
taken for [R] to decrease from • The second half-life is the time taken for [P] to increase
½[R]0 to ¼[R]0. from ½[P]f to ¾[P]f i.e. to produce 50% of the remaining
50% (or the next 25%).

LO8(c)(i): show understanding that the half-life of a first-order reaction is independent of concentration
LO8(c)(ii): use the half-life of a first-order reaction in calculations
For a reaction that is first order with respect to [R], the half-life is independent of [R] and is related to
the rate constant, k, by the following equation:

t½ = ln 2
k

where k is the rate constant in rate equation rate = k[R]

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Hwa Chong Institution 2023 06 – Reaction Kinetics

Why is the half-life of a first order reaction constant? (Background Info):

To prove this, we need to apply some calculus.

d[R]
rate = – dt
= k[R]

On integrating [R]t = [R]0 e−kt [R]0 = [R] at time = 0; [R]t = [R] at time = t
ln[R]t = ln[R]0 – kt

Substitute [R]t = ½[R]o and t = t½, ln½[R]0 = ln[R]0 – kt½

ln2
t½ =
k

In addition, we can also show that [R] after n half-lives = [R]0 × (½)n

Exercise 4.1

(a) The reaction of iodine with propanone in the presence of aqueous acid is zero order with
respect to iodine. Which diagram represents the variation of [I2] with time? (worked example)

[J98/3/12]
Answer: B

The gradient of the graphs at any point tells us the rate of reaction at that point in time.

In option A, the gradient is 0. This means that there is no rate of reaction, meaning the reaction
does not even occur.

In option B, the graph is a straight-line graph. This means that the rate, which is represented by the
gradient of the graph, is constant throughout. Therefore rate of reaction is independent of the [I2]
and it is zero order with respect to iodine.

In option C, the gradient is decreasing over time, so the rate of reaction decreases when [I2]
decreases. Hence it cannot be zero order with respect to iodine.

The last graph shows a graph with a rate that is slow at the beginning, increases over time, then
decreasing again nearing the end of the reaction. It is definitely not zero order with respect to
iodine.

You can also view the video explanation via this link.

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Hwa Chong Institution 2023 06 – Reaction Kinetics

(b) The following reaction was believed to be of first order.

X → products

In an experiment, [X], the concentration of X, varied with time

as shown in the graph.

What can the graph be used for?

1 to determine the rate of reaction at any given instant
2 to check whether the reaction is of first order throughout
3 to determine the half-life of the reaction
[N92/4/34] modified

Exercise 4.2

(a) The rate of removal of the pain-killing drug paracetamol from the body is a first order reaction
with a rate constant, k = 0.26 hr–1. How long will it take to remove 75% of the paracetamol that
a patient consumes? (worked example) [PrelimIJC14/I/15]

ln2 ln2
half-life = = hr
𝑘 0.26
Since [R] after n half-lives = [R]0 × (½)n
1
1 – 0.75 = 0.25 = 1 × ( )𝑛  n = 2
2
ln2
Time taken = 2 × = 5.3 hr
0.26

You can also view the video explanation via this link.

(b) Lead is the final product formed by a series of changes in which the rate-determining stage is
the radioactive decay of uranium-238. This radioactive decay is a first-order reaction with a
half-life of 4.5 × 109 years. What would be the age of a rock sample, originally lead-free, in
which the molar proportion of uranium to lead is now 1:3? [PromoNYJC12/I/18]

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4.1.2 Rate-concentration graphs

Besides concentration-time graphs, another way to find the order is to use rate-concentration graphs.
To obtain a rate-concentration graph, we find the gradient of the concentration-time graph at various
points to obtain the rates. These rates can then be plotted against their corresponding concentrations.

For a particular reactant R that may affect the reaction rate, we express it as: rate = k[R]m

How do we tell the order of reaction, m, with respect to [R] from a rate-concentration graph?

Figure 4 shows three possible rate-concentration graphs.

rate / mol dm–3 min–1 rate / mol dm–3 min–1 rate / mol dm–3 min–1

0 0 0
[R] /mol dm–3 [R] /mol dm–3 [R] /mol dm–3
(a) (b) (c)
Figure 4

When studying rate-concentration graphs, look at the shape of the graphs. It is also useful to deduce
the mathematical equation of the graph.

• If the graph is a horizontal line (Figure 4a), rate is constant when [R] changes or rate is
independent of [R], i.e. rate = k[R]0. The reaction is zero order with respect to [R].

• If the graph is a straight line passing through the origin (Figure 4b), rate is directly proportional
to [R], i.e. rate = k[R]1. The reaction is first order with respect to [R].

• If the graph is a parabola (Figure 4c), the order of reaction with respect to [R] is not 1. In order to
confirm the order of reaction, we should plot a graph that is a straight line.

For example, if the order of reaction is 2, the rate equation is rate = k[R]2. We can plot rate on the
y-axis and [R]2 on the x-axis as shown in Figure 5a. Alternatively, we can also obtain the log form
of the rate equation: lg rate = lg k + 2lg[R]. When lg rate is plotted against lg [R], the gradient is
the order of reaction (Figure 5b).

rate / lg rate
mol dm–3 min–1
gradient
= order of reaction
lg k

0 0 lg [R]
2 2 –6
[R] /mol dm
(a) (b)
Figure 5

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Exercise 4.3 (worked example)

In tetrachloromethane at 45 oC, dinitrogen pentaoxide, N2O5, decompose as follows:

N2O5 → 2NO2 + ½O2

The rate of the reaction was measured for different concentrations of N2O5. The results are shown
in the table below.
[N2O5]
2.21 2.00 1.79 1.51 1.23 0.82
/ mol dm−3
rate
22.7 x 10−6 21.0 x 10−6 19.3 x 10−6 15.7 x 10−6 13.0 x 10−6 8.3 x 10−6
/ mol dm−3 s−1

(a) Plot a graph of rate against [N2O5].

(b) Use your graph to find the order of the reaction with respect to [N2O5].

Since the graph is a straight line passing through the origin, rate is directly proportional to
[N2O5]. Hence, the reaction is first order with respect to [N2O5].

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(c) Write the rate equation for the reaction.

rate = k[N2O5]

(d) Calculate the rate constant, giving its units.

This is a graph of rate vs [N2O5].

Hence, k = gradient of graph = 24 × 10–6 / 2.3 = 1.04 × 10−5 s−1

(e) Sketch the graph of [N2O5] against time. Mark clearly the value of the half-life on your graph.
e, t½ = ln2/k

4.1.3 Rate-time graphs

Rate-time graphs are less useful because they do not offer much more information than the
concentration-time graphs on which they are based. To obtain a rate-time graph, we find the gradient
of the concentration-time graph at various points to obtain the rates. These rates can then be plotted
against time.

Figure 6 shows the rate-time graphs for reactions which are zero, first and second order with respect
to [R] respectively.

zero order first order second order

rate / mol dm–3 min–1 rate / mol dm–3 min–1 rate / mol dm–3 min–1

0 0 0
time /min time /min time /min
• rate remains constant, • rate decreases • rate decreases exponentially
except when the reaction exponentially with time with time
is complete • decrease is faster compared
to a first order reaction
Figure 6

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4.2 Determining order of reaction using initial rates method

LO8(b)part: construct and use rate equations of the form rate = k [A]m [B]n (limited to simple cases of single-step reactions and of multi-
step processes with a rate-determining step, for which m and n are 0, 1 or 2), including: (i) deducing the order of a reaction by the initial
rates method (v) calculating an initial rate using concentration data
LO8(d): calculate a rate constant using the initial rates method

The initial rates method is studying how the initial rate changes when the initial concentration of a
reactant is changed, and hence determine the order of reaction with respect to that reactant.
Typically, the initial concentration of all other reactants are kept constant.

Initial rate is found from the gradient of tangent at time = 0 of a concentration-time graph
(Section 2.2). Initial rate can also be approximated to average rate using a ‘clock’ method
(Section 5.2).

Exercise 4.4 (worked example)

In investigations of the reaction, 2A(aq) + 2B(aq) + C(aq) → products, the following results are
obtained.
Initial concentration / mol dm–3 Initial rate of reaction
Experiment
[A] [B] [C] / mol dm–3 s–1
1 0.010 1.00 0.50 2.0  10–3
2 0.030 1.00 0.50 6.0  10–3
3 0.030 2.00 0.50 2.4  10–2
4 0.030 2.00 0.25 2.4  10–2
5 0.040 2.50 0.40 ?

(a) Determine the order of reaction with respect to A, B and C.

Let the rate equation be: rate = k [A]x [B]y [C]z
rate2 k (0.03)x (1.0)y (0.5)z rate3 k (0.03)x (2.0)y (0.5)z
= =
rate1 k (0.01)x (1.0)y (0.5)z rate2 k (0.03)x (1.0)y (0.5)z
6 × 10−3 (0.03)x 2.4 × 10−2 2y
= =
2 × 10−3 (0.01)x 6 × 10−3 1y
3 = 3x 4 = 2y
 order of reaction w.r.t. [A] = x = 1  order of reaction w.r.t. [B] = y = 2

rate3 k (0.03)x (2.0)y (0.5)z

=
rate4 k (0.03)x (2.0)y (0.25)z
2.4 × 10−2 (0.5)z
= = 2z
2.4 × 10−2 (0.25)z
 order of reaction w.r.t. [C] = z = 0
Alternative method (by inspection):
Comparing experiments 1 and 2, [B] and [C] are constant, when [A] is increased 3 times,
initial rate increased 3 times. rate ∝ [A], the reaction is first order with respect to [A].
In experiments 2 and 3, [A] and [C] are unchanged. When [B] is increased 2 times,
initial rate increased 4 times. rate ∝ [B]2, order of reaction with respect to [B] = 2 .
Compare experiments 3 and 4, only [C] is changed but the initial rate does not change.
 reaction is zero order with respect to [C].

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(b) Write the rate equation for the reaction.

rate = k [A] [B]2
(c) Calculate the rate constant for the reaction, indicating units.
rate 2.0×10−3
From experiment 1, k = 2 = = 0.200 mol–2 dm6 s–1
[A][B] 0.010×1.002
(Note: you can choose to use any experiment, the answer will still be the same.)
(d) Calculate the initial rate for Experiment 5.
initial rate for Experiment 5 = k [A] [B]2 = 0.2  0.04  (2.5)2 = 0.0500 mol dm–3 s–1

You can also view the video explanation via this link.

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Hwa Chong Institution 2023 06 – Reaction Kinetics

Exercise 4.5
(a) (worked example) Trichloromethane reacts with aqueous sodium hydroxide according to the
equation shown below.
2CHCl3 + 7OH– → CO + HCO2– + 6Cl– + 4H2O

Some data were recorded in order to study the kinetics of the reaction:
Expt Initial [CHCl3] / mol dm–3 Initial [OH–] / mol dm–3 Initial rate / mol dm–3s–1
1 0.100 0.120 1.0  10–4
2 0.050 0.240 1.0  10–4
3 0.050 0.480 2.0  10–4

If k is the rate constant, what is the rate equation?

A rate = k[OH–] B rate = k[CHCl3] [OH–]
C rate = k[CHCl3]2 [OH–] D rate = k[CHCl3] [OH–]2

Comparing experiments 2 and 3, [CHCl3] and [OH−] are constant, when [OH−] is increased 2
times, initial rate increased 2 times. rate ∝ [OH−], the reaction is first order with respect
to [OH−].
Let the rate equation be: rate = k [CHCl3]x [OH−]
rate2 k (0.050)x (0.240)
=
rate1 k (0.100)x (0.120)
1.0×10−4 (0.050)x
= ×2  x=1
1.0×10−4 (0.100)x
 order of reaction w.r.t. [CHCl3] = x = 1
rate = k[OH–]

(b) Hydrogen peroxide reacts with acidified iodide ions, liberating iodine. In investigations of this
reaction, the following results were obtained.

Initial concentrations of reactants / mol dm–3 Initial rate of formation of iodine

[H2O2] [I−] [H+] / mol dm–3 s–1
0.010 0.010 0.10 2.0 x 10–6
0.030 0.010 0.10 6.0 x 10–6
0.030 0.020 0.10 1.2 x 10–5
0.030 0.020 0.20 1.2 x 10–5

Which statements follow from these results?

1 The rate equation for the reaction can be written: rate = k[H2O2][I–].
2 The reaction is zero order with respect to the acid.
3 The rate constant is 2 x 10–1 mol–2 dm6 s–1.

A 1, 2 and 3 are correct

B 1 and 2 only are correct
C 2 and 3 only are correct
D 1 only is correct
[N96/IV/34]

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(c) The table shows experimental results obtained for the following reaction:
2XO(g) + O2(g) → 2XO2(g)

Partial pressure of XO Partial pressure of O2

Relative rate
(in arbitrary units) (in arbitrary units)
100 100 1.00
100 25 0.25
50 100 0.50
50 ? 0.125

What is the missing value of the partial pressure of O2 in the table?

A 25 B 40 C 50 D 75
[N90/1/13]

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Summary

The rate equation is an experimentally determined equation that relates the rate of reaction to the
concentrations of the reactants raised to appropriate powers.

rate = k [A]m [B]n

effects of temperature and
catalyst are included in k

The order of reaction can be determined from concentration-time graphs or rate-concentration

graphs. Alternatively, we can determine initial rates and apply the initial rates method.

Complete the table below by sketching the graphs for a particular reactant that may affect the
reaction rate where rate = k[reactant]m (m = 0, 1 or 2).

zero order first order second order

rate = k[reactant]0 = k rate = k[reactant]1 rate = k[reactant]2

rate rate rate

0 [reactant] 0 [reactant] 0 [reactant]

[reactant] [reactant] [reactant]

0 time 0 time 0 time

[product] [product] [product]

0 time 0 time 0 time

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5 EXPERIMENTAL TECHNIQUES FOR STUDYING RATE OF REACTION

LO8(e): devise a suitable experimental technique for studying the rate of a reaction, from given information

In Section 4, we looked at two ways to determine order of reaction: using graphs e.g. concentration-
time graph and using the initial rates method. In this section, we will look at how experiments can be
carried out to obtain the data to plot the graphs or to obtain initial rates.

There are two approaches we can use:

• sampling method – involves taking samples from a reaction mixture at regular time intervals to
analyse a reactant or product so that we know how fast it is consumed or produced; the data
collected is used to plot ‘concentration’-time graphs.
• ‘clock’ method – involves recording the time taken for the reaction to occur to a small extent; the
time taken gives us an approximation of initial rates.

5.1 Sampling method

Depending on the reaction we are studying, the concentration of a ‘chosen’ reactant or product may
be determined by titration or by measuring a physical property which changes as the reaction
proceeds (e.g. the volume of gas produced, colour intensity of the reaction mixture etc.). Measuring
a physical property can be more convenient because it does not ‘disturb’ the reaction. Both the titres
and the physical properties can be related to changes in concentration of a reactant or product.

5.1.1 Sampling and titration

The acid-catalysed iodination of propanone can be studied by sampling followed by titration.
H+
CH3COCH3(aq) + I2(aq) ⎯⎯→
⎯ CH3COCH2I(aq) + H+(aq) + I–(aq)

The experiment consists of the following steps:

Step 1 Preparation of reaction mixture Step 2 Withdrawal of sample
Reactants and acid catalyst
of known volumes and
concentrations are mixed thoroughly
A small fixed sample
e.g. 10.0 cm3 is withdrawn
stop-watch started from the reaction mixture
at the instant of using a pipette before the
mixing time of e.g. 5 min.

The reaction mixture should be placed in a

thermostatically controlled water bath as rate is
affected by temperature.
Step 3 Quenching of reaction in sample Step 4 Analysis of sample by titration
At exactly 5 min (in this e.g.), excess NaHCO3(aq) is Titrate iodine remaining in the
added into the withdrawn sample (to remove the acid quenched sample with aqueous
catalyst). This slows down the reaction significantly sodium thiosulfate, Na2S2O3(aq),
such that it may be regarded as virtually stopped. of known concentration,
using starch as indicator.
excess NaHCO3(aq)
Repeat steps 2 to 4 at 10 min,
15 min, etc., to collect sufficient
withdrawn sample number of data points to plot a
placed in conical flask ‘concentration’-time graph.

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There are several points to note for a sampling and titration method:
• The concentration of the reactants and products in the samples that are withdrawn (at various
times) are the same as the concentrations in the reaction mixture.

• To determine the concentration of a reactant or product at a specific time, the reaction in the
sample should not continue to take place while it is being analysed. Hence, quenching of the
sample must be done before the titration by adding a large volume of cold water to slow down
the reaction (by rapid dilution and cooling) or by neutralising an acidic reactant with a base or
vice-versa which will stop the reaction completely.

• Since the titre is proportional to the concentration of the reactant (or product),
a titre-time graph would be equivalent to a concentration-time graph. The order of reaction can
then be determined from the graph (see Section 4.1.1).

• All other factors that might affect the rate should be kept constant:
• Temperature can be kept constant by placing the reaction mixture in a thermostatically
controlled water bath.

Figure 7. A thermostatically controlled water bath

• The other reactants which are not being ‘monitored’ are used in large excess (around 10 times
more concentrated). During the course of the reaction, their concentrations vary so little that
they ‘appear’ constant. We assume they do not affect the rate, i.e. we say the reaction is
pseudo zero order with respect to these reactants. Their actual order may not be zero and
has to be determined by further experiments.

For example, in the acid-catalysed iodination of propanone, we follow the changes in [I2] so propanone
and H+ have to be in large excess. The graph of [I2] vs time reflects the order w.r.t. [I2] only if
[propanone] and [H+] do not vary much during the course of reaction.

Reactant Initial concentration /mol dm–3 Concentration at the end of the reaction /mol dm–3
I2 0.002 0
propanone 0.4 0.4 – 0.002 = 0.398
H+ 0.4 0.4 + 0.002 = 0.402
H+ is not used up during the reaction because it is a catalyst; its concentration increases because it is also being
produced by the reaction.

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Generic procedure for sampling followed by titration

1. To prepare the reaction mixture, measure _(volume)_ cm3 of __(reactant X)__ into a 250 cm3
beaker (or conical flask) using a _(volume)_ cm3 measuring cylinder.
2. Measure _(volume)_ cm3 of __(last reactant)_ using a measuring cylinder. Add __(last
reactant)__ to the mixture and start the stop-watch at the same time. Swirl to ensure mixing.
3. Before _(your chosen time, say 5 min from the start of the reaction)__, pipette 10.0 cm3 of the
reaction mixture into a conical flask.
4. At (your chosen time), quench the withdrawn sample by adding to it _(volume)_ cm3 of
__(suitable quenching reagent). Record the exact time of quenching (but don’t stop the stop-
watch!).
5. Carry out the titration of the quenched sample. (Details of titration steps needed. Refer to the
Planning section in Topic 4 Reactions & Stoichiometry)
6. Before ___(each of your subsequent chosen times)___, repeat steps 3 and 4. Carry out the
titration of each quenched sample. (At least 5 samples are collected to obtain data points to plot
the graph.)
Note:
• Only one accurate titration is possible for each withdrawn sample.
• The reactant under study should be isolated, i.e. the other reactants should be in large excess
(around 10 times more concentrated), so that the order of reaction with respect to that reactant
alone can be determined.
• A burette cannot be used to add the last reactant (Step 2) as it has to be added rapidly.

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Exercise 5.1 [N91/3/3 modified] (worked example)

A dilute solution of hydrogen peroxide can be used to bleach hair. It decomposes slowly in aqueous
solution according to the following equation:

2H2O2(aq) → 2H2O(l) + O2(g)

A solution with an original concentration of 3.0 mol dm–3 was placed in a bottle contaminated with
transition metal ions, which act as catalysts for the decomposition. The reaction was followed by
withdrawing 10.0 cm3 portions at various times and titrating with acidified 0.1 mol dm–3 KMnO4(aq).
(5 mol of H2O2 react with 2 mol of KMnO4)

The following results were obtained:

Time /min 0 5 10 15 20 25 30
Volume of KMnO4 /cm3 30.00 23.40 18.30 14.20 11.10 8.70 6.80

(a) Plot a graph of volume of KMnO4 against time and use it to find the order of reaction with
respect to hydrogen peroxide.

t1 = t2 = 14 min, half-life is constant at 14 min

 reaction is first order with respect to [H2O2]

At time t, volume of KMnO4  [H2O2]mixture

Hence, graph of volume of KMnO4 vs time is equivalent to graph of [H2O2]mixture vs time.
We can use the graph of volume of KMnO4 vs time to deduce the order w.r.t. [H2O2].

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(b) Write the rate equation for the reaction and calculate the rate constant, indicating its units.

rate = k [H2O2]

ln2 ln2
k= = = 0.0495 min–1
𝑡1⁄2 14

(c) Calculate the concentration of the H2O2 at the time the first portion was withdrawn. Hence
estimate how long the solution had been in the contaminated bottle.

Amount of H2O2 in 1st portion = 5/2  amount of MnO4– used in 1st titration
= 5/2  30/1000  0.1
= 7.50  10–3 mol
7.5×10−3
[H2O2] at the time the first portion was withdrawn = × 1000 = 0.750 mol dm–3
10

3.0 mol dm–3 → 1.5 mol dm–3 → 0.750 mol dm–3

Two half-lives have passed.
 the solution had been in the bottle for 2  14 = 28 min

You can also view the video explanation via this link.

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Hwa Chong Institution 2023 06 – Reaction Kinetics

5.1.2 Sampling and measuring a physical property

• Measuring volume of gas produced

This method is useful for reactions which produce gaseous products. For example, the reaction,
2H2O2(aq) → 2H2O(l) + O2(g), may be studied by measuring the volume of O2 gas produced using a
graduated gas syringe or via the water displacement method.

Generic procedure for sampling via gas collection

The generic procedure is similar to the ones stated in the Planning section in Topic 3 The Gaseous
State. In that section, two different set-ups were shown. We shall use set-up A as an example:

1. Using an electronic balance, weigh accurately about (mass) g of (solid reactant) in a weighing
bottle.
2. Using a measuring cylinder, transfer (volume) cm3 of (aqueous reactant) into a 250 cm3 conical
flask.
3. Carefully lower the weighing bottle containing (solid reactant) into the conical flask, ensuring the
reactants do not mix. Insert the stopper to ensure a closed set-up.
4. Set up the apparatus as shown in the diagram (draw an appropriate diagram – refer to Planning
section in Topic 3 The Gaseous State).
5. Record the initial reading (x cm3) on the gas syringe.
6. Shake the conical flask to mix the reactants and start the stopwatch at the same time.
7. Continue to gently swirl the flask and record the reading on the gas syringe every ___(your chosen
time interval)___ minute until the reaction is complete.

The experimental results can be used to plot a

volume of O2 gas graph of volume of O2 gas produced against
time.

rate at time t The volume of O2 produced is proportional to

the concentration of O2 at time t. The rate of
change in volume of O2 (gradient of tangent at
time t) is directly proportional to the rate of
reaction at time t.

Hence, Figure 8 is equivalent to a product

concentration-time graph.

To determine the order of reaction with

t
time respect to [H2O2], look at the shape of the
Figure 8. A typical graph of volume against time for a graph and check if the half-life is constant (see
reaction that gives off a gas Section 4.1.1).

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• Measuring a change in absorbance using a colorimeter

This method is suitable for a reaction in which one of the substances (reactant or product) is coloured
or has a different colour from the others.
H+
CH3COCH3(aq) + I2(aq) ⎯⎯→
⎯ CH3COCH2I(aq) + H+(aq) + I–(aq)
brown

For example, the reaction between iodine and propanone can be studied using this method.

A colorimeter measures the amount of light which is absorbed as it passes through a coloured solution
– recorded as the absorbance of the solution. The more concentrated the coloured species is in the
solution, the more light it will absorb and the greater the absorbance. The absorbance can be
measured at regular time intervals using the colorimeter, and the rate of reaction is directly
proportional to the rate of change in absorbance.

Figure 9. A simplified diagram of a colorimeter

• Measuring a change in electrical conductivity

This method is applicable for a reaction in aqueous solution in which there is a change in the
concentration of ions (hence electrical conductivity).

BrO3−(aq) + 5Br−(aq) + 6H+(aq) → 3Br2(aq) + 3H2O(l)

For example, the reaction between bromate(V) and bromide ions results in a decrease in
concentration of ions. The electrical conductivity of the aqueous solution can be measured at regular
time intervals using a conductivity meter, and the rate of reaction is directly proportional to the rate
of change in conductivity.

• Measuring a change in gas pressure

This method is suitable for reactions which involve a change in the number of moles of gases (hence
total pressure).

For example, the reaction, N2(g) + 3H2(g) → 2NH3(g) shows a reduction in number of moles of gases,
hence total pressure decreases as the reaction proceeds. The total pressure of the reacting system is
measured at regular time intervals by connecting the reaction flask to a manometer. The gaseous
system is kept in a fixed-volume reactor maintained at constant temperature. Rate of reaction is
directly proportional to the rate of change in pressure.

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Exercise 5.2 (worked example)

Hydrogen peroxide reacts with potassium manganate(VII) as follows:

2MnO4– + 5H2O2 + 6H+ → 2Mn2+ + 5O2 + 8H2O

Suggest how two physical properties can be measured to study the rate of this reaction.

Measure intensity of purple colour of MnO4– using a colorimeter. The intensity of the purple colour
is an indication of the concentration of MnO4–.
Measure volume of O2 gas using a graduated gas syringe.

Exercise 5.3
Suggest methods of measuring the rates of the following reactions:
(a) zinc powder with aqueous copper sulfate (hint: write out the chemical equation first)
(b) oxidation of KI(aq) by K2S2O8(aq), S2O82–(aq) + 2I–(aq) → 2SO42–(aq) + I2(aq)
(c) esterification: CH3CO2H + C2H5OH → CH3CO2C2H5 + H2O
(d) (CH3)3CBr + H2O → (CH3)3COH + H+ + Br–
(e) 2NO(g) + O2(g) → 2NO2(g)

5.2 ‘Clock’ method and initial rate

A sampling method can be very tedious if the analysis is by titration. An alternative is to use a ‘clock’
method.

A ‘clock’ method involves measuring the time taken for the reaction to occur to a small extent. The
reaction is set up to produce a prominent change e.g. colour change, when a small fixed volume (e.g.
5 cm3) of gas or small amount of precipitate is formed. The time taken for the prescribed change to
occur may be used as an approximation of the initial rate of the reaction.

By comparing the initial rates of two reaction mixtures, in which a different initial concentration of
one reactant is used, we can deduce the order of reaction with respect to that reactant. Alternatively,
the graph of initial rate vs initial concentration can be plotted and the reaction order deduced from
the shape of the graph (see Section 4.1.2).

5.2.1 Reaction of S2O82− and I− (Iodine Clock)

The reaction between S2O82− and I− can be followed using a ‘clock’ method. The two reactants are
mixed with a known small amount of sodium thiosulfate, Na2S2O3, and a little starch indicator.

S2O82−(aq) + 2I−(aq) → 2SO42−(aq) + I2(aq) Reaction (1)

I2(aq) + 2S2O32−(aq) → 2I−(aq) + S4O62−(aq) Reaction (2)

Reaction (1) is the reaction whose kinetics is to be investigated. Initially, the I2 produced in reaction
(1) reacts with the S2O32− to produce colourless products in reaction (2). Hence, the characteristic blue-

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black colour of the I2-starch complex is not observed. When all the S2O32− has been used up, the I2,
which is still being produced by reaction (1), reacts with the starch to give a blue-black colour.

The time taken, t, for this colour to appear may be used as an approximate measure of the initial rate
of reaction (1). This is only an approximate value as it assumes that the concentration-time graph is
a straight line from the origin to the point when the blue-black colour appears (Figure 10). The
approximation is valid provided the reaction occurs to a small extent, i.e. the change in [I2], y, is small.

[I2] true initial rate

[I2] when
Na2S2O3 is y
used up measured
initial rate
time
t
Figure 10

d[I2 ] 𝑦
When y is small, initial rate = ≈ (i.e. the average rate)
dt 𝑡

If a fixed amount of Na2S2O3 is used in each reaction mixture, then y is constant, i.e. the blue colour
appears for each reaction mixture after the same amount of I2 is produced. We can then say
𝟏
initial rate ∝ .
𝒕
The shorter the time, t, the faster the initial rate. We can simply compare the time taken for two
experiments to compare their initial rates. For example, if the time taken is halved, the initial rate is
doubled.

To find the order of reaction with respect to [I−], we prepare two reaction mixtures: Experiment 1 with
[I−] = 0.2 mol dm−3, and Experiment 2 with [I−] = 0.1 mol dm−3. The rate of Experiment 1 is
𝑦 𝑦
approximately equal to 𝑡 , and the rate of Experiment 2 is approximately equal to 𝑡 (Figure 11).
1 2

[I2]
Experiment 1: [I−] = 0.2 mol dm−3
The ratio of times taken gives the ratio of
𝑟𝑎𝑡𝑒 𝑦/𝑡 𝑡
the rates: 𝑟𝑎𝑡𝑒1 = 𝑦/𝑡1 = 𝑡2
2 2 1
y Experiment 2:
[I - ]1
[I−] = 0.1 mol dm−3 Since
0.2
= 0.1 = 2, we can compare this
[I - ]2
ratio to that of the initial rates to deduce
the order of reaction with respect to [I−].

t1 t2 time
Figure 11

To find the order of reaction with respect to [S2O82−], we can prepare reaction mixtures with different
initial concentrations of S2O82− and analyse the results as above for I−.

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5.2.2 Reaction of S2O32− and H+ (Sulfur Clock)

The reaction between hydrochloric acid and thiosulfate ions can also be studied using a ‘clock’
method.
Na2S2O3(aq) + 2HCl(aq) → S(s) + SO2(g) + 2NaCl(aq) + H2O(l)
pale yellow ppt

The fine precipitate of sulfur produced gradually makes the solution opaque. The time taken for the
cross under the beaker to just become obscured may be used as an approximate measure of the initial
rate.

Unlike the iodine clock in Section 5.2.1, we do not have to add another chemical to the reaction
mixture to ‘act’ as the clock. By using the same cross, we ensure that the amount of sulfur produced
each time in the different reaction mixtures (with different reactant concentration) are fixed.

HCl(aq) + Na2S2O3(aq)

white paper with a “cross”

marked on it

Figure 12. Experimental setup for the reaction between Na2S2O3(aq) and HCl(aq)

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To determine the order of reaction with respect to a reactant A, we measure the initial
rates for a number of experiments in which the concentration of A is varied while keeping the
concentrations of other reactants constant. Initial rates are often obtained by timing the formation
of a small, fixed amount of product.

Generic procedure for ‘clock’ method to obtain initial rates

1. To prepare the reaction mixture, measure _(volume)_ cm3 of __(reactant X)__ into a 250 cm3
beaker (or conical flask) using a measuring cylinder.
Repeat for all other reactants except for the last reactant which kick–starts the reaction.
2. Measure _(volume)_ cm3 of __(last reactant)__using a measuring cylinder. Add __(last
reactant)__ to the mixture and start the stop–watch at the same time. Swirl to ensure mixing.
3. Stop the stop–watch when _(state distinct visual change)_ is observed. Record the time taken,
t.
4. Repeat steps 1 to 3 with different volumes of __(reactant studied)__ and deionised water,
keeping the total volume constant. (Use a table to show the list of different volumes to use in
each experiment.)

Note:
• The distinct visual change can be when sufficient precipitate is formed to just obscure a mark;
or when a particular colour first appears.
• The total volume of the mixture is kept constant so that [A]initial is directly proportional to the
volume of reactant A. E.g., when volume of A is doubled, [A]initial is doubled; when volume of A
is unchanged, [A]initial is kept the same.
1
• obtained in this way is a measure of the initial rate of reaction, hence comparing the values
t
1 1
of and volume of A can give us the order w.r.t. A e.g. when volume of A is doubled and
t t
is also doubled, it shows that the reaction is first order w.r.t A. Alternatively, plotting the values
1
of vs volume of A will effectively give us the rate-concentration graph, the shape of which
t
will allow us to determine the order w.r.t. A (see Section 4.5).
• Measuring cylinders are usually used to measure the volumes of liquids (common capacities:
10 cm3, 25 cm3, 50 cm3, 100 cm3). A burette may be used if a chemical is to be added in a small
quantity which has to be exactly the same quantity for all experiments. However, a burette
cannot be used to add the last reactant (Step 2) which has to be added rapidly.

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Summary

Experimental methods to determine m in

rate = k [A]m [B]n
for reaction aA + bB → products

Sampling Method 'Clock' Method

• Measure [A] or [product] at regular time intervals • Measure the time for a small and fixed prescribed
in one reaction mixture (visual) change in at least 2 reaction mixtures
• Initial [B] is used in large excess where
 pseudo-zero order w.r.t. [B] • initial [A] is different
 rate = k'[A]m where k' = k[B]n  constant • initial [B] is the same

How to measure [A] or [product] in a reaction How to vary [A] in different reaction mixtures?
mixture over time?
Vary vol. of A and keep total volume constant
• Remove samples to titrate (Section 5.1.1) E.g.
• Measure vol. of gas produced (Section 5.1.2) Expt VA / cm3 VB / cm3 Vwater / cm3 t/s
• Measure absorbance of mixture (Section 5.1.3) 1 10 20 0 t1
etc. 2 5 20 5 t2

How to determine m from results? How to determine m from results?

• Plot ‘concentration’-time graph (Section 4.1.1) • Initial rates method (Section 4.2)
𝑟𝑎𝑡𝑒1 [𝐴]1 𝑚 𝑡2 10 𝑚
E.g. since Vtitre  [A], plot titre vs time graph E.g. = ቀ ቁ  = ቀ ቁ
𝑟𝑎𝑡𝑒2 [𝐴]2 𝑡1 5
Solve for m
If half-life is
titre/ cm3
constant, order
• Plot ‘rate-concentration’ graph (Section 4.1.2) if
w.r.t. [A] = 1
there are 5 or more sets of results
1
E.g. since VA  [A] and initial rate  , plot
𝑡
1
vs VA graph
𝑡
1/t / s–1
Straight line through
the origin
Straight line graph  rate is directly
titre/ cm3
 rate is constant proportional to [A]
 rate is indept. of  rate = k[A]
[A]  first order w.r.t. [A]
 zero order w.r.t. VA / cm3
[A]

To determine the order w.r.t. [B], perform

Experiment 3 where vol. of B is varied but vol. of A
and total volume are the same as those in
To determine the order w.r.t. [B], repeat the same Experiment 1.
experiment with a different initial [B]. Determine the E.g. VA = 10 cm3, VB = 10 cm3, Vwater = 10 cm3
initial rates from the 2 graphs and use the initial rates
method to determine the value of n.

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6 COLLISION THEORY, ACTIVATION ENERGY AND MAXWELL-BOLTZMANN DISTRIBUTION

6.1 Collision Theory

The Collision Theory states that to react, the reactant particles must collide with sufficient energy and
with the correct orientation.

These collisions are the effective collisions which will result in product formation.

6.2 Activation energy and Maxwell-Boltzmann distribution

LO8(a)part: explain and use the term: activation energy
LO8(g): show understanding, including reference to the Boltzmann distribution, of what is meant by the term activation energy

The activation energy of a reaction (Ea) is the energy barrier the reactants must overcome in
order to become the products.

In any sample, the particles present will possess a range of energies. In order to estimate the fraction
of collisions that have sufficient energy to overcome the activation energy barrier, we need to know
their energy distribution. For gases, the distribution of energies can be represented by the Maxwell-
Boltzmann energy distribution curve (refer to Topic 3 The Gaseous State for explanation on the shape
of the curve).

No. of particles Most particles have a moderate amount

of energy (value on x-axis gives the most
probable energy)
There are very
few particles
with very low
There are very few
kinetic
particles with very high
energies.
kinetic energies.

0 kinetic energy
Ea

Figure 13. The Maxwell-Boltzmann energy distribution curve

The total area under the graph represents the total number of molecules present.

The shaded area represents the fraction of molecules that have kinetic energies greater than or equal
to Ea, the activation energy for a particular reaction. This fraction is usually small.

In general,
• Reactions with low Ea are fast because a large proportion of molecules have sufficient energy to
overcome the energy barrier. Examples of such kinetically favourable reactions include:
• reactions between two free radicals
• reactions between ions of opposite charge
• acid-base (neutralisation) reactions

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• Reactions with high Ea are slow because only a small proportion of molecules have sufficient
energy to overcome the energy barrier. Examples of such kinetically unfavourable reactions
include:
• reactions between two neutral molecules or involve breaking strong covalent bonds
• reactions between ions of similar charge
• reactions where a bond breaks to form free radicals (which are usually highly unstable)

6.3 Molecular orientation

Consider the reaction, NO2Cl + Cl → NO2 + Cl2, where a collision between a NO2Cl molecule and a Cl
atom forms a NO2 molecule and a Cl2 molecule.

Figure 14. A correctly oriented collision

In a poorly oriented collision, the two colliding particles "bounce off" without any reaction.

Figure 15. A poorly oriented collision

6.4 Activation energy and energy profile diagram

LO7(b): Construct and interpret an energy profile diagram, in terms of the enthalpy change of the reaction and of the
activation energy

An energy profile diagram (or reaction pathway diagram) shows the change in the energy of the
reactants as they become the products. The activation energy, Ea, as well as the enthalpy change, H,
of a reaction are also reflected in such a diagram.
Figure 16 shows the energy profile diagram for an exothermic single-step reaction.
energy / kJ mol−1

H

reaction progress

Figure 16. Energy profile diagram for a single-step, exothermic reaction, A + BC → AB + C

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• Single-step reactions have a single transition state (or activated complex). Transition states are
hypothetical species that cannot be isolated. They correspond to the energy maxima i.e. the peaks
in the energy profile diagram.

• The activation energy, Ea, is measured from the energy level of the reactants to the energy level
of the transition state.

• Enthalpy change, ∆H, is the difference between the energy levels of the products and reactants.

The magnitude of the activation energy barrier does not depend on the magnitude of H. ‘How fast’
a reaction occurs depends on its Ea, not H. An exothermic H tells us the products are energetically
more stable than the reactants. However, if the Ea is high, the rate of reaction is negligible at room
temperature. For example, the combustion of methane is highly exothermic (–890 kJ mol–1) but a
mixture of methane and oxygen do not react at room temperature until a spark is introduced.

Figure 17 shows the energy profile diagram for an exothermic two-step reaction. A two-step reaction
has two transition states and an intermediate. An intermediate is a definite species which is formed
during the reaction but are not part of the final products (as they are consumed in a later step).
Intermediates are relatively reactive with energy higher than the reactants and products, but may be
stable enough to be detected or isolated. Unlike a transition state (which occurs at an energy
maximum), an intermediate occurs at an energy minimum, i.e. the valleys in the energy profile
diagram.

The first step in Figure 17a has a larger Ea so it is the slower step while the second step in Figure 17b
is the slower step as it has a larger Ea.

transition transition
energy / kJ mol−1 energy / kJ mol−1
state 1 transition state 2
state 2

Ea2
intermediate

Ea2

Ea1 transition
state 1

Ea1 intermediate
reactants reactants
H < 0 products H < 0 products

reaction progress reaction progress

(a) (b)

Figure 17. Energy profile diagrams for a two-step reaction. In (a), step 1 is slower than step 2. In (b), step 2 is slower than step 1.

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7 REACTION MECHANISM

7.1 Reaction mechanism and rate-determining step

LO8(a)part: explain and use the term: rate-determining step

Many chemical reactions are too complex to occur in one simple step. Instead, the reaction may involve a
series of steps.

A reaction mechanism is a sequence of elementary steps that adds up to the overall reaction. It shows us how
the reaction actually takes place at the particulate level – how the atoms in the reactants rearrange to
form the products and the order in which bonds are broken and formed. Reaction mechanisms are
postulated from kinetics studies which include experiments to obtain the rate equation (see Sections
4 and 5) and experiments to test the mechanism (see examples on 87).

Elementary steps cannot be broken down into simpler steps. The number of particles (atoms,
molecules or ions) reacting in an elementary step is the molecularity of that step. Unimolecular
reactions involve only 1 particle; bimolecular reactions involve the collision of 2 particles; termolecular
reactions involve the collision of 3 particles. Molecularity does not apply to an overall reaction.

Elementary steps must be physically reasonable. It seldom involves the collision of 3 particles (low
probability) or collision between ions of the same charge (high Ea).

In the example below, the mechanism consists of two elementary steps:

• Step 1 is unimolecular; one A reacts in this step.
• Step 2 is bimolecular; one B reacts with one E (which is an intermediate).

step 1: A → E + D (slow)
step 2: E + B → C (fast)
overall equation: A + B → C + D

The rate-determining step (r.d.s.) is the slowest (elementary) step in a mechanism. In a single-step
mechanism, the only step must be the rate-determining step. In a multi-step mechanism, the step with
the highest activation energy is the r.d.s. (see Figure 17).

The rate of the r.d.s. is essentially the overall rate of the reaction. Any step before the r.d.s. should also
affect the overall rate. Any step that takes place after the r.d.s. has no effect on the overall rate.

In the example above, step 1 is the slower step of the two, hence it is the rate determining step. The rate
of step 1 (r.d.s.) gives the overall rate of the reaction. This means that if experiments are done to measure
the reaction’s rate, we are measuring the rate of step 1.

The rate of step 1 is affected by changes in [A]. Since one A reacts in that step, when [A] is doubled,
number of A reacting per unit time doubles so rate is also doubled, implying the order of reaction
w.r.t. [A] is one. Hence, we can relate the order of reaction (obtained from experiments) to the
molecularity of the r.d.s. (and any steps before it since they also affect the overall rate). This will be
elaborated further using the examples in Section 7.2.

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7.2 Reaction mechanism and rate equation

7.2.1 Verifying that a reaction mechanism is consistent with rate equation

LO8(b)part: construct and use rate equations of the form rate = k [A]m [B]n (limited to simple cases of single-step reactions and of multi-
step processes with a rate-determining step, for which m and n are 0, 1 or 2), including: (iii) verifying that a suggested reaction
mechanism is consistent with the observed kinetics

Given a rate equation, we can verify if a suggested reaction mechanism is consistent with it.

Consider the reaction, X + 2Y → XY2, with the experimentally determined rate equation: rate = k[Y]2.

Are the following mechanisms consistent with the rate equation?

Mechanism 1: X + Y → XY (slow) Mechanism 2: 2Y → Y2 (slow)

XY + Y → XY2 (fast) Y2 + X → XY2 (fast)

Deductions from the rate equation:

• [Y] appears in the rate equation  [Y] affects the rate so Y must react either in the r.d.s or in the
steps before it.
• The order of reaction w.r.t. [Y] is 2, hence a total of two Y will react in these steps.
• [X] does not appear in the rate equation  [X] does not affect the rate so it should only react
after the r.d.s.

Mechanism 1 is inconsistent with the rate equation. The slow step in Mechanism 1 involves one X
reacting with one Y. This is inconsistent with the 2nd and 3rd bullet points.

Mechanism 2 is consistent with the rate equation. The slow step in Mechanism 2 involves two Y
reacting. X is not involved in the slow step.

It is also important to ensure the elementary steps add up to the overall stoichiometric equation as shown:
2Y → Y2 (slow)
Y2 + X → XY2 (fast)
2Y + X → XY2 (overall)

Exercise 7.1 (worked example)

For the reaction, X + 2Y → XY2, the experimental rate equation is found to be: rate = k[Y]2.
Suggest if the following mechanism is consistent with the rate equation. Explain your answer fully.

2Y ⇌ Y2 (fast)
Y2 + X → XY2 (slow)

[Y] appears in the rate equation hence [Y] affects the rate. Y must react either in the r.d.s or in the
steps before it. The order of reaction w.r.t. [Y] is 2, hence a total of two Y will react in these steps.
[X] does not appear in the rate equation hence [X] does not affect the rate. X should only react after
the r.d.s.
The mechanism is inconsistent with the rate equation. The slow step is the second step so the overall
rate is also affected by the first step. Hence, rate is affected by both [X] and [Y].
Note: Y2 is an intermediate. The concentrations of intermediates do not appear in the rate equation
(since they do not appear in the overall stoichiometric equation). See Section 7.2.2 Mechanism 5 for
the correct rate equation for the given mechanism. In Mechanism 5, you may treat X as O2 and Y as
NO.

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Exercise 7.2 [N1999/3/33modified] (worked example)

Which suggested mechanism is consistent with the experimentally determined rate equation?

rate equation suggested mechanism

1 rate = k1 [NO]2[H2] 2NO(g) + H2(g) → N2O(g) + H2O(g) (slow)
N2O(g) + H2(g) → N2(g) + H2O(g) (fast)

2 rate = k2 [H2][I2] H2(g) → 2H(g) (slow)

2H(g) + I2(g) → 2HI(g) (fast)

3 rate = k3 [HBr][O2] 2HBr(g) + O2(g) → 2HBrO(g) (slow)

HBrO(g) + HBr(g) → H2O(g) + Br2(g) (fast)

Option 1 is correct.
Since NO and H2 are in the slow step, they appear in the rate equation.
rate = k[NO]2[H2] since 2 molecules of NO and 1 molecule of H2 reacts in the slow step.

Option 2 is correct. There is only 1 molecule of H2 reacting in the slow step.

rate = k[H2]

Option 3 is not correct.

There are 2 molecules of HBr and 1 molecule of O2 reacting in the slow step.
rate = k[HBr]2[O2]

You can also view the video explanation via this link.

7.2.2 Predicting order of reaction from a reaction mechanism

LO8(b)part: construct and use rate equations of the form rate = k [A]m [B]n (limited to simple cases of single-step reactions and of multi-
step processes with a rate-determining step, for which m and n are 0, 1 or 2), including: (iv) predicting the order that would result from
a given reaction mechanism

Given a reaction mechanism, we can construct the rate equation by deducing the order of reaction w.r.t. a
reactant from the rate determining step and the steps before it.

Mechanism 3: CH3CH2Br + OH− → CH3CH2OH + Br−

Recall that in a single-step mechanism, the only step must be the rate-determining step.
The coefficient of CH3CH2Br and OH− in this r.d.s. are both 1. Hence, the order of reaction w.r.t.
[CH3CH2Br] and [OH−] are both 1. Thus, the rate equation is: rate = k[CH3CH2Br][OH−].

Mechanism 4: Step 1 NO2 + F2 → NO2F + F (slow)

Step 2 NO2 + F → NO2F (fast)

The r.d.s. is the first step. The coefficient of NO2 and F2 in the r.d.s. are both 1. Hence, the order of
reaction w.r.t. [NO2] and [F2] are both 1. Thus, the rate equation is: rate = k[NO2][F2] and the overall
stoichiometric equation is: 2NO2 + F2 → 2NO2F (sum of the elementary steps).

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Mechanism 5: Step 1 NO + O2 ⇌ NO3 (reversible, fast)

Step 2 NO3 + NO → 2NO2 (slow)
The overall stoichiometric equation is: 2NO + O2 → 2NO2

Unlike Mechanism 4, the r.d.s. is not the first step. The rate equation cannot be rate = k2[NO3][NO]
since NO3 is an intermediate which does not appear in the stoichiometric equation, and therefore its
concentration does not appear in the rate equation. To obtain the overall rate equation, we need to
look at the rate equation of the r.d.s. i.e. step 2:

Rate equation for step 2 is rate = k2[NO3][NO] ----- (i) where k2 is the rate constant for step 2

Since NO3 is an intermediate, we need to substitute [NO3] with the reactants concentrations, by using
steps before this r.d.s. i.e. step 1:
[NO3 ]
Since step 1 is an equilibrium, we can write: Kc =
[NO][Ο2 ]
(Kc will be discussed in Topic 7 Chemical Equilibria)

Rearranging, [NO3] = Kc[NO][O2] ----- (ii)

Substitute (ii) into (i), rate = k2Kc[NO][O2][NO] = k2Kc[NO]2[O2]

Hence the overall rate equation is: rate = k[NO]2[O2] where k = k2Kc

In summary,
• The elementary steps must add up to the overall stoichiometric equation.
• Reactants whose concentrations appear in the rate equation react before or at the r.d.s. (in order to
affect the reaction rate).
• Reactants whose concentrations do not appear in the rate equation react after the r.d.s.
• The concentrations of intermediates do not appear in the rate equation (since they do not appear
in the overall stoichiometric equation).
Note: A homogeneous catalyst (see Section 9.1) does not appear in the overall stoichiometric equation, but
its concentration appears in the rate equation.
• If the r.d.s. is the first step, the order w.r.t. a reactant is equal to its coefficient in the r.d.s.
• If the r.d.s. is not the first step, the order w.r.t. a reactant is derived from its coefficient in the
r.d.s. and the steps before the r.d.s.

Exercise 7.3 (worked example)

The reaction between nitric oxide, NO, and oxygen is one of the reactions involved in atmospheric
pollution from car exhausts.
Kinetics studies have shown that the reaction is third order overall, and it has been suggested that
the mechanism involves the following two steps.
fast
2NO ⎯⎯
⎯→ N2O2
slow
N2O2 + O2 ⎯⎯⎯→ 2NO2
What is the rate equation for the overall reaction?
A rate = k [NO]2 [N2O2] B rate = k [N2O2] [O2]
2
C rate = k [NO] [O2] D rate = k [N2O2]2 [O2]
[N05/3/1]

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N2O2 is an intermediate as it is produced in the first step and consumed in the second step.
Intermediates do not appear in the rate equation, so A, B, and D cannot be correct.
The rate equation based on the slow step is rate = k[N2O2][O2]. N2O2 (the intermediate) is produced
from 2 NO molecules. We can replace [N2O2] with [NO]2. Hence the correct rate equation is C.
You can view the video explanation via this link.

Experiments techniques to verify mechanisms (Background Info)

Two techniques used to verify postulated mechanisms are described below.

• Isotopic labeling – for example, when esters labeled with 18O are reacted with water (a hydrolysis
reaction), the 18O appears in the alcohol and not in the carboxylic acid group. This shows that the
C−O bond (1), and not the C−O bond (2), is the one that is broken.

Figure 18. Hydrolysis of ethyl ethanoate to give ethanoic acid and ethanol

• Kinetic isotope effect – for example, the C−D bond is slightly harder to break than the C−H bond.
This means that if this bond is broken during the rate-determining step, a compound containing
C−D bonds reacts more slowly than a compound with C−H bonds; if the reaction rate is the same
rate for both compounds, the breakage of this bond does not occur in the slow step.
C6H6 and C6D6 reacts with NO2+ at the same rate. This shows that the rate-determining step is the
initial attack by NO2+, and not the elimination of the proton, H+.

Figure 19. Mechanism for the nitration of benzene

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8 FACTORS AFFECTING RATES OF REACTION

According to the collision theory, a reaction occurs only if the particles collide with sufficient energy
and correct orientation. At the molecular level, the rate of reaction depends on two factors:

• the collision frequency

The simplest way to increase the collision frequency is by increasing the concentration of the reactants,
and for gaseous reactions, the pressure (Section 8.1).

• the proportion of the particles that have sufficient energy to overcome the activation energy
A typical fraction might be one in ten thousand million (1 in 1010) which is very small. We can
increase this fraction by:
• increasing the energy of the collisions (Section 8.2),
• finding another route with a lower activation energy (Section 8.3).

8.1 Effect of concentration or pressure on rate

LO8(f): explain qualitatively, in terms of frequency of collisions, the effect of concentration changes on the rate of a reaction

At a higher concentration (or pressure), there are more reactant particles per unit volume. The
reactant particles are closer together and collide more frequently. Frequency of effective collisions
increases. Hence, rate of reaction increases.

(a) low reactant concentration (b) high reactant concentration

Figure 20. Effect of concentration on frequency of collisions

Recall that it is possible the order of reaction with respect to a reactant is zero, i.e. the concentration
of this reactant does not appear in the rate equation. In this case, changing its concentration would
have no effect on the rate.

For example, the rate equation for the acid-catalysed iodination of propanone
H+
CH3COCH3(aq) + I2(aq) ⎯⎯→
⎯ CH3COCH2I(aq) + H+(aq) + I–(aq)

is rate = k[CH3COCH3][H+]. Increasing the concentration of iodine will not increase the reaction rate.

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8.2 Effect of temperature on rate and rate constant

LO8(h): explain qualitatively, in terms of both the Boltzmann distribution and of collision frequency, the effect of temperature change
on a rate constant (and hence, on the rate) of a reaction

What is the effect of temperature change on rate?

When temperature is increased, the reactant particles have greater average kinetic energy. They
move more quickly and so collide more frequently. More importantly, the proportion of particles that
have kinetic energies greater than or equal to the activation energy increases (see Figure 21).
Frequency of effective collisions hence rate of reaction increases.

No. of molecules proportion of molecules

T1 T2 > T1
with KE  Ea at T1

+ proportion of molecules
T2 with KE  Ea at T2

0 kinetic energy
Ea
Figure 21. Maxwell-Boltzmann distribution showing the effect of temperature change on the proportion of particles with
kinetic energies greater than or equal to the activation energy
What is the effect of temperature change on the rate constant?

From the rate equation, rate = k [A]m[B]n

If [A] and [B] are kept constant, rate ∝ k
When temperature increases, rate increases so k must have increased.

In other words, since an increase in temperature, while keeping concentrations the same, increases
the rate of a reaction, the rate constant must have increased.

Alternatively, the Arrhenius equation, k = Ae−Ea/RT (Section 3.3) can also be used to show that when
temperature increases, rate constant k increases exponentially.

Exercise 8.1 [J2003/I/12] (worked example)

It is often said that the rate of a typical reaction is roughly doubled by raising the temperature by
10 oC.
What explains this observation?

A Raising the temperature by 10 oC doubles the average energy of each molecule.

B Raising the temperature by 10 oC doubles the velocity of each molecule.
C Raising the temperature by 10 oC doubles the number of molecular collisions in a given time.
D Raising the temperature by 10 oC doubles the number of molecules having more than a
certain minimum energy.

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From the Boltzmann Distribution, it is clear that the main reason for an increase in rate of reaction is
due to the increase in proportion of particles having kinetic energy greater than or equal to the
activation energy. D is correct.

8.3 Effect of catalyst on rate and rate constant

LO8(i): (i) explain that, in the presence of a catalyst, a reaction has a different mechanism, i.e. one of lower activation energy, giving a
larger rate constant (ii) interpret this catalytic effect on a rate constant in terms of the Boltzmann distribution

A catalyst is a substance that speeds up a chemical reaction by providing an alternative reaction

pathway of lower activation energy (see Figure 22), while remaining chemically unchanged at
the end of the reaction.

energy uncatalysed reaction

/ kJ mol−1

Ea (uncatalysed)

catalysed reaction

Ea’ (catalysed)
ΔH is not affected by
reactants
presence of catalyst
H
products

progress of reaction
Figure 22. Energy profile diagram for a reaction, with and without a catalyst
What is the effect of a catalyst on rate?

Since a catalyst provides an alternative reaction pathway of lower activation energy (see Figure 22),
the proportion of particles that have kinetic energies greater than or equal to the lower Ea increases
(see Figure 23). Frequency of effective collisions hence rate of reaction increases.

No. of molecules
proportion of molecules
with KE  Ea

+ proportion of molecules
with KE  Ea'

0 kinetic energy
E a' Ea
(with catalyst)

Figure 23. Maxwell-Boltzmann distribution showing the effect of catalyst on the proportion of particles with kinetic energies
greater than or equal to the activation energy

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What is the effect of a catalyst on the rate constant?

From the rate equation, rate = k [A]m[B]n

If [A] and [B] are kept constant, rate ∝ k
In the presence of a catalyst, rate increases so k must have increased.
In other words, since a catalyst increases the rate of a reaction, while keeping concentrations the
same, the rate constant must have increased.

Alternatively, in the presence of a catalyst, the reaction proceeds via a different mechanism that is of
lower Ea (see Figure 22), giving a larger rate constant k (see Arrhenius equation: k = Ae−Ea/RT).

Other factors that affect rate:

Effect of surface area (of solids) on rate

For a chemical reaction involving a solid, only the particles on its surface are available for reaction.
If the solid reactant is in a more finely divided state, the surface area of the boundary between the
reactants (e.g. between the solid and a solution) is larger. Hence, collision frequency increases,
reaction rate increases.

For example, powdered calcium carbonate reacts faster with acid than lumps of the solid do.

Effect of light on rate

Reactions that are affected by light are called photochemical reactions. They tend to be slow in the
dark but take place rapidly in the presence of light. When the reactant molecules absorb light energy,
the average kinetic energy of the particles increases, hence increasing the fraction of reacting particles
with enough energy to overcome the activation energy barrier.
Examples of photochemical reactions include:
• breakdown of silver bromide to silver and bromine (used in black-and-white photography):
AgBr → Ag + ½ Br2
• reaction of hydrogen with chlorine which is slow in the dark but explosive in sunlight:
H2(g) + Cl2(g) → 2HCl(g)
• chlorination of alkanes:
CH4 + Cl2 ⎯⎯ ⎯⎯→ CH3Cl + HCl
UV light

Did you know?

Photochromic sunglasses darken on exposure to ultraviolet (UV) radiation.
Photochromic or photochromatic lenses have millions of particles of
substances such as silver chloride embedded in them. When exposed to UV
rays, as in direct sunlight, the particles undergo a chemical reaction that
causes them to change shape. The new structure absorbs portions of the
visible light, causing the lenses to darken. The number of particles that change
shape varies with the intensity of the UV rays. When you go indoors and out
of the UV light, a different chemical reaction takes place. The absence of UV
radiation causes the particles to "snap back" to their original shape, resulting
in the loss of their light absorbing properties. In both directions, the entire
process happens very rapidly.
[Source: http://science.howstuffworks.com/innovation/science-questions/question412.htm]

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Exercise 8.2
The energy diagram represents the reaction occurring with and without a catalyst.

Which of the following statements are correct?

1 E2 is the activation energy for the catalysed reaction.

2 The enthalpy change of reaction is (E2 – E3).
3 The enthalpy change of reaction is reduced by using a catalyst.

A 1, 2 and 3 are correct

B 1 and 2 only are correct
C 2 and 3 only are correct
D 1 only is correct

∆H = E2 – E3
= E1 – E 4

Hence options 1 and 2 are correct. Option 3 is incorrect because ∆H is constant even when the catalyst
is added.

You can view the video explanation via this link.

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9 CATALYSIS
LO8(a)part: explain and use the term: catalysis

Catalysis refers to the process of increasing the rate of a reaction with a catalyst. This is preferred over
increasing temperature which may increase cost and decompose the reactants or products.

Catalysts may be homogeneous or heterogeneous. A homogeneous catalyst acts in the same phase
as the reactants and is uniformly mixed with them. A heterogeneous catalyst acts in a different phase
from the reactants. There is also an important of class of catalysts called enzymes.

What does same phase and different phase mean? (Background Info):
If you look at a mixture and can see a boundary between two of the components, those substances are in
different phases. If you cannot see a boundary between the components, they are in the same phase.
For example, a mixture of water and oil (both liquids) consists of two phases; you could see the boundary
between them. A mixture of various chemicals in a single solution consists of one phase.

A homogeneous catalyst must be involved in the rate-determining step in order for it to affect the
rate of reaction. As such, the concentration of the homogeneous catalyst usually appears in the rate
equation for the catalysed pathway, even though it does not appear in the overall balanced
stoichiometric equation. For example, the iodination of propanone catalysed by H+ ions:
H+
CH3COCH3(aq) + I2(aq) ⎯⎯→
⎯ CH3COCH2I(aq) + H+(aq) + I–(aq)

has the rate equation, rate = k[CH3COCH3][H+].

Heterogeneous catalysis often involves a solid catalyst interacting with gaseous or liquid reactants.
Since solids do not have a ‘concentration’, the effect of heterogeneous catalysts is included in the
value of the rate constant, k.

9.1 Homogeneous catalysis

Homogeneous catalysis usually involves the formation of an intermediate between the catalyst and
one of the reactants. The catalyst is then regenerated in a later step of the reaction. The catalysed
reaction may involve two or more steps, each of which must has a lower activation energy than the
uncatalysed reaction.

9.1.1 Mode of action of homogeneous catalysis: Catalytic role of Fe2+ in the I–/S2O82– reaction
LO8(j)part: outline the different modes of action of homogeneous and heterogeneous catalysis, including: (iv) catalytic role of Fe2+ in
the I–/S2O82– reaction

Iodide ions react with peroxodisulfate ions in the redox reaction:

2I−(aq) + S2O82−(aq) → I2(aq) + 2SO42−(aq)

The uncatalysed reaction is slow as the repulsion between the two negative ions results in a high
activation energy. The reaction is catalysed by some transition metal cations e.g. Fe2+, and involves
the following steps:

Step 1: 2Fe2+(aq) + S2O82−(aq) → 2Fe3+(aq) + 2SO42−(aq)

Step 2: 2Fe3+(aq) + 2I− (aq) → 2Fe2+(aq) + I2(aq)

Overall equation: 2I−(aq) + S2O82−(aq) Fe2+ (aq) I2(aq) + 2SO42−(aq)

⎯⎯⎯⎯→

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The catalyst Fe2+ and the intermediate Fe3+, being positively charged, easily attract the negative S2O82–
and I− respectively. Thus, in the catalysed pathway, each step has a lower activation energy than the
uncatalysed reaction (see Figure 24).
uncatalysed reaction
energy
/ kJ mol−1
catalysed reaction

2I− + 2SO42−
+ 2Fe3+ Ea(step 2)
2I− + S2O82−
+ 2Fe2+ Ea(step 1)
I2 + 2SO42− + 2Fe2+

progress of reaction

Figure 24. Energy profile diagram for the reaction, 2I−(aq) + S2O82−(aq) → I2(aq) + 2SO42−(aq), with and without a catalyst

Exercise 9.1 (worked example)

Write equations to show how Fe3+ catalyses the redox reaction between iodide ions and
peroxodisulfate ions and explain why Fe3+ can be described as a homogeneous catalyst.

2I−(aq) + S2O82−(aq) → I2(aq) + 2SO42−(aq)

Step 1: 2Fe3+(aq) + 2I− (aq) → 2Fe2+(aq) + I2(aq)

Step 2: 2Fe2+(aq) + S2O82−(aq) → 2Fe3+(aq) + 2SO42−(aq)

Fe3+ is acting as a homogeneous catalyst as it is in the same phase as I− and S2O82−. In addition, it is
regenerated (or not used up) at the end of reaction.

9.1.2 Mode of action of homogeneous catalysis: Catalytic role of NOx in the oxidation of atmospheric
SO2
LO8(j)part: outline the different modes of action of homogeneous and heterogeneous catalysis, including: (iii) the catalytic role of
atmospheric oxides of nitrogen in the oxidation of atmospheric sulfur dioxide

Nitrogen dioxide may catalyse the oxidation of SO2 to SO3 in the atmosphere in the following steps:

Step 1: SO2(g) + NO2(g) → SO3(g) + NO(g)

Step 2: NO(g) + ½O2(g) → NO2(g)
Overall equation: SO2(g) + ½O2(g) → SO3(g)

In the presence of moisture in air or rainwater, SO3 produces H2SO4 resulting in acid rain.

SO3(g) + H2O(l) → H2SO4(aq)

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Exercise 9.2 [J97/I/2 modified] (worked example)

Nitrogen dioxide in the atmosphere contribute to the formation of acid rain by catalysing the oxidation
of SO2 to SO3. Write equations to show how this occurs, and state the type of catalysis.
NO2(g) + SO2(g) → NO(g) + SO3(g)
NO(g) + ½O2(g) → NO2(g)
NO2 is acting as a homogeneous catalyst.

9.2 Heterogeneous catalysis

In heterogeneous catalysis, the catalytic action occurs at the ‘active sites’ on the surface of the
catalyst. A larger surface area exposes more active sites and increases the rate of reaction. The
catalyst is usually made into pellets, wire gauze or finely-powdered form spread on ceramic, silica or
asbestos support.

Many heterogeneous catalysts are transitions metals or their compounds:

Reaction Catalyst
Manufacture of ammonia (Haber Process) finely divided Fe(s) or
N2(g) + 3H2(g) ⇌ 2NH3(g) Fe2O3(s)
One of the reactions involved in the manufacture of sulfuric acid
V2O5(s)
(Contact Process): 2SO2(g) + O2(g) ⇌ 2SO3(g)
Hydrogenation of alkenes
Ni(s) or Pt(s)
CH2=CH2(g) + H2(g) → CH3CH3(g)
Removal of oxides of nitrogen, CO and unburnt hydrocarbons in the Pt(s), Pd(s), Rh(s) in the
exhaust gases from car engines catalytic converter

C=C double bond

surface of nickel catalyst

Figure 25. Catalytic hydrogenation of alkenes is used in the conversion of inedible vegetable oils to edible margarine

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9.2.1 Mode of action of heterogeneous catalyst: Haber process

LO8(j)part: outline the different modes of action of homogeneous and heterogeneous catalysis, including: (i) the Haber process

The mode of action of heterogeneous catalyst is explained below with reference to the reaction in the
Haber process: N2(g) + 3H2(g) ⇌ 2NH3(g), catalysed by finely divided iron.

(a) (b) (c) (d) (e) (f)

Figure 26. Mode of action of heterogeneous catalysis in the Haber Process

The three stages involved are:

• Adsorption (Figure 26a): The gaseous reactant molecules (N2 and H2) are adsorbed onto the active
sites by formation of weak attraction forces. This process brings reactant molecules closer
together (increasing their surface concentration), weakens the covalent bonds in the reactant
molecules, thus lowering the activation energy, and orientates reactant molecules correctly for
reaction to occur.

• Reaction (Figure 26b-e): Reaction occurs where bonds are broken and new bonds are formed.

• Desorption (Figure 26f): Product molecule (NH3) desorbs from the catalyst surface so that active
sites are exposed for further reaction.

The rate of reaction is controlled by how fast the gaseous reactants are adsorbed and how fast the
products are desorbed. When the active sites are fully occupied (i.e. when the catalyst is saturated),
there is no increase in reaction rate even if the concentration of reactants or pressure of the system
is increased. Since rate is no longer affected by [reactant], order of reaction with respect to [reactant]
becomes zero when the catalyst is saturated.

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9.2.2 Application of heterogeneous catalysis: Catalytic removal of harmful gases in the exhaust
gases from car engines
LO8(j)part: outline the different modes of action of homogeneous and heterogeneous catalysis, including: (ii) the catalytic removal of
oxides of nitrogen in the exhaust gases from car engines

The combustion of petrol in car engines not only gives carbon dioxide and water but also three harmful
products:
• oxides of nitrogen (from the reaction between N2 and O2 from the air, under the high
temperatures in the car engine)
• carbon and carbon monoxide (from incomplete combustion)
• unburnt hydrocarbon

Catalytic converters are used to remove these harmful gases by oxidising or reducing them.

• reduction of NO to N2: CO + NO → CO2 + ½N2

• oxidation of CO to CO2: CO + ½O2 → CO2

• oxidation of hydrocarbons to CO2 and H2O: hydrocarbon + O2 → CO2 + H2O

The exhaust gases are passed through the converter, which contains metals such as platinum and
rhodium coated on a honeycomb support (see Figure 27). The harmful gases are adsorbed onto the
surface of the metals, go through a reaction and the harmless gases then desorb from the surface.

Figure 27. A catalytic converter

Catalytic converters only work with unleaded petrol because lead ‘poisons’ the catalyst in the
converter (i.e. destroy their catalytic action).

Exercise 9.3 [J95/IV/39 modified]

A catalytic converter converts harmful gases from the exhaust system of a car into carbon dioxide,
nitrogen and water vapour.
Which processes take place in the catalytic converter?

1 Carbon monoxide and hydrocarbons react together.

2 Carbon monoxide and nitrogen oxide react together.
3 Platinum and rhodium catalyse redox reactions.

A 1, 2 and 3 are correct

B 1 and 2 only are correct
C 2 and 3 only are correct
D 1 only is correct

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9.3 Autocatalysis

In autocatalysis, the reaction is catalysed by one of its products. For example, Mn2+ ions catalyse the
reaction between manganate(VII) ions and ethanedioate ions:

2MnO4−(aq) + 16H+(aq) + 5C2O42−(aq) → 2Mn2+(aq) + 10CO2(g) + 8H2O(l)

autocatalyst

Figure 28 shows the characteristic concentration-time graph for an autocatalytic reaction. Compare
this graph to the concentration-time graphs in Section 4.1.1.

The reaction rate is slow at the

start so the gentle gradient.
concentration
of reactant
The reaction speeds up as the autocatalyst is produced so
the gradient increases.

The reaction slows down due to decreasing

concentrations of reactants. It eventually
stops when a reactant is used up.

time
Figure 28. Typical concentration-time graph for a reaction in which autocatalysis occurs

Exercise 9.4 [J02/I/11, N89/3/10] (worked example)

Which curve is obtained if the rate of reaction is plotted against time for an autocatalytic reaction
(i.e. a reaction in which one of the products catalyses the reaction)?

A B C D

As the reaction starts, the rate is slow because very little catalyst is present. As the autocatalyst is
produced, the rate increases and reaches a maximum before falling due to the falling concentration
of reactants (which would slow down the rate).

You can view the video explanation via this link.

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9.4 Biological catalysts – Enzymes

9.4.1 Catalytic action of enzymes

LO8(k): describe enzymes as biological catalysts which may have specific activity

Enzymes are biological catalysts that speed up chemical reactions in living cells. They are proteins,
which are polymers made up of hundreds of units of amino acids. Enzymes are mainly globular
proteins which are soluble in water. Hence they are homogeneous catalysts, though the mechanism
of action resembles heterogeneous catalysis.

The mechanism, described as a ‘lock-and-key’ hypothesis, is illustrated in Figure 29. It may be

simplified as the following two steps:

enzyme + substrate ⇌ enzyme-substrate complex (fast)

enzyme-substrate complex → enzyme + products (slow, rate-determining)

The substrate first binds to the active site of the enzyme to form the enzyme-substrate complex.
Within the complex, the substrate molecule then undergoes reaction (bond reorganisation and/or
reaction with other molecules). Finally, the products are released from the enzyme and diffuse away.
The active site is empty again and ready to take in another substrate.

Substrate: the reactant that binds to the enzyme’s active site

Active site: specific point on the enzyme where reaction takes place

Figure 29. ‘Lock-and-Key’ mechanism of enzymes

Most enzymes are highly specific, catalysing only one reaction, or one group of similar reactions.
Only a reactant molecule of the correct size and shape can attach to the enzyme’s active site.

Enzymes are highly efficient. Enzyme-catalysed reactions have very low activation energies. Virtually
every collision of the substrate with the active site leads to reaction. Hence, despite the low body
temperature and concentrations, reactions in living cells take place rapidly.

Enzymes extracted from organisms are used in many industrial processes such as the manufacture of
antibiotics and laundry detergents. Genetically engineered enzymes have also been used to make
useful compounds such as 1,3-propanediol for making polymers, esters used in cosmetics and drugs
for treatment of diabetes and cancer.

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Some examples of enzyme-catalysed reactions are as follows:

• Hydrogen peroxide, produced in many metabolic reactions, is harmful to cells. It is rapidly

decomposed to water and oxygen in the presence of the enzyme, catalase:

catalase
H2O2(aq) ⎯⎯⎯⎯→ H2O(l) + ½O2(g)

Activation energies for the decomposition of hydrogen peroxide (for your information)
uncatalysed catalyst: platinum catalyst: catalase
Ea / kJ mol–1 76 50 8

• Yeast contains a mixture of enzymes called zymase, which converts sucrose into ethanol and
carbon dioxide:
zymas e
C12H22O11(aq) + H2O(l) ⎯⎯⎯
⎯→ 4CH3CH2OH(aq) + 4CO2(g)
sucrose ethanol

9.4.2 Relationship between [substrate] and rate of an enzyme-catalysed reaction

LO8(l): explain the relationship between substrate concentration and the rate of an enzyme-catalysed reaction in biochemical systems

Figure 30 shows the characteristic relationship between rate of an enzyme-catalysed reaction and
[substrate]. Compare this graph to the rate-concentration graphs in Section 4.1.2.

rate of first order w.r.t. [substrate]

reaction

zero order w.r.t. [substrate]

maximum
rate

0 [substrate] /mol dm–3

Figure 30. Graph of rate of an enzyme-catalysed reaction against substrate concentration

At low [substrate], the enzyme concentration is greater than substrate concentration. The rate of
reaction increases proportionally with increasing substrate concentration as shown by the straight
line graph. The reaction is first order with respect to the [substrate].

At high [substrate], all the active sites are filled (i.e. saturated) with substrate molecules. Further
increase in [substrate] does not affect the rate as shown by the horizontal line. The reaction is now
zero order with respect to the [substrate].

To further increase the maximum rate of reaction, the concentration of the enzyme has to be
increased.

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Exercise 9.5 [N2001/III/34] (worked example)

The graph shows the results of an investigation of the initial rate of hydrolysis of maltose by the
enzyme amylase. In the experiments, the initial concentration of maltose was varied but that of
amylase was kept constant.
initial rate
of reaction

[maltose]
Which conclusions can be deduced from these results?
1 When [maltose] is low, the rate is first order with respect to [maltose].
2 When [maltose] is high, the rate is independent of [maltose].
3 When [maltose] is high, the rate is independent of [amylase].

A 1, 2 and 3 are correct

B 1 and 2 only are correct
C 2 and 3 only are correct
D 1 only is correct

Option 3 is not true because at high [maltose], initial rate is independent of [maltose] since changing
[maltose] will not change the rate as the enzyme’s active sites are saturated.

It is possible to increase the maximum rate of reaction by increasing the concentration of the enzyme
itself, i.e. increasing [amylase]as this will increase the number of active sites.

You can view the video explanation via this link.

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9.4.3 Effects of temperature and pH on enzyme activity

Each enzyme has an optimum set of temperature and pH at which it functions best. Changes in these
conditions will cause the enzymes to denature. The denatured enzyme loses their globular structure,
i.e. the active site changes shape and can no longer bind to the substrate (see Figure 31).

Figure 31. Denaturation of enzymes

Denaturation: Process where the (globular)

structure of proteins is changed and it loses
its three-dimensional shape.

Figure 32 shows the effect of temperature and pH changes on the rate of enzyme activity.
optimum pH
rate of enzyme activity

rate of enzyme activity

optimum
temperature

temperature/°C pH
(a) (b)
Figure 32. Enzyme activity is affected by (a) temperature and (b) pH

LOOKING AHEAD
Transformation of matter involves the study of the spontaneity (thermodynamics), rate (kinetics) and
extent of chemical reactions (concept of equilibrium). Concepts learnt in Topic 5 Chemical Energetics
and Topic 6 Reaction Kinetics will be used again in Topic 7 Chemical Equilibria to explain concepts
related to the extent to which a reaction proceeds.

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07 Chemical Equilibria
GUIDING QUESTIONS
● What are the characteristics of a system that has reached dynamic equilibrium? How can we
describe such a system at equilibrium?
● Why would systems tend towards a state of equilibrium?
● What happens when a system at equilibrium is disturbed?
● What are the factors to consider for optimal yield in a reversible reaction?

LEARNING OUTCOMES
Students should be able to:
9(a) explain, in terms of rates of the forward and reverse reactions, what is meant by a reversible
reaction and dynamic equilibrium
9(b) state Le Chatelier’s Principle and apply it to deduce qualitatively (from appropriate
information) the effects of changes in concentration, pressure or temperature, on a system
at equilibrium
9(c) deduce whether changes in concentration, pressure or temperature or the presence of a
catalyst affect the value of the equilibrium constant for a reaction
9(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]
9(e) calculate the values of equilibrium constants in terms of concentrations or partial pressures
from appropriate data
9(f) calculate the quantities present at equilibrium, given appropriate data (such calculations will
not require the solving of quadratic equations)
9(g) show understanding that the position of equilibrium is dependent on the standard Gibbs
free energy change of reaction, G⚪
[Quantitative treatment is not required]
9(h) describe and explain the conditions used in the Haber process, as an example of the
importance of an understanding of chemical equilibrium in the chemical industry

REFERENCES
1. Peter Cann and Peter Hughes (2015), Chemistry, Hodder Education, Chapter 9
2. Martin S. Silberberg (2009), Chemistry: The Molecular Nature of Matter and Change, 5th Edition,
McGraw Hill, Chapter 17

LOOKING BACK
Theoretically all reactions may be considered as reversible and occur to different extents. The
position of equilibrium where a reaction lies, is related to the thermodynamics of the reaction,
which we learnt under Topic 5 Chemical Energetics & Thermodynamics. Here we shall find out how
the standard Gibbs free energy change, G⚪, and the equilibrium position are related. Also relevant
are concepts from Topic 6 Reaction Kinetics, as we consider the rates of forward and backward
reactions, and how their concentration-time graphs look like in a reversible reaction.

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1 INTRODUCTION

Many chemical reactions appear to go to completion, converting reactants to products until the
limiting reactant is used up. An example is the combustion of methane:

CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)

A reaction is considered as having gone to completion if any reactants in the final mixture are present
at such low concentrations that they cannot be detected when the mixture is analysed. In practical
terms, this means that if the reaction is more than 99% complete, it can be regarded as having gone
to completion. Reactions that go to completion may be represented using the concentration-time
graph below:

Concentration

product reaction completed at this

time

limiting amount of limiting reagent decreases to

reactant zero

0 time

Figure 1. Concentration-time graph for reactions that go to completion

However, there are other reactions which may not go to completion. At the end of these reactions, a
detectable amount of reactant remains, mixed with the product. Such reactions are called reversible
reactions.

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2 Reversible Reactions
LO9(a)part: explain, in terms of rates of the forward and reverse reactions, what is meant by a reversible reaction

A reversible reaction is one which can occur in both directions.

A double-headed arrow ‘⇌’ is used to denote a reversible reaction.

Examples of reversible reactions include:

Haber Process: N2(g) + 3H2(g) ⇌ 2NH3(g)
Contact Process: 2SO2(g) + O2(g) ⇌ 2SO3(g)
Esterification: CH3CO2H(l) + CH3CH2OH(l) ⇌ CH3CO2CH2CH3(l) + H2O(l)

Reversible reactions may be represented using the concentration-time graph below:

Concentration

State of equilibrium reached

at this time

product

reactant
amount of limiting reagent does not
decrease to zero
0 time

Figure 2. Concentration-time graph for a reversible reaction

2.1 Dynamic Equilibrium

LO9(a)part: explain, in terms of rates of the forward and reverse reactions, what is meant by dynamic equilibrium

A reversible reaction will reach a state of equilibrium where no overall change of reactant and product
concentrations is observed. It seems as though the reaction has stopped, but it is actually not the case.
The forward reaction continues to occur since reactants are still present! The reason why
concentrations are not changing is because the reverse reaction is also going at exactly the same rate,
turning the ‘new’ products back into reactants.

A dynamic equilibrium refers to a reversible reaction in which the forward and reverse reactions are
both taking place at the same rate resulting in no overall changes in concentrations.

The word ‘dynamic’ means that the reactions are still taking place although there is no observable
change, i.e. the equilibrium is not static. An analogy of dynamic equilibrium is that of a child running
up an escalator which is moving in the opposite direction. When the child and the escalator are moving
at the same rate, the position of the child appears unchanged (although he is still running). An analogy
of static equilbrium would be that of two children on a see-saw. At ‘equilibrium’, the see-saw remains
horizontal (i.e. not moving up or down) and the positions of the children are fixed.

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(a) Analogy of dynamic equilibrium (b) Analogy of static equilibrium

Figure 3

Consider the decomposition of N2O4 into its monomers:

N2O4(g) forward reaction 2NO2(g)

colourless ⇌ brown
backward reaction
+

1.00 mol of colorless N2O4(g) is added into a 1 dm3 flask. The flask is sealed and maintained at a
particular temperature e.g. 200 oC. Figure 4 shows the concentration-time graph and the rate-time
graph for the decomposition reaction.
Concentration / mol
dm–3

[NO2]

[N2O4]

t1 t1

a) Concentration-time graph b) Rate-time graph

Figure 4. Decomposition of N2O4 into its monomers

● At time = 0 (start of reaction), only N2O4 is present. Then the forward reaction starts to occur: N2O4
decomposes to form brown NO2 gas.
● As [N2O4] decreases, rate of forward reaction (ratef) decreases. On the other hand, [NO2] increases
so rate of reverse reaction (rateb) increases.
Observation: The contents of the flask slowly turn pale brown and darken.

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● At time = t1, the system reaches dynamic equilibrium. [N2O4] and [NO2] remain constant i.e. there
is no net change in concentrations (note [N2O4] does not decrease to zero) and ratef = rateb (but
not zero).
Observation: Intensity of the brown colour stops changing.

In this example, the flask has to be sealed as equilibrium can only be achieved in a closed system,
one in which no substances are lost to or gained from the surroundings. An open system allows
substances to escape or to enter and equilibrium cannot be established.

Consider the thermal decomposition of CaCO3: CaCO3(s) ⇌ CaO(s) + CO2(g)

In an open system, CO2 once formed escapes and is not present to react with CaO. Eventually, all the
CaCO3 is decomposed, i.e. forward reaction goes to completion. In the closed system, CO 2 is able to
react with CaO to form CaCO3. Eventually, the system reaches equilibrium. Further heating will not
change the amount of CaCO3, CaO and CO2.

(a) Heating CaCO3 in an open container (b) Heating CaCO3 in a closed container
Figure 5

Equilibrium can be achieved “from either direction”. This means that we can establish equilibrium
starting with either the reactants or products (or actually any amounts of reactants and products).
This is illustrated in Figure 6 using the reaction N2(g) + 3H2(g) ⇌ 2NH3(g).
Gas Pressure

Gas Pressure

H2
H2
NH3
NH3 N2
N2

Time Time

(a) Approaching equilibrium from the reactants side (b) Approaching equilibrium from the product side
Figure 6

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Exercise 2.1 (Worked Example)

Some NO2 was placed in a closed vessel. Sketch a graph showing how the pressure of each substance
varies over time until equilibrium is reached.
2NO2(g) ⇌ 2NO(g) + O2(g)

Let x (in Pa) be the increase in PO2.

The change in the partial pressures of the reactants and the products must follow the stoichiometry
of the chemical equation. Hence as PO2 changes by x Pa, it must mean that PNO2 & PNO change by 2x
Pa. This is reflected in the relative height of the changes shown in the graph. Note also that the
pressures of all the 3 compounds reaches the new equilibrium values at the same time. This time,
teqm, signifies that a new equilibrium position has been achieved.

Pressure/ Pa

2x
NO2

NO
2x O2
x
time/ min
teqm

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3 EQUILIBRIUM CONSTANT

3.1 Expression for Equilibrium Constant

LO9(d): deduce expressions for equilibrium constants in terms of concentrations, K c, and partial pressures, Kp [treatment of
the relationship between Kp and Kc is not required]

The Equilibrium Law states that for any system at equilibrium, the product of the concentrations of
each product (raised to the power equal to its coefficient in the equation) divided by the product of
the concentrations of each reactant (raised to the power equal to its coefficient in the equation) has
a constant value called the equilibrium constant, K, at a constant temperature.

Equilibrium constant can be expressed in terms of:

● concentration (in mol dm–3), denoted by Kc
● partial pressure (usually in Pa or atm), denoted by Kp

Consider the reversible reaction: aA + bB ⇌ cC + dD

Ceqm Deqm
c d
C D
c d

 A eqm B eqm which is simplified to Kc =  A  B 

a b a b
Kc =

If the above is a gaseous system,

(pC )c (pD )d
a b
we can write Kp = (p A ) (pB ) (since [gas]  Pgas)
nA
 p total
where partial pressure of A = pA = total no. of moles of gases

The units of Kc or Kp depend on their expressions. Using the above expressions, units of Kc are
(mol dm–3)(c+d) – (a+b) and units of Kp are (Pa)(c+d) – (a+b) or (atm)(c+d) – (a+b).

Relationship between Kc and Kp (Background Info)

nA pA
If the mixture behaves as an ideal gas, [A] = V = RT (by rearranging pV = nRT)
Since R and T are constant, [A]  PA

pc c pd d
( ) ( )
C D
c d RT
p
RT
pb b
(pc )c (pd )d
Substitute into Kc, Kc = Aa Bb ( a )a
= RT
( ) a b
RT = (pa ) (pb ) (RT)(a+b)–(c+d)
Kc = Kp (RT)(a+b)–(c+d)

When the number of moles of gases is the same on each side of the stoichiometric equation, Kc = Kp!

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Exercise 3.1
For each of the following reactions, write the equilibrium constant expressions, Kc and Kp, and state
the units. Assume that gas pressure is measured in Pa.

Equilibrium Kc & units Kp & units

(a) N2(g) + 3H2(g) ⇌ 2NH3(g) [NH3 ]2 (PNH3 )2

Kc = mol−2 dm6 Kp = Pa–2
[N2 ][H2 ] 3 (PN2 )(PH2 )3

(b) 2NH3(g) ⇌ N2(g) + 3H2(g)

(c) ½N2O4(g) ⇌ NO2(g)

3.2 Equilibrium constant for reactions involving pure liquids and solids

Consider the following equilibria involving pure liquids and solids:

(a) CaCO3(s) ⇌ CaO(s) + CO2(g)
(b) CH3CO2H(l) + C2H5OH(l) ⇌ CH3CO2C2H5(l) + H2O(l)
(c) CO2(aq) + H2O(l) ⇌ H2CO3(aq)

Reaction (a) is an example of heterogeneous equilibrium as the components are in different phases.
Reactions (b) and (c) are examples of homogeneous equilibria as the components are in the same
phase.

Applying the Equilibrium Law, the equilibrium constant expression for reaction (a) may be written as:
CaOCO2 
K = CaCO3  (note: [CaCO3] and [CaO] are constant)
CaCO3 
Rearranging, K × CaO = [CO2] (group the constant terms together)
–3
Kc = [CO2] mol dm

or Kp = pCO2 Pa

Hence, when writing equilibrium constant expressions for heterogeneous equilibria, we omit the
concentration of pure solids or liquids as they are considered a constant.

Why are the concentrations of pure solids or liquids considered constant? (Background Info)

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n m density
concentration of pure solid = V = Mr V = Mr = constant (since density and Mr are constant)

This also applies to the concentration of a pure liquid. For example,

1 g cm−3
−1
 1000 cm3
[H2O(l)] = 18 g mol = 55.5 mol dm–3

The concentration of liquids which are acting as a solvent remains almost constant since a solvent is
present in large excess so the changes, if any, will be negligible.

H2CO3 
Hence, for reaction (c), Kc = CO2  (no units)

Connecting Equilibrium and Kinetics: Equilibrium Constant and Rate Constant (Background Info)

For a reversible reaction:

ratef
A + B C
rateb

The equilibrium constant K can be derived from Kinetics.

If the reaction proceeds in a single step, rate of forward reaction, ratef = kf [A][B]
and rate of backward reaction, rateb = kb[C]
At dynamic equilibrium,
ratef = rateb
kf [A][B] = kb[C]

kf
=
C
k b A B

kf
∴ K = kb

This expression is true only if the chemical reaction proceeds in a single step. Many reactions do not
proceed in one step but through complicated multi-step mechanisms.

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4 Position of Equilibrium and Equilibrium Constant

The position of equilibrium refers to the composition of an equilibrium mixture, i.e. the relative
proportion of products to reactants in an equilibrium mixture. Position of equilibrium may lie on the
right (i.e. towards the products) or lie on the left (i.e. towards the reactants).

The magnitude of Kc or Kp is a measure of the position of equilibrium or the extent to which reactants
are converted into products (i.e. how far the forward reaction occurs).

● A small K means the position of equilibrium lies on the left. The extent of conversion of reactants
into products is small, so the proportion of products to reactants is low.

● A large K means the position of equilibrium lies on the right. The extent of conversion of reactants
into products is large, so the proportion of products to reactants is high.

Figure 7. Magnitude of K is a measure of the position of equilibrium

The magnitude of Kc or Kp gives no information about the rate of reaction (how fast the reaction
occurs). Some slow reactions may eventually yield a large amount of product e.g. rusting of iron.
Others reach equilibrium quickly but reacts only to a small extent e.g. dissociation of weak acids.
Knowing the extent of a reaction allows us to adjust the conditions to get a high yield.

The equilibrium constant, K, is not the same as the position of equilibrium. The position of equilibrium
can shift, but K is a constant which changes only with temperature.

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5 Position of Equilibrium and Le Chatelier’s Principle

LO9(b): state Le Chatelier’s Principle and apply it to deduce qualitatively (from appropriate information) the effects of changes
in concentration, pressure or temperature, on a system at equilibrium
LO9(c): deduce whether changes in concentration, pressure or temperature or the presence of a catalyst affect the value of
the equilibrium constant for a reaction

Changes in conditions such as concentration, pressure or temperature, can disturb the position of
equilibrium of a system. The system reacts in a way to re-attain equilibrium. The changes in the
position of equilibrium can be predicted (qualitatively) from Le Chatelier’s Principle.

Le Chatelier’s Principle states that if the conditions of a system at equilibrium are changed, the
position of equilibrium shifts so as to reduce that change.

5.1 Effect of Changes in Concentration

Consider the equilibrium: N2(g) + 3H2(g) ⇌ 2NH3(g)

What is the effect of adding some N2 to the equilibrium mixture?

● When some N2 is added to the equilibrium mixture, concentration of N2 increases.
● By Le Chatelier’s principle, position of equilibrium shifts to the right to consume some of the N2
so as to decrease concentration of N2.
● Concentration of H2 will also decrease while that of NH3 will increase.

Figure 8 shows how the concentrations of N2, H2 and NH3 changes with time, when N2 is added at t1.

initial new
equilibrium equilibrium
3.0
H2
H2
2.43
2.38
concentration

NH3
2.0
NH3

1.31

N2 N2
0.5

time
t1 t2

Figure 8. Changes in concentration after some N2 is added at t1

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Key points to note:

● At t1, [N2] increases sharply due to the addition of N2.

● As predicted, [NH3] at the new equilibrium position is higher than its original concentration.
● [N2] still ends up higher than before the addition at t1. The position of equilibrium can only shift
to reduce (not completely remove) the change.
● [H2] ends up lower than before because some reacted with the added N2.
● Most importantly, although the position of equilibrium shifted to the right, the value of
equilibrium constant, Kc, remains the same.
[NH3 ]2 22
3
Before t1 (initial equilibrium), Kc = [N2 ][H2 ] = (0.5)(3) = 0.30 mol–2 dm6
3

[NH3 ]2 2.382
3
After t2 (new equilibrium), Kc = [N2 ][H2 ] = (1.31)(2.43) = 0.30 mol–2 dm6
3

Changing [N2] affects the position of equilibrium but does not change the value of Kc.

As the above is a gaseous system, the partial pressure of N2 is also increased when some N2 is added
since [N2]  PN2. Hence, we can say that changing the partial pressure of a gaseous component, by
adding some of that component e.g. N2, will have the same effect as changing its concentration.

Consider another equilibrium: CaCO3(s) ⇌ CaO(s) + CO2(g)

Adding more CaCO3 or CaO will not affect the position of equilibrium because the position of
equilibrium is unaffected by pure solids or liquids since their concentrations are considered constant
(see Section 3.2).

Exercise 5.1 (Worked Example)

Consider the reaction in equilibrium below:
Fe3+ (aq) + SCN– (aq) ⇌ [FeSCN]2+(aq)
pale yellow colourless blood-red
State and explain the observations when NaSCN(s) is added to the above equilibrium mixture.

The NaSCN(s) added dissolves in the aqueous solution, [SCN–] increases.

By Le Chatelier’s principle, position of equilibrium shifts to the right to decrease [SCN–].

Thus the red colour darkens / deepens.

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Exercise 5.2
Haemoglobin (Hb) is a protein found in red blood cells. They are large proteins that contain heme
groups in them. Each haemoglobin molecule contains four heme groups, and each heme group
contains an iron at its active sites which allow for reversible binding to O2 molecule. Each Hb can
bind up to four oxygen molecules and the binding occurs in successive steps.
The entire system of oxygen transport and delivery in the body depends on the pickup and release
of O2 by haemoglobin according to the series of equilibria:

Hb + O2 ⇌ Hb(O2)
Hb(O2) + O2 ⇌ Hb(O2)2
Hb(O2)2 + O2 ⇌ Hb(O2)3
Hb(O2)3 + O2 ⇌ Hb(O2)4

Heme group

(a) With reference to the above series of equilibria, comment on the position of equilibrium
(i) in oxgen-starved muscles where 𝑃𝑂2 is low

(ii) in the lungs where 𝑃𝑂2 is high

(b) How do people at high altitude (low 𝑃𝑂2 ) adapt?

5.2 Effect of Changes in Total Pressure

For a system with gaseous components, changing the volume of the container changes the total
pressure. The change in total pressure can cause the position of equilibrium to shift. The effect on
systems containing only liquids and solids is negligible as liquids and solids are nearly incompressible.

Consider the same equilibrium: N2(g) + 3H2(g) ⇌2NH3(g)

What is the effect of decreasing the volume of the container?

● If the volume of the container is decreased, the pressure will increase (Figure 9b).
● The system will try to reduce the pressure by reducing the total number of gas molecules.
● Hence, the position of equilibrium will shift right towards the side with fewer moles of gas.

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= N2
➔ ➔
= H2
= NH3

at the instant when volume

initial equilibrium new equilibrium
is decreased
N2 molecule: 2 units N2 molecule: 2 units N2 molecule: 1 unit ( by 1 unit)
H2 molecule: 6 units H2 molecule: 6 units H2 molecule: 3 units ( by 3 units)
NH3 molecule: 3 units NH3 molecule: 3 units NH3 molecule: 5 units ( by 2 units)
(a) (b) (c)
Figure 9. Changes in the no. of molecules when volume of container decreases

Figure 9 shows that when [NH3] increases by 2 units, [N2] and [H2] decrease by 1 unit and 3 units
respectively. Overall, there is a decrease of 2 units of gas molecules. At the new equilibrium (Figure
9c), the pressure is lower than the pressure immediately after volume decreases (Figure 9b).
Figure 10 shows how the concentration of N2, H2 and NH3 changes with time, when volume of the
container is decreased at t1.
initial new
equilibrium equilibrium

H2
3.67
concentration

H2
3.0 2.89
NH3
NH3
2.0

N2 N2
0.5 0.56

time
t1 t2
Key pointsFigure
to note:
10. Changes in concentration after pressure is increased by reducing volume of container at t 1

● At t1, [N2], [H2] and [NH3] all increase sharply due to the reduction in volume of container.
● As predicted, since the position of equilibrium shifts right, [NH3] is higher than its concentration
at t1 when the volume of container is decreased, but [N2] and [H2] are lower.
● Similar to changing concentration, although the position of equilibrium shifted to the right, the
value of equilibrium constant, Kc, remains the same.

In some reactions, the total number of moles of gases on each side of the stoichiometric equation
are the same i.e. number of moles of gases do not change during reaction. For example,

H2(g) + I2(g) ⇌2HI(g)

In this case, changes in pressure have no effect on the position of equilibrium.

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Exercise 5.3
Consider the following system at equilibrium:
N2O4(g) ⇌ 2NO2(g)
colourless brown

How would increasing the total pressure affect the position of the equilibrium? What would you
observe?

When the total pressure increases, by Le Chatelier’s principle, the position of equilibrium shifts to
the left so as to decrease the pressure by favouring the reaction that results in fewer moles of
gases. Thus less NO2 will be present and intensity of brown colour decreases.

5.3 Effect of Changes in Temperature

The effect of temperature on the position of equilibrium depends on the enthalpy change of the
reaction.

Consider the equilibrium: N2(g) + 3H2(g) ⇌ 2NH3(g) Hr = −92 kJ mol−1

What is the effect of decreasing the temperature of the equilibrium mixture?

● When temperature is decreased, the system will try to produce additional heat by favouring the
exothermic reaction.
● Since the forward reaction is exothermic in this equilibrium, by Le Chatelier’s Principle, the
position of equilibrium shifts to the right.
● Hence, [NH3] increases while [N2] and [H2] decreases.

If a forward reaction is endothermic, the position of equilibrium would shift to the left instead.

Figure 11 shows how the concentrations of N2, H2 and NH3 changes with time when temperature is
decreased at t1.
initial new
equilibrium equilibrium
3.0
H2 NH3
2.6
concentration

2.0 2.1
H2
NH3

N2
0.5 N2
0.2
time
t1 t2
Figure 11. Changes in concentration after temperature is decreased at t1
Key points to note:

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● Unlike changes in concentration or pressure, at t1, [N2], [H2] and [NH3] did not change sharply.
● As predicted, at the new equilibrium position, [NH3] increases while [N2] and [H2] decreases.
● Unlike changes in concentration or pressure, changes in temperature affects both the position of
equilibrium and the value of the equilibrium constant.
[NH3 ]2 22
3
Before t1 (initial equilibrium), Kc = [N2 ][H2 ] = (0.5)(3) = 0.3 mol–2 dm6
3

[NH3 ]2 2.62
3 3
After t2 (new equilibrium), Kc = [N2 ][H2 ] = (0.2)(2.1) = 3.8 mol–2 dm6
When the forward reaction is exothermic, a decrease in temperature increases the value of Kc or
Kp.

Why does K increase when temperature decrease for exothermic reactions? (Background Info)

kf
In Section 3.2 Background Info, we derived the relationship: K = k b .

The Arrhenius equation (Topic 6 Reaction Kinetics) shows that when temperature is decreased, rate
constant, k, will decrease. Hence when temperature is decreased, both the rate constants of the
forward and backward reactions, kf and kb, will decrease. So both the forward and backward reactions
become slower.

However, since the forward reaction is exothermic, the backward reaction has a larger activation
energy. Hence, kb will decrease more than kf when temperature decreases so K increases since
kf
K = kb .
Because the rate of the backward reaction decreases more than that of the forward reaction, the
system would favour the forward reaction to produce additional heat (as predicted by Le Chatelier’s
Principle).

Alternatively, the van’t Hoff equation can be used to show how the equilibrium constant, K, increases
when temperature is decreased for exothermic reactions:

𝐻𝑜 1 𝑆𝑜
𝑙𝑛 𝐾 = − ( )+
𝑅 𝑇 𝑅

Section 9 (Background Info) will show the derivation of the van’t Hoff equation from thermodynamics.

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Exercise 5.4
Watch the video “Effect of Temperature on Cobalt Complex” on Google site and answer the
following questions. The equation for the reaction in the video is given below.

[Co(H2O)6]2+(aq) + 4Cl–(aq) ⇌ [CoCl4]2–(aq) + 6H2O(l)

pink blue

(a) What was the colour of the solution of cobalt(II) ions at room temperature?

(b) What did you observe when the solution was heated?

(c) What did you observe when the solution was cooled in an ice bath?

(d) Using your answers in (b) and (c), deduce whether the reaction (as shown in the equation) is
exothermic or endothermic. Explain your answer.

5.4 Effect of Presence of a Catalyst

In Topic 6 Reaction Kinetics we learnt that a catalyst is a substance that speeds up a chemical reaction
by providing an alternative reaction pathway of lower activation energy, while remaining chemically
unchanged at the end of the reaction.

energy
/ kJ mol1
Ea forward Ea backward
(uncatalysed) change in Ea (uncatalysed)

Ea forward
Ea backward
(catalysed)
(catalysed)

reactants

products

progress of reaction

Figure 12. Effect of adding a catalyst on activation energies

● A catalyst lowers the activation energy of both forward and backward reactions by the same
amount. Hence, both forward and backward reaction rates increase by the same extent.
● The time taken to reach equilibrium is shortened.
● However, the position of equilibrium (i.e. extent of conversion of products into reactants or yield)
is not affected.
● The value of equilibrium constant, Kc or Kp, is also unaffected by the presence of a catalyst.

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6 The Reaction Quotient

Consider the reversible reaction: aA + bB ⇌ cC + dD

Cc Dd
At any instant, Qc = Aa Bb where [ ] denotes the instantaneous concentration in mol dm–3

Units of Qc is (mol dm–3)(c+d) – (a+b)

Qc and Kc have the same expressions and units. However, at a given temperature, Qc can take on any
value while Kc has a constant value. When Qc = Kc, the system is at equilibrium.

We can compare the values of Qc and Kc to determine the direction in which a reaction will proceed
towards equilibrium.

● If Qc < Kc, reaction will proceed in the forward direction to consume more reactants and form
more products until Qc equals to Kc (i.e. until system reaches equilibrium).
● If Qc > Kc, reaction will proceed in the backward direction to form more reactants and consume
more products until Qc equals to Kc (i.e. until system reaches equilibrium).

Using the above, the changes in the position of equilibrium due to changes in concentration or
pressure can be predicted (quantitatively).

Exercise 6.1 (Worked Example)

Consider the reaction: N2(g) + 3H2(g) ⇌ 2NH3(g)
There are 0.249 mol of N2, 3.21 × 10–2 mol of H2 and 6.42 × 10–4 mol of NH3 in a 3.50 dm3 reaction
vessel at 375 °C. The numerical value of the equilibrium constant, Kc, is 1.20 at this temperature.
Decide whether the system is at equilibrium. If it is not, predict in which direction the reaction will
proceed to achieve equilibrium.

We first convert the quantities of each compound from moles to mol dm –3 as the Qc expression
contains concentration terms.
[N2] = 0.249 / 3.50 = 7.114 × 10−2 mol dm–3
[H2] = (3.21 × 10–2) / 3.50 = 9.171 × 10–3 mol dm–3
[NH3] = (6.42 × 10–4) / 3.50 = 1.834 × 10–4 mol dm–3

[NH3 ]2 (1.834×10−4 )2
Qc = = = 0.613 mol–2 dm6
[N2 ][H2 ]3 (7.114×10−2 )(9.171×10−3 )3

Qc  Kc so the system is not at equilibrium.

Since Qc < Kc, reaction will proceed in the forward direction
to increase [NH3], and decrease [N2] and [H2], until Qc = Kc.

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Exercise 6.2
Predict and explain what would be observed when water is added to a pink solution containing the
following equilibrium.
Co(H2O)62+(aq) + 4Cl–(aq) ⇌ CoCl42–(aq) + 6H2O(l)
pink blue

Effect of adding an inert gas to an equilibrium (Application Example)

Consider the equilibrium: 2NO2(g) ⇌ N2O4(g)

When an inert gas (e.g. argon) is added to this equilibrium mixture at constant total pressure, it is
incorrect to conclude, using Le Chatelier’s Principle, that the position of equilibrium is not affected
since pressure is constant. In actual fact, the position of equilibrium shifts left.

We can explain this by comparing the values of Qp and Kp.

𝑝 𝑁 2 𝑂4
The reaction quotient is written as: 𝑄𝑝 = (𝑝 2 ----- (i)
𝑁𝑂2 )

𝑁 2 𝑂4 𝑁𝑂2
Since 𝑝𝑁2𝑂4 = × 𝑃𝑡𝑜𝑡𝑎𝑙 and 𝑝𝑁𝑂2 = × 𝑃𝑡𝑜𝑡𝑎𝑙 ,
𝑡𝑜𝑡𝑎𝑙 𝑡𝑜𝑡𝑎𝑙

𝜂 𝑁 2 𝑂4 𝜂
upon substitution into (i) and simplification, 𝑄𝑝 = ( 2 × 𝑃𝑡𝑜𝑡𝑎𝑙 ----- (ii)
𝑁𝑂2 ) 𝑡𝑜𝑡𝑎𝑙

When argon is added at constant pressure, the total moles of gases, ηtotal, increases. Since the other
terms in equation (ii) are not changed, Qp increases. This makes Qp > Kp. Hence, the position of
equilibrium shifts left.

On the other hand, if argon is added to the mixture at constant volume, it is incorrect, again, to
conclude that since total pressure increases, position of equilibrium will shift to the right. In actual
fact, the position of equilibrium remains unchanged. This can also be explained using equation (ii).

Assuming the gases behave ideally (and obeys the ideal gas equation pV = nRT), when volume and
temperature are constant, pressure, ptotal is directly proportional to the total moles of gases, ηtotal.
Adding argon at constant volume cause both ηtotal and ptotal to increase, but their ratio remains the
same. Hence Qp (in equation (ii)) is unchanged and still equals to Kp, i.e. Qp = Kp so there is no effect
on the position of equilibrium.

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7 CALCULATIONS IN CHEMICAL EQUILIBRIUM

LO9(e): Calculate the values of equilibrium constants in terms of concentrations or partial pressures from appropriate data
LO9(f): Calculate the quantities present at equilibrium, given appropriate data (such calculations will not require the solving
of quadratic equations)

Exercise 7.1 (Worked Example)

For the reaction, CH3CO2H(l) + C2H5OH(l) ⇌ CH3CO2C2H5(l) + H2O(l),
3
a 10.0 cm mixture contained the following initial amounts in mol: ethanoic acid, 0.0525; ethanol,
0.0515; ester, 0.0314; water, 0.0167.

The equilibrium amount of ethanoic acid was found to be 0.0255 mol. Calculate the equilibrium
amounts (in mol) of ethanol, ester and water. Hence, calculate Kc for the reaction.

We construct an ICE (initial, change, equilibrium) table to help simplify the thought process in
working out the quantities of each compound in the chemical equation. Fill in the initial amounts
of each compound as given in the question. We can work out that the change in amount of
ethanoic acid is as follows:
nethanoic acid reacted at equilibrium = 0.0525 – 0.0255 = 0.0270 mol

This then means that the changes in quantity for the other compounds in the equation is the
same, since the stoichiometric ratio is 1 : 1 for all of them. The reactants therefore change by –
0.0270 while the products change by + 0.0270. The equilibrium quantities are then easily calculated by
adding or subtracting the change from the initial values respectively.

CH3CO2H + C2H5OH ⇌ CH3CO2C2H5 + H2O

initial amt / mol 0.0525 0.0515 0.0314 0.0167

change / mol – 0.0270 – 0.0270 + 0.0270 + 0.0270
equilibrium amt / mol 0.0255 0.0245 0.0584 0.0437

[ester][water] (0.0584⁄𝑉 )(0.0437⁄𝑉 )

Kc = = = 4.085 (no units)
[ethanoic acid][ethanol] (0.0255⁄𝑉 )(0.0245⁄𝑉 )

𝑛𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒𝑠
*Do remember to show that concentration =
𝑣𝑜𝑙𝑢𝑚𝑒

Exercise 7.2
In the reaction shown below, 4.0 mol of H2 and 2.0 mol of I2 are allowed to react in a 2.0 dm3 vessel
at 440 oC. The equilibrium concentration of HI is 1.9 mol dm–3.
H2(g) + I2(g) ⇌ 2HI(g)
Calculate the value of the equilibrium constant, Kc, for the reaction at 440 oC.

H2(g) + I2(g) ⇌ 2HI(g)

initial conc. / mol dm–3
change / mol dm–3
equilibrium conc. / mol dm–3

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Exercise 7.3 (Worked Example)

A gaseous mixture of 0.500 mol of H2 and 0.500 mol of I2 was placed in a reaction flask (with
constant volume) at 430 oC.
Given that the equilibrium constant, Kc, for the reaction, H2(g) + I2(g) ⇌ 2HI(g), is 54.3 at
430 oC, calculate the equilibrium number of moles of H2, I2 and HI.

Let x be the no. of moles of H2 reacted.

H2(g) + I2(g) 2HI(g)

initial amount / mol 0.500 0.500 0
change / mol –x –x + 2x
equilibrium amount / mol 0.500 – x 0.500 – x 2x

( )
2
2x
[HI] 2 V
(2 x)2
Kc = =
( ) = = 54.3
2
[H2 ][I2 ] 0.5− x
(0.5 − x)2
V
where V = volume of reaction flask

2x
 = 54.3 = 7.369
0.5 − x
2x = 3.684 – 7.369x
3.684
x= = 0.393 mol
9.369

At equilibrium,
nH2 = 0.500 – 0.393 = 0.107 mol = nI2
nHI = 2  0.393 = 0.786 mol

Exercise 7.4
Kc for the dissociation reaction R(aq) ⇌ S(aq) is 0.50 at 75 oC. A solution of R, with initial concentration
of 15.0 mol dm–3, is allowed to reach equilibrium at the same temperature. Calculate the equilibrium
concentration of R and S.

Exercise 7.5 (Worked Example)

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Consider the reaction: PCl5(g) ⇌ PCl3(g) + Cl2(g)

(a) PCl5 is 30.0% dissociated at a certain temperature and a pressure of 1.01 × 105 Pa. Determine
the value of Kp for the dissociation at this temperature.
(b) Calculate the pressure needed to achieve the degree of dissociation of PCl5(g) as 0.485, at the
same temperature.
nPCl5 dissociated
initial nPCl5
Note: In (b), degree of dissociation of PCl5 = = 0.485

(a) Consider basis of working: 1 mol of PCl5 present initially

At equilibrium, nPCl5 dissociated = 0.3 mol
Note that the change is described in % rather than an absolute value. In such cases, it is simply easier
to set the starting amount as 1 mole. Any starting amount may be used (e.g. 10 mol) but 1 mole is
a small value and easy to deal with, hence it was used in the worked solution that follows.

PCl5(g) ⇌ PCl3(g) + Cl2(g)

initial amount / mol 1 0 0
change / mol – 0.3 + 0.3 + 0.3
equilibrium amount / mol 1 – 0.3 = 0.7 0.3 0.3 Total = 1.3

equilibrium mole fraction 0.7 0.3 0.3

1.3 1.3 1.3
equilibrium partial pressure / Pa 0.7 0.3 0.3
× PT × PT × PT
1.3 1.3 1.3
PT = 1.01 × 105 Pa (after dissociation)
pPCl pCl
3 2
=
( 0.3
1.3
 PT )(10..33  PT )
Kp =
pPCl 5
(10..37  PT ) = 9.989 × 103 Pa

(b) Let initial nPCl5 be 1 mol, nPCl5 dissociated = 0.485 mol

PCl5(g) PCl3(g) + Cl2(g)
initial amount / mol 1 0 0
equilibrium amount / mol 1 – 0.485
0.485 0.485 Total = 1.485
= 0.515

Let pressure needed be PT in Pa. At the same temperature, KP remains constant.

( 0.485
1.485
 PT )(10..485
485
 PT ) (0.485)2 PT
Kp =
(1.485  PT )
0.515 =
(1.485)(0. 515)
= 9.989 103 Pa (KP from a)

 total pressure needed, PT = 3.248 104 Pa

nPCl5 dissociated
Note: In (b), degree of dissociation of PCl5 = = 0.485
initial nPCl5

Exercise 7.6 [HCI Prelim 2006]

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Carbon monoxide and hydrogen react according to the following equation.

CO(g) + 2H2(g) ⇌ CH3OH(g)
A 62.8 mol sample of carbon monoxide was added to 146 mol of hydrogen. When equilibrium was
reached at a given temperature, the mixture contained 26.2 mol of methanol and the total pressure
was 9.50 MPa.
(i) Write an expression for the equilibrium constant, Kp, for this reaction.
(ii) Calculate Kp at this temperature, giving its units.
(iii) Some hydrogen gas was added to the equilibrium system, and the partial pressure of
methanol increased to 2.0 MPa at the new equilibrium. What is the new equilibrium partial
pressure of hydrogen?

Exercise 7.7
A sample of pure NO2 gas when heated to 1000 oC decomposes according to the following equation:
2NO2(g) ⇌ 2NO(g) + O2(g)

The equilibrium constant Kp is 158 atm. Analysis shows that the partial pressure of oxygen is
0.25 atm at equilibrium. Calculate the partial pressure of NO and of NO2 in the equilibrium mixture.

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Determining Kc for an equilibrium reaction

Scenario:
To plan an experiment to determine a value of the equilibrium constant Kc of a given reaction, and
to verify that a change in concentration has no effect on the value of Kc.

Approach:
Depending on the nature of the participating reactants and products, the techniques used in the
experiment will vary greatly.
In general, bear the following in mind:
● Most reversible reactions take time to reach equilibrium, and therefore your plan must allow
time for the equilibrium to be established (ranging from a few minutes to several days
depending on the reaction).
● All Kc values are dependent on temperature, and so the temperature must be maintained
(usually in a water bath), and be recorded.
● Your experiment must collect the data on all initial amounts of reactants and products, and the
equilibrium amount of one of them. The rest of the equilibrium amounts can then be worked
out using the Initial-Change-Equilibrium (ICE) table.
● To verify that a change in concentration has no effect on Kc, you need to set up several (usually
five) different reaction mixtures with different starting concentrations of the reactants /
products.

Examples:
1. Esterification of ethanoic acid by ethanol
CH3CO2H(l) + C2H5OH(l) CH3CO2C2H5(l) + H2O (l)
Hydrochloric acid is added to the mixture as a catalyst (it enables the equilibrium to be reached
in a much shorter time without affecting the Kc value).
The equilibrium mixture can be titrated with standard NaOH; this gives the total amount of
acids (HCl and CH3CO2H) present at equilibrium. Subtracting the amount of HCl from this total
amount will give the equilibrium amount of CH3CO2H, from which the Kc can be determined
using the ICE table.
2. Formation of the iron(III)-thiocyanate complex
[Fe(H2O)6]3+(aq) + SCN–(aq) [Fe(SCN)(H2O)5]2+(aq) + H2O (l)

The [Fe(SCN)(H2O)5]2+complex ion typically has a deep red colour. A colorimeter could be used to
determine the equilibrium concentration of the complex ion. Usually, a calibration curve of
absorbance against concentration is first determined using solutions of known concentrations of
the complex. Then the equilibrium concentrations of various mixtures can be determined using the
calibration curve. Once again, the Kc can be determined from the ICE table.

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8 HABER PROCESS
LO9(h): Describe and explain the conditions used in the Haber process, as an example of the importance of an understanding
of chemical equilibrium in the chemical industry

The principles of Chemical Equilibria and Reaction Kinetics play an important part in the design and
working conditions of an industrial process. The conditions are chosen so that reactants are converted
into products as quickly as possible (a kinetics problem) and as completely as possible (an equilibrium
problem).

The Haber process is used to manufacture ammonia from nitrogen and hydrogen.

N2(g) + 3H2(g) ⇌ 2NH3(g) Hr = −92 kJ mol−1

The reaction is slow and does not go to completion. Figure 13 shows that a high yield of NH3 is
produced by low temperature and high pressure.

Figure 13. Effect of temperature and pressure on percentage yield of NH 3 in the Haber process.

However, the optimal conditions used in the Haber process are:

● Temperature: 450 C
● Pressure: 250 atm
● Catalyst: finely divided iron catalyst

● A low temperature would favour the forward exothermic reaction and increase the yield of NH3
but the reaction would be too slow to be economical. In practice, the operating temperature is
kept at a moderate temperature of about 450 C.
● A catalyst is used to increase the rate of reaction thus increasing efficiency without affecting yield.
● A high pressure favours the forward reaction as it reduces the number of moles of gases but the
cost and maintenance of the equipment would be too high. In practice, the operating pressure is
relatively high at 250 atm.
● The yield of NH3 is further increased by removing it as it forms as this continuously shifts the
position of equilibrium to the right.

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N2 + H2 Reaction Chamber
compressor
(catalysts)

NH3 + N2 + H2

Ammonia
Condenser
Unreacted N2 + H2
Liquid NH3

Storage Tanks

Figure 14. Simplified schematic diagram of the Haber process

Exercise 8.1 [J2003/P2/Q3]

In the Haber Process, ammonia is synthesised from its elements.
(a) Write an equation for the Haber Process and state whether it is endothermic or exothermic.
(b) What are three usual operating conditions of the Haber Process?
(c) Explain the considerations which lead to the temperature you have stated in (b) being used.
(d) Under certain conditions the equilibrium pressures of the three gases are
nitrogen 44.8 atm
hydrogen 105.6 atm
ammonia 37.2 atm
(i) Write an expression for the equilibrium constant, Kp, for the Haber Process.
(ii) Calculate Kp from these data, giving the units.2)2/(44.8)(105.6)3 = 2.62 x 10–5 atm–2

Exercise 8.2
Which of the following graphs correctly represents the percentage of ammonia obtainable in the
Haber process at different temperatures?

A B C D

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FRITZ HABER (Background Info)

‘A scientist belongs to his country in times of war and to all mankind in

times of peace.’ – Fritz Haber (1868–1934), German Chemist

The main areas of Fritz Haber’s research were electrochemistry and catalysis. Much of his work shaped
the world we live in today. His work on the synthesis of ammonia (which won him the Nobel Prize in
Chemistry in 1918) and the development of mustard gas (used in chemical warfare) sparked much
debate, demonstrating the dilemmas and impact of the scientific applications on society and the
environment.

Haber’s motivation for developing a method for producing ammonia was to increase the supply of
fertilisers due to the limited supply of natural fertilisers. Many predicted that there could be massive
starvation in Europe unless this was done. While ammonia is a precursor for the production of nitrates
for fertilisers, Haber’s work also boosted the nitrate supply for the manufacturing of explosives in
Germany in the early 1900s, which indirectly prolonged World War I. In addition, massive use of
fertilisers caused the ‘bloom’ of phytoplankton resulting in the depletion of oxygen and death of
aquatic animals (known as eutrophication).

Mustard gas was a horrible instrument of war that caused much suffering. Ironically, many
compounds related to mustard gas could be used as anti-cancer agents.

Haber was eventually driven out of Germany before World War II despite his loyalty to his country,
due to his Jewish ancestry.

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9 Equilibrium Constant and Gibbs Free Energy (connecting Equilibrium and

Thermodynamics)
LO9(g): Show understanding that the position of equilibrium is dependent on the standard Gibbs free energy change of
reaction, G⚪ [Quantitative treatment is not required]

Recall in Topic 5 Chemical Energetics & Thermodynamics, that standard Gibbs free energy change of
reaction (∆G⚪) is the change in Gibbs free energy needed to convert reactants into products at 1 bar
and constant temperature (usually at 298 K). Its sign can be used to predict where the position of
equilibrium (POE) lies for a reversible reaction.

A negative value for ∆G⚪ represents a driving force in the forward direction, and POE lies to the right.
A positive value represents a driving force in the reverse direction, and POE lies to the left.

Relation between ∆G⚪ and K (Useful Tool)

For a reversible reaction taking place under non-standard conditions, the Gibbs free energy change,
ΔG, is related to the standard Gibbs free energy change, ∆G⚪, according to this equation:

∆G = ∆G⚪ + RT ln Q

where R is the gas constant

T is temperature in Kelvin
Q is the reaction quotient

For a reaction at equilibrium, Q = K and ΔG = 0, and the previous equation may be written as:

0 = ∆G⚪ + RT ln K

Rearranging the equation gives us:

∆G⚪ = –RT ln K

This equation provides a useful link between these two essential ideas, standard Gibbs free energy
change and equilibrium constant, both are measures of the extent of a reversible reaction.

The table below summarises how the sign for ∆G⚪ can provide information on POE.

Dominant species at
∆G⚪ Position of equilibrium K
equilibrium

− lies to the right product >1

+ lies to the left reactant <1

The more negative the ∆G⚪, the greater the proportion of products present and the larger the value
of K.

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Exercise 9.1 [N2017 P1 Q14]

The graph shows how ∆G⚪ changes with temperature for the reaction shown.

H2O(g) + CO(g) ⇌ H2(g) + CO2(g)

Equimolar amounts of H2O and CO were introduced into a sealed container and allowed to reach
equilibrium.

At which points will the concentration of H2 be greater than the concentration of H2O at
equilibrium?

A 1 and 2 B 1 only C 2, 3 and 4 D 3 and 4 only

and POE lies more to the left. Hence at equilibrium, the proportion o

Temperature dependence of Equilibrium Constant (Background Info):

We now have an equation that relates standard free energy change for a reaction to the equilibrium
constant:
𝐺 𝑜 = −𝑅𝑇 𝑙𝑛 𝐾

In thermodynamics, we can derive an equation for how free energy change for a reaction depends on
temperature:
𝐺 𝑜 = 𝐻 𝑜 – 𝑇𝑆 𝑜

We can therefore combine these two equations to obtain an equation for how the equilibrium
constant depends on temperature.
−𝑅𝑇𝑙𝑛 𝐾 = 𝐻 𝑜 – 𝑇𝑆 𝑜

Dividing both sides by RT gives:

𝐻 𝑜 𝑇𝑆 𝑜
−𝑙𝑛𝐾 = −
𝑅𝑇 𝑅𝑇

Rearranging, we get:

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𝐻𝑜 1 𝑆𝑜
𝑙𝑛𝐾 = − (𝑇 ) + --- van’t Hoff equation
𝑅 𝑅

1
If we plot ln K on the y-axis and (T in Kelvins) on the x-axis, we obtain a straight line from which the
𝑇
𝐻𝑜 𝑆𝑜
gradient (− 𝑅
), and the y-intercept ( 𝑅 ) can be used to find H⚪ and S⚪ respectively.

LOOKING FORWARD
In this topic, we looked at general concepts related to the chemical equilibria of reversible reactions.
These concepts will be revisited in Topic 13 Solubility Equilibria and Topic 14 Acid-Base Equilibria,
where we shall apply them to understand precipitation reactions and acid-base reactions at a deeper
level.

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08 Introduction to Organic Chemistry

GUIDING QUESTIONS
● What are the main classes of organic compounds?
● What are some terms commonly used in the description of organic reactions and reactivities?
● What are the main types of organic reactions?
● How do electrons flow in polar organic reactions?

LEARNING OUTCOMES
Students should be able to:
11.1 (a) interpret, and use the nomenclature, general formulae and displayed formulae of the following
classes of compound:
(i) hydrocarbons (alkanes, alkenes and arenes)
(ii) halogen derivatives (halogenoalkanes and halogenoarenes)
(iii) hydroxyl compounds (alcohols and phenols)
(iv) carbonyl compounds (aldehydes and ketones)
(v) carboxylic acids and derivatives (acyl chlorides and esters)
(vi) nitrogen compounds (amines, amides, amino acids and nitriles)
*students are expected to be able to interpret and use the following types of representations
in the description of organic molecules: empirical formula, molecular formula, structural
formula, full structural or displayed formula, skeletal formula and stereochemical formula.
11.1 (b) interpret, and use the following terminology associated with organic reactions:
(i) functional group
(ii) degree of substitution: primary, secondary, tertiary, quaternary
(iii) homolytic and heterolytic fission
(iv) carbocation
(v) free radical, initiation, propagation, termination (Refer also to Topic 10 Alkanes)
(vi) electrophile (Lewis acid), nucleophile (Lewis base)
(vii) addition, substitution, elimination, condensation, hydrolysis
(viii) oxidation and reduction
[in equations for organic redox reactions, the symbols [O] and [H] are acceptable]
11.1 (c) interpret, and use the following terminology associated with organic reactivities:
(i) delocalisation
(ii) electronic effect (electron-donating and electron-withdrawing effect)
(iii) steric effect (steric hindrance)
11.1 (d) describe sp3 hybridization, as in ethane molecule, sp2 hybridization, as in ethene and benzene
molecules, and sp hybridization, as in ethyne molecule (Refer to Topic 2 Chemical Bonding and
Topic 12 Arenes)
11.1 (e) explain the shapes of, and bond angles in, the ethane, ethene, benzene and ethyne molecules
in relation to σ and π carbon-carbon bonds (Refer to Topic 2 Chemical Bonding and Topic 12
Arenes)
11.1 (f) predict the shapes of, and bond angles in, molecules analogous to those specified in 11.1 (e)
11.1 (g) apply 11.1 (b) and 11.1 (c) to the understanding of mechanisms in terms of organic structure
and bonding

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Hwa Chong Institution 2023 08 – Introduction

11.1 (h) recognise that the mechanisms of polar reactions involve the flow of electrons from electron-
rich to electron-poor sites
*students are expected to be able to interpret and use the curly arrow notation to represent
the movement of electrons in organic reaction mechanisms.
REFERENCES
1. Peter Cann and Peter Hughes, Chemistry for Advanced Level, 5th Ed., Hodder Education, Chapter
12
2. John McMurry, Organic Chemistry, 8th Ed., Brooks/Cole, Chapter 2

LOOKING BACK
The study of organic chemistry in the A-Level syllabus is based on the chemistry of different functional
groups. Besides the first two general topics on Introduction and Isomerism, each topic in organic
chemistry will cover one functional group: its nature, physical properties, chemical reactivity,
reactions and mechanisms.

The properties and reactivities of the functional groups can be explained using concepts in Topic 1
Atomic Structure and Topic 2 Chemical Bonding: atomic orbitals, hybridization, electronegativity,
covalent bonding, and intermolecular forces. Their reactions and mechanisms can be understood
based on concepts in Topic 4 Reactions & Stoichiometry (stoichiometry, redox, acid-base reactions),
Topic 5 Energetics & Thermodynamics (bond energies, enthalpy changes) and Topic 6 Reaction
Kinetics (rate equations, orders of reaction, transition states, intermediates).

Besides drawing on knowledge from previous topics, the organic topics themselves are also closely
linked because each functional group can be converted to other functional groups via reactions. It is
helpful to draw up a concept map at the end of all the organic topics to get a visual overview of all
possible reactions and functional group conversions.

1 INTRODUCTION

The study of organic chemistry is centred on the structures, properties and reactions of organic
compounds. Organic compounds are compounds that contain carbon, and usually hydrogen and/or
halogens. Other elements such as oxygen, nitrogen, phosphorus and sulfur can also be present. (Note
that carbon dioxide, carbonates, cyanides are not considered organic compounds.)

Carbon can form many compounds because:

● a carbon atom can form covalent bonds to as many as 4 other atoms
● it can form stable and strong covalent bonds with other carbon atoms and/or atoms of many
different elements
● it can form different types of bonds, e.g. single, double and triple bonds
● it can form long chains or rings of carbon atoms

Due to the unique properties above, carbon atoms can bond with one another and with atoms of different
elements in a multitude of ways, to form large numbers of organic compounds. Fuels, plastics, painkillers,
antibiotics and vitamins are organic compounds that have become vital to our present way of life.

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Hwa Chong Institution 2023 08 – Introduction

2 CLASSES OF ORGANIC COMPOUNDS

Organic compounds can be classified based on the:

● types of carbon chain (Section 2.1)
● functional groups present (Section 2.2)

2.1 Types of carbon chain

Organic compounds can be grouped based on whether they are saturated, contain rings or aromatic
systems, e.g.:

Aliphatic compounds
● compounds with open chains of carbon atoms, e.g. propane
● may be unbranched or branched
● may contain single, double or triple bonds or combinations of these

Alicyclic compounds
● compounds with closed rings of carbon atoms, e.g. cyclohexane:

Aromatic compounds
● compounds containing at least one aromatic system such as a benzene ring:

Organic compounds (aliphatic or alicyclic) containing only single bonds are saturated. Compounds with
at least one double or triple bond or aromatic ring are unsaturated.

2.2 Functional groups

LO11.1(b)part: interpret, and use the following terminology associated with organic reactions: (i) functional group

Organic compounds can be grouped into different classes based on functional groups they contain.
Functional groups refer to particular atoms or a group of atoms within an organic molecule, that define
the physical properties and chemistry of that compound.

The following page shows the classes of organic compounds in the A Level syllabus, with their
corresponding functional groups.

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Class of organic Characteristic group of atoms present Name of Functional Group

compound
Hydrocarbons N.A. (only C–C and C–H bonds present) alkane
C=C alkene
arene
e.g. benzene: (C6H6)
Halogen derivatives C–X where X: halogen chloroalkane, bromoalkane etc.
chloroarene, bromoarene etc.
e.g. benzene ring attached to X (C6H5X)
Hydroxy compounds C–OH primary/secondary/tertiary alcohol
phenol
e.g. benzene ring attached to OH (C6H5OH)
Carbonyl compounds aldehyde

–CHO or
ketone

–C=O or
Carboxylic acids carboxylic acid
–CO2H or
Carboxylic acid acyl chloride, acyl bromide etc.
derivatives
–COX or
ester

–CO2R or where R: alkyl group

Nitrogen compounds C–NR2 where R: alkyl group or H primary/secondary/tertiary amine
amide

–CONR2 or where R: alkyl group or H

amino acid e.g. carboxylic acid, amine

–CN or nitrile
nitro

–NO2 or

Table 1. Classes of organic compounds and names of functional groups

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2.2.1 Homologous series

A homologous series is a family of compounds containing the same functional group, and each successive
member increases by one –CH2– unit.

Compounds of the same homologous series:

1. can be represented by a general molecular formula
2. show a regular trend in physical properties
3. can usually be prepared by similar methods
4. have similar chemical properties

An example of a homologous series is that of alkanes, with general molecular formula C nH2n+2. The table
below shows the trend in the boiling point of the first six members of the series.

Formula Name Boiling point / °C

CH4 methane –162
CH3CH3 ethane –89
CH3CH2CH3 propane –42
CH3CH2CH2CH3 butane 0
CH3CH2CH2CH2CH3 pentane 36
CH3CH2CH2CH2CH2CH3 hexane 69
Table 2. Homologous series of alkanes

2.2.2 Degree of Substitution

LO11.1 (b)part: interpret, and use the following terminology associated with organic reactions: (ii) degree of substitution: primary,
secondary, tertiary, quaternary

Some organic compounds are classified based on how many substituents (usually alkyl or aryl) are joined
to the carbon atom bearing the functional group.

A substituent refers to an atom or group of atoms that takes the place of a hydrogen atom on the
hydrocarbon chain.

● An alkyl group is a type of substituent derived from alkanes by removing a hydrogen atom:

No. of carbons atoms in the alkyl group name structure

1 methyl –CH3
2 ethyl –CH2CH3
3 propyl –CH2CH2CH3
4 butyl –CH2CH2CH2CH3
Table 3. Examples of alkyl groups

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Hwa Chong Institution 2023 08 – Introduction

● An aryl group is a type of substituent derived from an aromatic ring (such as a benzene ring) by
removing a hydrogen atom. An example of an aryl group is the phenyl group, represented by

A useful way of classifying alcohols is to place them in one of the three categories: primary (1o), secondary
(2o) and tertiary (3o). Figure 1 shows primary, secondary, and tertiary alcohols have one, two and three
alkyl or aryl groups (represented by R) attached respectively, to the carbon bearing the OH group. The
same classification can be applied to halogenoalkanes, radicals and carbocations.

For amines, however, it is the number of alkyl or aryl groups attached to the nitrogen atom, that
determines whether an amine is primary, secondary or tertiary. Note that there can be a quaternary (4o)
ammonium cation when the nitrogen atom uses its lone pair to form a fourth bond to an alkyl (or aryl)
group.

alcohols

halogenoalkanes
(X = F, Cl, Br etc.)

amines

Figure 1. Different degrees of substitution for alcohols, halogenoalkanes and amines

Exercise 2.1
The structure below shows a molecule of an antibiotic drug. Circle and name the functional groups
present.

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3 TYPES OF FORMULAE FOR ORGANIC COMPOUNDS

LO11.1(a)part: interpret, and use the general formulae and displayed formulae of classes of compounds
*students are expected to be able to interpret and use the following types of representations in the description of organic
molecules

There are six types of formulae that can be used to represent organic compounds. We shall illustrate
them by using lactic acid:

Empirical Formula
● simplest ratio of the number of atoms of the elements present in one molecule, e.g. lactic acid: CH2O

Molecular Formula
● actual number of atoms of the elements present in one molecule, e.g. lactic acid: C3H6O3

Structural Formula
● shows how the atoms of a molecule are joined together in an unambiguous way, with minimal detail,
e.g. lactic acid: CH3CH(OH)CO2H

Displayed (or full structural) Formula

● detailed structure of molecule showing the relative placing of atoms and all the bonds between them,
e.g. lactic acid:

Figure 2. Displayed formula of lactic acid

● rings of atoms are often represented by their skeletal formulae (explained next):

Figure 3. Skeletal formulae of carbon rings

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Hwa Chong Institution 2023 08 – Introduction

Skeletal Formula
● simplified representation derived from the displayed formula by removing hydrogen atoms (and their
bonds) and carbon atoms from alkyl chains, leaving just the carbon–carbon bonds in the carbon
skeleton and the functional groups, e.g. lactic acid:

Figure 4. Skeletal formula of lactic acid

● each C–C bond in the carbon skeleton is a line (each end of the line is a carbon atom)
● double and triple lines indicate double and triple bonds respectively
● partial skeletal representations are also used where they are unambiguous, e.g. lactic acid:

Figure 5. Partial skeletal formulae of lactic acid

Stereochemical Formula
● show the 3-D spatial arrangement of bonds, atoms and groups around an atom, usually a
stereochemical centre (Topic 9 Isomerism), e.g. lactic acid:

Figure 6. Different stereochemical formulae of lactic acid

● solid wedges ( ) indicate bonds pointing out of the plane of the paper towards you
● dashed wedges or hashed lines ( ) indicate bonds pointing into the plane of the paper away
from you
● lines ( ) indicate bonds in the plane of the paper

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Hwa Chong Institution 2023 08 – Introduction

Exercise 3.1
Complete the following table by writing the different types of formulae for compounds A and B.

Compound A
Type of formula Compound B
(Worked Example)

Empirical formula C10H19ON

Molecular formula C10H19ON

Structural formula CH3CH(OH)CH(CN)(CH2)2C(CH3)3

Displayed formula

Skeletal formula

(given)

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Hwa Chong Institution 2023 08 – Introduction

4 NOMENCLATURE
LO11.1(a)part: interpret, and use the nomenclature of classes of compounds

Many organic molecules have 'common names' derived from living organisms or sources from which they
were originally extracted from; e.g. formic acid isolated from ants (‘ants’ in Latin: formica), acetic acid
(‘vinegar’ in Latin: acetum), menthol (‘peppermint’ in Latin: Mentha piperita) etc. However, this naming
becomes unsatisfactory for organic compounds entirely synthesised in the lab (no plant/animal source)
and when the number of compounds becomes too large to remember specific names for each of them.

4.1 IUPAC Nomenclature

Chemists have devised a logical and systematic form of nomenclature, which has been adopted by the
International Union of Pure and Applied Chemistry (IUPAC). Following a set of internationally recognised
rules, chemists can now translate names of organic compounds they have not previously encountered,
into its structural formula, and vice versa.
A systematic name for an organic compound is often based on the ‘parent’ hydrocarbon. Each name
consists of the following components (not all will be present, depending on the complexity of the
molecule):
1. Stem
2. Suffix
3. Prefix
4. Locant
5. Stereochemical identifier

For example:

Stem
The stem specifies the number of carbon atoms in the longest carbon chain in the molecule and indicates
the type of carbon-carbon bonds (single, double, triple):

(a) number of carbon atoms in the longest carbon chain

Stem meth- eth- prop- but- pent- hex- hept- oct- non- dec-
No. of carbon atoms in
1 2 3 4 5 6 7 8 9 10
the longest carbon chain

If the carbon atoms are joined in a ring, ‘cyclo’ is added in front of the stem.

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Hwa Chong Institution 2023 08 – Introduction

(b) type of carbon-carbon bond(s) present in the longest carbon chain:

stem longest carbon chain contains:

-an all C–C single bonds
-en one C=C double bond
-dien two C=C double bonds
-trien three C=C double bonds
-yn one C≡C triple bond

Suffix
The suffix specifies the highest priority functional group in the molecule, identified according to the
following hierarchy:

Group Name as suffix

Carboxylic acid, –CO2H (highest priority) -oic acid
Ester, –CO2R -oate
Acyl halide, –COX -oyl halide
Amide, –CONR2 -amide
Nitrile, –CN -nitrile
Aldehyde, –CHO -al
Ketone, –COR -one
Alcohol, –OH -ol
Amine, –NR2 -amine
Alkene, C=C -ene
(lowest priority)
Arene e.g. -benzene

Prefix
Prefix(es) specify the other groups present in the molecule. The use of ‘di’, ‘tri’, ‘tetra’, ‘penta’ etc.
indicates multiple substitution of the same group. Different prefixes in a name are placed in alphabetical
order.

Group Name as prefix

Nitrile, –CN cyano
Aldehyde, –CHO formyl
Ketone, –COR oxo
Alcohol, –OH hydroxy
Amine, –NR2 amino
Nitro, –NO2 nitro
Chloro, –Cl; Bromo, –Br chloro; bromo
Arene e.g. phenyl
Alkyl groups methyl, ethyl, propyl, butyl etc.

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Hwa Chong Institution 2023 08 – Introduction

Locant
Locants are numbers attached to the front of each prefix and the suffix, to specify the position of each
group in the molecule. The rule is to number the carbon atoms in the longest carbon chain from one end
to the other, making sure that the suffix is given the smallest number as its locant. The locant can be
omitted if the position of the group is obvious without it.

Stereochemical identifier
For compounds that exhibit stereoisomerism (Topic 9 Isomerism), the name of the stereoisomer is placed
in front, for instance: cis-but-2-ene, trans-but-2-ene.

For example:

5 4 3 2 1

3,4-dichloro-3-methylpentan-1-ol

1. The longest carbon chain has five C atoms and has all C-C single bonds (stem: pentan-)
2. The suffix (highest priority functional group) is identified as the alcohol functional group –OH
(suffix: -ol)
3. Number the C atoms along the longest carbon chain such that
(i) the smallest number is given to the suffix (C bonded to –OH group numbered as C1)
(ii) the smallest set of numbers is given to the groups identified as prefixes
4. Identify the prefixes (substituents) and assign their individual locant (position in the molecule)
• One –CH3 substituent on C3 position (3-methyl)
• Two –Cl substituents on C3 and C4 positions (3,4-dichloro)
Placing the prefixes in alphabetical order: 3.4- dichloro-3-methyl. (This alphabetical order does
not take into consideration ‘di’, ‘tri’, ‘tetra’ etc, This means that the “dichloro” substituents are
placed before “methyl” in the name despite the presence of “d” in “dichloro” as we still follow
the first letter of the original name of the substituent i.e. “c” in chloro.)
Note: Use commas (,) to separate numbers and use hyphens (-) to separate numbers and words.
5. The systematic IUPAC name of the molecule is obtained by putting together the prefixes, stem and
suffix: 3,4-dichloro-3-methylpentan-1-ol

Further examples of compounds and their systematic IUPAC names:

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Hwa Chong Institution 2023 08 – Introduction

In subsequent organic chemistry topics, we shall look in greater detail at the IUPAC nomenclature of
compounds containing specific functional groups.

Exercise 4.1
1. Draw the structures of the following compounds:

(a) (Worked Example) 3-bromocyclohexanol (b) ethylbenzene

2. What are the systematic IUPAC names of the following compounds?

(a) (Worked Example) (b)

3-hydroxybutanal

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Hwa Chong Institution 2023 08 – Introduction

5 KEY IDEAS IN ORGANIC REACTIONS

5.1 Types of organic reactions

LO11.1(b)part: interpret, and use the following terminology associated with organic reactions: (vii) addition, substitution,
elimination, condensation, hydrolysis (viii) oxidation and reduction

In addition to acid-base reactions (transfer of Substitution

H+ ions) learnt in Topic 4 Reactions and
Stoichiometry, there are seven types of
reactions applicable to organic reactions.

When one atom or group of atoms replaces

Study carefully the changes that occur in each
another atom or group in a molecule.
type of reaction so that you can recognise
them in novel reactions. e.g.

Addition Elimination

When an organic molecule, usually containing a When a double bond (e.g. C=C) is formed with the
double bond (e.g. C=C), reacts with another removal of a molecule (from adjacent carbon
molecule to give only one product. The π bond of atoms) e.g. H2O from a molecule of an alcohol, or
the double bond breaks to form two new σ bonds. HX from a molecule of a halogenoalkane. Opposite
Opposite of elimination. of addition.

e.g. e.g.

Condensation Hydrolysis

When two molecules come together to form a When a molecule is split into two by the action of
bigger molecule, with the elimination of a small water, often catalysed by dilute acids or dilute
molecule such as water or HCl etc. alkalis.
*Not the same as elimination which requires
formation of a new double bond.

e.g. e.g.

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Hwa Chong Institution 2023 08 – Introduction

Oxidation Reduction

When O atoms are added to the molecule OR H When O atoms are removed from the molecule or
atoms are removed from the molecule. H atoms are added to the molecule.

The oxidation number of an atom in the functional The oxidation number of an atom in the functional
group must increase. group must decrease.
e.g. when methanal, HCHO is oxidised to e.g. when methanal, HCHO is reduced to
methanoic acid, HCO2H: methanol, CH3OH:
● oxidation no. of C in methanal = 0 ● oxidation no. of C in methanal = 0
● oxidation no. of C in methanoic acid = +2 ● oxidation no. of C in methanol = –2

Writing balanced redox equations in organic chemistry

The symbol [O] is used to denote the oxygen atoms added, and [H] is used to denote the H atoms
added.
For oxidation reactions, add H2O to balance the H and then [O] to balance the remaining O.
For reduction reactions, add H2O to balance the O and then [H] to balance the remaining H.
e.g. oxidation of methanal to methanoic acid: e.g. reduction of methanal to methanol:

Exercise 5.1
(a) The following are examples of organic reactions. State what type of reaction is taking place.

(i) (Worked Example)

(not balanced)

Ans: Oxidation

(ii)

(iii)

(b) Potassium manganate(VII) can be used to oxidise ethene to carbon dioxide. Write a balanced
equation for this oxidation of ethene.

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Hwa Chong Institution 2023 08 – Introduction

5.2 Mechanisms of organic reactions

*students are expected to be able to interpret and use the curly arrow notation to represent the movement of electrons in organic
reaction mechanisms

The mechanism of a reaction is a detailed description of which bonds break, which bonds form, and the
sequence in which they occur in the reaction. Since bonds consist of shared electrons, a mechanism shows
how electron(s) move to break bonds and form new bonds when reactants are converted to products.

In organic chemistry we use the curly arrow notation to show the movement of electrons:
The tail of the arrow represents the source of the electron(s) e.g. an unpaired electron, lone pair or a
bond while the head of the arrow represents where the electron(s) go to e.g. an atom or a new bond.

To represent the movement of a single electron, we use a partial head or ‘fish-hook’ arrow:

To represent the movement of a pair of electrons, we use a full head arrow:

5.2.1 Bond Breaking represented by curly arrow notation

LO11.1 (b)part: interpret, and use the following terminology associated with organic reactions: (iii) homolytic and heterolytic
fission (iv) carbocation (v)part: free radical

Homolytic fission
● Breaking of a covalent bond where the bonding pair of electrons are given equally to each atom.
Since this involves movement of single electrons, we use the fish-hook arrow:

Figure 7. Homolytic fission of a covalent bond

● Results in the formation of free radicals, i.e. species containing unpaired electron(s) and are highly
reactive. They readily form bonds with other atoms or molecules.

Example: In the homolytic fission of a C–H bond in methane, the C atom and H atom each take one
electron from the bonding pair of electrons to form two radicals.

Figure 8(a). Example of a homolytic fission of C–H bond in methane

Figure 8(b) shows the actual electron distribution and movement:

Figure 8(b). Actual electron distribution and movement of electrons in the homolytic fission of C–H bond in methane

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Hwa Chong Institution 2023 08 – Introduction

Heterolytic fission
● Breaking of a covalent bond where both bonding electrons are given to one of the atoms, usually
the more electronegative atom. Since this involves movement of a pair of electrons, we use the full
head arrow:

Figure 9. Heterolytic fission of a covalent bond

● Results in the formation of ions.

In heterolytic fission of a C–X bond, either the carbocation or carbanion can be formed, depending
on the electronegativity of X relative to that of C.

● Heterolytic fission forming carbocations

- Carbocations are species containing a positively-charged carbon atom, which has only six
electrons in its outer shell.

- In the C–Cl bond below, chlorine is more electronegative than carbon, so it takes both the
bonding electrons to form the chloride ion. The carbon atom loses its electron (originally used
to form the C–Cl bond) and a carbocation is formed.

Figure 10(a). Example of a heterolytic fission to form a carbocation

- Figure 10(b) shows the actual electron distribution and movement:

Figure 10(b). Actual electron distribution and movement of electrons in the heterolytic fission of C–Cl bond

● Heterolytic fission forming carbanions

- Carbanions are species containing a negatively-charged carbon atom, which has a full octet
of electrons in its outer shell.

- In the C–Li bond below, carbon is more electronegative than Li, so it takes both the bonding
electrons to form the carbanion. The lithium atom loses its electron (originally used to form
the C–Li bond) and a lithium cation is formed.

Figure 11. Example of a heterolytic fission to form a carbanion

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5.2.2 Bond Formation represented by curly arrow notation

● via movement of single electron

The ‘fish-hook’ arrow shows the movement of an unpaired electron from radical Z• to X in molecule XY,
forming the new bond.

Figure 12. Bond formation via single electron movement

At the same time, X–Y bond undergoes homolytic fission, forming the radical Y•.

● via movement of electron pairs

The full head arrow shows the movement of the lone pair of electrons from Z– ion to X in molecule XY,
forming the new bond.

Figure 13. Bond formation via electron pair movement

At the same time, X–Y bond undergoes heterolytic fission, forming the anion Y–.

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5.2.3 Polar Reactions and their Mechanisms

LO11.1 (b)part: interpret, and use the following terminology associated with organic reactions: (vi) electrophile (Lewis acid),
nucleophile (Lewis base)
LO11.1(g): apply 11.1 (b) and 11.1 (c) to the understanding of mechanisms in terms of organic structure and bonding
LO11.1(h): recognise that the mechanisms of polar reactions involve the flow of electrons from electron-rich to electron-poor sites

In polar reactions, heterolytic fission and bond formation occur. Electron pairs move from electron-rich
to electron-poor sites. Electron-rich sites are termed “nucleophilic” and electron-poor sites are termed
“electrophilic”.

The diagram below shows a mechanism of a polar reaction:

Figure 14. Example of a mechanism of a polar reaction

● OH– ion has a lone pair of electrons and is electron-rich. It donates its lone pair to the electron-poor
(electron-deficient) carbon in CH3Br. Hence in this mechanism, OH– acts as the nucleophile.

● CH3Br contains the partial positively-charged carbon atom which is electron-deficient. Hence CH3Br
is acting as the electrophile, and its electrophilic site is at the δ+ carbon atom.

Electrophile
An electrophile is a species that accepts an electron pair to form a covalent bond in a reaction. It is
electron-deficient due to having:
● a positively-charged centre (e.g. H+, NO2+, and carbocations like CH3+), or
● an induced or permanent partial positive charge "δ+" (e.g. polarised Br2, HBr)
Electrophiles are also known as Lewis acids.

Nucleophile
A nucleophile is a species that donates an electron pair to form a covalent bond in a reaction. It is
electron-rich and possesses electrons that can be shared, such as:
● lone pairs of electrons (H2O, NH3, OH–, CN−, carbanions)
● π bond (e.g. ethene, benzene)
Nucleophiles are also known as Lewis bases.

Did you know?

The terms nucleophile and electrophile were introduced by British chemist, Christopher Kelk Ingold, in
1933. Derived from the word philos – which means “love” in Greek – electrophile means “electron-loving”
and nucleophile means “nucleus-loving”!

● Placement of each curly arrow in a mechanism is very important: the tail of the first arrow is placed
precisely at the source of the electron pair i.e. the lone pair on OH– (not at the negative charge, or O
or H!), while the head of the arrow is placed exactly at the atom where the new covalent bond forms
i.e. at the carbon atom in CH3Br.

● The second curly arrow represents a heterolytic fission. Its tail starts precisely from the C–Br bond
which is to be broken (i.e. the source of electron pair) and ends with its head pointing exactly at the
Br atom, the atom which receives both electrons, to form Br– ion.

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Hwa Chong Institution 2023 08 – Introduction

The result of the movement of electron pairs is that a new C–O bond is formed, and the C–Br bond is
broken in this reaction. When faced with a novel polar reaction, try to identify the exact bonds broken
and formed, as well as the nucleophile and electrophile, to deduce a possible mechanism.

5.2.4 Non-Polar Reactions and their Mechanisms

In non-polar reactions, homolytic fission and bond formations with radicals occur via movement of single
electrons. Unlike polar reactions, they do not involve ions.

Figure 15 below shows two radicals combining to form a new bond. Fish-hook arrows describe the
movement of each unpaired electron from its source (the radical) to the location in between the two
atoms i.e. where the new bond forms.

Figure 15. Representing bond formation with radicals using curly arrows

Most organic reactions in the A Level syllabus are polar reactions, with mechanisms involving
electrophiles and nucleophiles. Only one mechanism is a non-polar reaction i.e. free radical substitution
in Topic 10 Alkanes.

Exercise 5.2
1. (Worked Example)
In the reaction below,
(a) identify the bonds broken and new bond formed
(b) identify the electrophile and nucleophile, label any relevant partial charges
(c) draw curly arrows to show the movement of electrons

(a) Br–Cl bond is broken; C–C π bond is broken; new C–Br bond is formed

(b) electrophile is BrCl, nucleophile is H2C=CH2, label + on Br and – on Cl in BrCl.

(c)

2. Draw a possible mechanism for the reaction below, using curly arrows notation:

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5.3 Factors Affecting Organic Reactivities

LO11.1 (c): interpret, and use the following terminology associated with organic reactivities: (i) delocalisation (ii) electronic effect
(electron-donating and electron-withdrawing effect) (iii) steric effect (steric hindrance)

5.3.1 Electronic Effects

Electronic effects influence the distribution of electrons in a particular chemical species and hence its
reactivity. They can be electron-withdrawing or electron-donating, depending on the functional groups
involved.

● Inductive effect
The inductive effect arises from the polarisation of electron density in a bond due to the electronegativity
of nearby atoms.

Consider chloroethane, propan-1-ol and ethylamine below. Cl, O and N are more electronegative than C,
hence they draw electron density away from carbon, resulting in a partial positive charge (δ+) on the
carbon next to them. This is the inductive effect.

Figure 16. Inductive effect in chloroethane, propan-1-ol and ethylamine molecules

Inductive effect occurs via σ bonds and decreases along the σ bond as we go further away from the
electronegative atoms. Hence in the above molecules, the carbon atoms further away from the one
labelled with δ+ also have a slight partial positive charge but which is much weaker due to greater
distance from the electronegative atoms.

Since -Cl, -OH and -NH2 groups draw electron density away from carbon adjacent to them, they are
inductively electron-withdrawing groups.

Alkyl groups, on the other hand, are inductively electron-donating groups. The reason is due to
hyperconjugation which will not be covered here. We shall see examples of how inductive electron-
withdrawing and electron-donating effects affect reactivities of organic compounds in subsequent topics.

● Delocalisation
Delocalisation of electrons occurs when p orbitals on 3 or more adjacent atoms overlap, forming a π
electron cloud in which the electrons from all the overlapping p orbitals can be found. These electrons
are said to be ‘delocalised’. This delocalisation of electrons in compounds generally results in stabilisation,
which is also known as the resonance stabilisation effect.

Consider the buta-1,3-diene molecule which has alternating single and double bonds:

(a) (b)
Figure 17(a). Buta-1,3-diene structure (b). Overlap of p orbitals of the carbon atoms in butadiene indicated by dotted lines

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Hwa Chong Institution 2023 08 – Introduction

The p orbitals of the four adjacent carbon atoms in buta-1,3-diene overlap and form a π electron cloud.
The π electrons in the two C=C double bonds of butadiene are delocalised throughout the π electron
cloud, and not just localised at their respective double bonds. As a result, the carbon-carbon bond labelled
 (in Figure 17a) has partial double bond character, and we expect it to be somewhat shorter and stronger
than a C–C single bond.

Organic molecules with delocalised electrons include benzene, carboxylic acids and amides. We will
discuss in subsequent topics how the delocalisation of electrons affects their reactivities.

In summary:

Inductive effect Delocalisation

● Due to difference in electronegativity ● Due to 3 or more p orbitals overlapping
between atoms in covalent bonds
● Occurs via σ bonds ● Occurs via a π electron cloud
● Gets weaker with distance ● Independent of distance

5.3.2 Steric Effect

Steric effect is another factor associated with the reactivities of organic molecules. Unlike electronic
effects that involve the distribution of electrons in σ bonds and π electron clouds, steric effect results
from the repulsion between electron clouds of groups or substituents, depending on their size and
number.

In Topic 6 Reaction Kinetics, the collision theory states that reactions occur only when reactant molecules
collide with each other with correct orientation and sufficient energy to overcome the activation energy
barrier. Molecules with bulky substituents crowded around their reactive sites would hinder the approach
of the other reactant for an effective collision. When steric effect hinders the rate of reaction, we call it
steric hindrance.

Consider the example below. Each halogenoalkane contains an electrophilic carbon atom, which can be
attacked by a nucleophile.
(a) (b)

δ+ δ+
Halogenoalkane

Approach of nucleophile (Nu:)

towards the electrophilic
carbon atom

Figure 18. Example of steric hindrance due to bulky substituents

Consider the size of the electron cloud of three CH3 groups to that of three H atoms. In (a), the
electrophilic carbon atom is ‘shielded’ from the incoming nucleophile’s approach, due to repulsion from
bulky CH3 groups. This reaction will be slower due to steric hindrance, compared to (b) where H atoms

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Hwa Chong Institution 2023 08 – Introduction

are small and provide less steric hindrance. The larger the groups and the greater the number of groups
crowding around the site of reaction, the greater the steric hindrance.

Exercise 5.3
(a) In the molecules below,
- identify the group(s) that are inductively electron-withdrawing
- label the partial charge on the carbon atom just adjacent to the group(s)

(i) (ii)

(b) (Worked Example)

State whether any delocalisation of electrons occur for the molecules below. Explain your answers.

(i) (ii) (iii)

(i) No delocalisation of electrons since p orbitals of only two adjacent atoms overlap.

(ii) There is delocalisation of electrons here because p orbitals of four adjacent atoms overlap.
The four p electrons in the C=O and C=C are delocalised over O-C-C-C.

(iii) No delocalisation of electrons since the two C=C double bonds are separated by an sp3
carbon, so the two adjacent p orbitals on one double bond cannot overlap with the p
orbitals of the other double bond.

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6 PRACTICAL ASPECTS OF ORGANIC CHEMISTRY

6.1 Distinguishing Tests

A distinguishing test is a simple chemical test that aims to confirm the presence of a particular compound,
or differentiate between organic compounds, through identification of key functional groups. Such tests
require an observable chemical change (e.g. colour change, appearance of precipitate, evolution of a gas,
etc.) and are usually quick tests carried out in test tubes (unlike in synthesis) without use of complicated
set-up or equipment (i.e. no reflux or distillation set-ups).

Planning an experiment involving distinguishing tests

You may be asked to:

● present the sequence of tests. (You may use a flowchart or table.)
● write the procedure with essential details of quantities and conditions for each test.
- In general, all tests are carried out in clean test-tubes using about 1 cm3 (or 1 cm depth) of
the unknown solution or 1 spatula of the unknown solid unless otherwise required.
- Reagents are added dropwise until no further change occurs.
- Heating, if required, is carried out using a water bath/oil bath/sand bath or a heating mantle.
● state the expected observations for both positive and negative tests.
● explain the chemistry underlying each test: type of reaction, identity of species responsible for
precipitate/gas/colour change observed, name or structure of functional group/structure of
organic product etc.

6.2 Synthesis

An organic synthesis generally involves carrying out a reaction to form the desired organic product with
reasonable yield and purity. Various strategies are used in syntheses to obtain high yield and good purity
of products. This usually involves careful sequencing of steps, controlled reaction conditions, complex
set-up and/or equipment, and often, the investment of time. The product must also be isolated (i.e.
separated from the reaction mixture) and purified.

The main stages in an organic synthesis are:

● Carrying out the reaction by heating the reaction mixture under reflux.
● Separation and purification of product by filtration, extraction with separating funnel, distillation or
recrystallisation.
● Checking purity of product by determining its melting or boiling point.
● Determining structure of the product via spectroscopy methods e.g. IR, UV, MS, NMR etc. (H3 Chem)

6.2.1 Carrying out the reaction

Compared to inorganic reactions between ionic compounds in solutions, organic reactions are generally
slow (as such reactions typically have high activation energy due to breaking covalent bonds) so the
organic reaction mixture needs to be heated for some time. You will be learning many reactions that
involve heating reagents under reflux in the A-level organic chemistry syllabus.

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Hwa Chong Institution 2023 08 – Introduction

Heating under reflux means to heat the mixture in a flask so that the solvent boils continually. A
condenser is placed vertically in the neck of the flask to condense the solvent vapour. This method allows
the temperature of the reaction mixture to be kept at the boiling point of the solvent, while minimizing
the loss of solvent, reactants or products due to evaporation.

Generic procedure for heating under reflux

1. Measure (mass/volume) of
water out
(reactant/reactants) using a (apparatus e.g.
measuring cylinder for liquids/micropipette for
small volumes <5cm3/electronic mass balance
and weighing bottle for solids). Transfer to a condenser
100 cm3 /250 cm3 round–bottom flask).

2. Set up the apparatus as shown in the diagram. water in

3. Gently heat the mixture under reflux for

(duration in minutes/hours). reaction mixture
with anti-bumping
water/oil bath granules or
magnetic stirring
bar
heat
Figure 19. A reflux set-up
Notes:
✔ As most organic compounds are volatile and flammable, heating is done using a water/oil/sand
bath or heating mantle (instead of a Bunsen flame).
✔ For very exothermic reactions (e.g. when diluting a concentrated acid), cooling may be necessary
when adding the reagents to each other, e.g. by immersing the reaction flask in an ice water bath.
✔ A dropping funnel is used if the reactant needs to be added slowly (see diagram below).

water out
condenser

dropping funnel water in

two-neck flask

Figure 20. Two-neck flask with dropping funnel and condenser

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Hwa Chong Institution 2023 08 – Introduction

6.2.2 Separation and Purification Techniques

One or more of the following techniques may be used to isolate and purify the crude product.

● Filtration
Used to separate a solid product from a solid-liquid mixture. The flask may be connected to a vacuum
pump for more rapid filtration.
Buchner funnel
Buchner funnel
filter paper

vacuum

Buchner flask
(250/500 cm3)

Figure 21. Vacuum filtration set-up

● Extraction
Extraction involves two immiscible (do not mix) solvents. The first solvent contains the reaction mixture
and crude product. A second solvent is chosen such that the solubility of the product in the second solvent
is greater than that in the first. The two liquids are shaken together in a separating funnel and left to
stand. The product will be extracted into the second solvent and obtained by evaporating the solvent.

Generic procedure for extraction

1. Place (crude organic product / reaction mixture) into a

separating funnel.
2. Using a measuring cylinder, add (volume) of (usually an acid
or base/suitable solvent) .
less dense layer
3. Stopper and shake well. Leave to stand to allow the two
immiscible layers to separate. denser layer

4. Collect the (usually organic) layer which is at the (top /

bottom) in a conical flask. Discard the (usually aqueous)
layer. Figure 22. Separating funnel
(common capacities: 50 – 500 cm3)
5. Add (drying agent) to the (usually organic) layer.
6. Filter and collect the (usually organic) layer (filtrate).
7. Evaporate the solvent to obtain the organic product.
Notes:
✔ As a precaution, when shaking the separating funnel, pressure should be released regularly
especially if a gas is produced e.g. when NaHCO3 (aq) is used to remove acid impurities, CO2 gas is
formed.

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 Hwa Chong Institution 2023 08 – Introduction

✔ Do not assume the aqueous layer is always the denser layer. (If you do not know the densities of
the compounds, check for the aqueous layer by adding water and noting which layer the water
enters.)
✔ Common drying agents: anhydrous calcium chloride (CaCl2), anhydrous sodium sulfate (Na2SO4) or
anhydrous magnesium sulfate (MgSO4).

● Distillation (for liquids)

Simple distillation is usually used to separate a volatile liquid from non-volatile impurities or to separate
two liquids that differ in boiling point by at least 10 C. See Figure 23(a) for the experimental setup. The
pure desired compound is collected at its boiling point, condensed and collected as the distillate. An
example of a reaction involving distillation is in the oxidation of primary alcohols to aldehydes, taught in
Topic 17 Carbonyl compounds.

To separate liquids with boiling points that are close to each other (< 10 C apart), fractional distillation
is used instead – see Figure 23(b).

thermometer thermometer water out

water out condenser
condenser fractionating
column
round-bottom water in
distillate
flask water in round-bottom
distillate flask
oil/water bath

heat with hot plate heating mantle

(a) simple distillation (b) fractional distillation

Figure 23. Experimental setup for distillation

● Recrystallisation (for solid products)

Recrystallisation is used to purify a crude product by dissolving it in a suitable solvent at or near boiling
point, and then cooling to allow the pure product to crystallise.

Generic procedure for recrystallisation

1. Dissolve the crude solid product in a minimal volume of hot solvent in a conical flask to obtain a
saturated solution.
2. Filter the hot solution to remove any solid impurities.
3. Cool the (saturated) solution in an ice-bath to allow the product to crystallise out.
4. Filter the solution to obtain the pure solid crystals as residue. Wash the crystals with a small
volume of cold solvent.
5. Collect the crystals and allow the crystals to dry.

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Hwa Chong Institution 2023 08 – Introduction

Notes:
✔ A suitable solvent would be one that dissolves the product when hot but not when cold.
✔ The solid may be dried in air or in a desiccator, shown below. If the solid is thermally stable, it can
be dried in an oven or under an infra-red lamp.

Figure 24. A desiccator

Exercise 6.1 (Worked Example)

Refer to the reflux set up in Figure 19 and answer the following questions.
i. What is the purpose of adding anti-bumping granules?
The anti-bumping granules will help the solution to boil evenly, thus preventing the solution
from boiling suddenly and violently (what is known as ‘bumping’), which might be dangerous.

ii. What is one advantage of using a magnetic stirrer instead of anti-bumping granules?
Using a magnetic stirring bar will prevent bumping just like anti-bumping granules. The
magnetic stirring bar can be easily removed using another piece of magnet, whereas the anti-
bumping granules can only be removed by filtration.

iii. Why should the condenser not be stoppered?

Stoppering the condenser will cause pressure to build up and might cause glassware to break.

Refer to the generic procedure for recrystallisation in Section 6.2.2 and answer the following questions.
i. What is the purpose of using “hot” solvent in step 1?
Hot solvent is used as compounds are generally more soluble at higher temperatures. As the
solution cools, the solubility of the compound in the solution decreases and the compound
recrystallises from the solution. Using hot solvent maximises the amount of compound to
recrystallise out at the lower temperatures (usually in ice-bath), thus increasing the yield.

ii. Why do we use only a “minimal” volume of the solvent in step 1? What happens when we
use too much solvent?
After recrystallization, some of the desired compound would still remain in solution even at
the lower temperatures. Hence when too much solvent is used, more compound would
remain dissolved and not be obtained as crystals.

iii. Why is “cold” solvent used to wash the crystals in step 4?

Cold solvent is used so as to minimize the amount of crystals that redissolve back into the
solvent. This is to maximise the yield of the desired compound.

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Hwa Chong Institution 2023 08 – Introduction

6.2.3 Checking purity of product

A simple way to check the purity of the product is by measuring its melting point (for solid) or boiling
point (for liquid) and comparing the value with reference tables or databases.

Most pure organic solids melt at a sharp temperature. Pure liquids are clear (not cloudy) and should distil
over a narrow temperature range (±2 °C) at the boiling point. Solid/liquid samples which melt/distil over
a wide range of temperatures indicate presence of impurities and moisture.

Other techniques to check purity of product include thin-layer chromatography (TLC) and infra-red (IR)
spectroscopy.

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Hwa Chong Institution 2023 09 – Isomerism

09 Isomerism
GUIDING QUESTIONS
• What is isomerism? What are the different types of isomerism?
• What are the structural criteria for exhibition of the different types of isomerism?
• How do the physical and chemical properties of different types of isomers differ?

LEARNING OUTCOMES
Students should be able to:
11.2(a) describe constitutional (structural) isomerism
11.2(b) describe cis-trans isomerism in alkenes, and explain its origin in terms of restricted rotation due to
the presence of π bonds [use of E, Z nomenclature is not required]
11.2(c) explain what is meant by a chiral centre
11.2(d) deduce whether a given molecule is chiral based on the presence or absence of chiral centres and/or
a plane of symmetry
11.2(e) recognize that an optically active sample rotates plane-polarised light and contains chiral
molecules
11.2(f) recognise that enantiomers have identical physical properties except in the direction in which
they rotate plane-polarised light [usage of the term diastereomers is not required]
11.2(g) recognise that enantiomers have identical chemical properties except in their interactions
with another chiral molecule
11.2(h) recognise that different stereoisomers exhibit different biological properties, for example in
drug action
11.2(i) deduce the possible isomers for an organic molecule of known molecular formula
11.2(j) identify chiral centres and/or cis-trans isomerism in a molecule of given structural formula

REFERENCES
1. Albert Lehninger, Principles of Biochemistry, 5th Edition, W.H. Freeman
2. Peter Cann, Chemistry for Advanced Level, Hodder Education
3. https://www.chemguide.co.uk/basicorg/isomerism
4. IUPAC Compendium of Chemical Terminology, The Gold Book,
http://goldbook.iupac.org/index.html

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Hwa Chong Institution 2023 09 – Isomerism

1 INTRODUCTION

Isomers are molecules with the same molecular formula, but different arrangement of the atoms.

Imagine that you have a model of a molecule. To create an isomer of this molecule, you have to take the
model apart, i.e. break the bonds and reconnect the atoms in a different way. If you make a ‘seemingly
different’ molecule just by rotating the original model as a whole or rotating about the single bonds, it is
not an isomer – it is still the same molecule!

For example, Figure 1 shows the same butane molecule, rotated about the centre C–C single bond:

Figure 1. The same butane molecule, rotated about its centre C–C bond

There are many ways a molecule of butane can possibly twist itself, because there is completely free
rotation around all the C–C single bonds. If you rotate the centre C–C bond through various angles, you
obtain different conformations of butane, not isomers. At room temperature, a particular molecule will
be constantly changing from one conformation to another due to free rotation of its single bonds e.g.
pentane:

Figure 2. Different conformations of the pentane molecule

When drawing isomers, take care not to draw repeats of the same isomer. For example, the following
structures all describe the same pentane molecule. They are not isomers.

Figure 3. Structural formulae of the same pentane molecule

Isomers have different IUPAC names, which tells us that they are different molecules.

In this topic, we will focus on the following types of isomerism: constitutional isomerism, cis-trans
isomerism and enantiomerism.

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Hwa Chong Institution 2023 09 – Isomerism

2 CONSTITUTIONAL (STRUCTURAL) ISOMERISM

LO11.2(a): describe constitutional (structural) isomerism

Constitutional isomers are molecules with the same molecular formula but different structural formula.
The physical and chemical properties of constitutional isomers can be very different due to different
carbon chains and functional groups. Constitutional isomerism can be categorised into three categories
– chain isomerism, positional isomerism and functional group isomerism. Do note that there is no need
to memorise these three terms – they are merely guides to help identify constitutional isomerism in
compounds.

2.1 Constitutional isomers with different carbon chains (chain isomers)

These isomers arise because of the possibility of branching in carbon chains. For example, pentane, 2-
methylbutane and 2,2-dimethylpropane are isomers with the molecular formula C5H12:

Figure 4. Constitutional isomers with different carbon chains due to branching

2.2 Constitutional isomers with different positions of same functional group (positional isomers)

These isomers arise because of the possibility of placing the functional group at different carbon atoms
in the carbon chain. For example, pent-1-ene and pent-2-ene are isomers with molecular formula C5H10,
where the position of the alkene (C=C) functional group differs.

With more functional groups, the number of possibilities increases:

1,1-diiodopropane 1,2-diiodopropane 1,3-diiodopropane 2,2-diiodopropane

This type of isomerism also occurs in ring systems:

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 Hwa Chong Institution 2023 09 – Isomerism

2.3 Constitutional isomers with different functional groups (functional group isomers)

These isomers arise when different functional groups consist of the same type of atoms and bonds. For
example, aldehydes and ketones can be constitutional isomers because they both consist of one oxygen
atom and a C=O bond. Hence propanal and propanone are isomers with molecular formula C3H6O:

The following molecule, which has an alkene and an alcohol functional group, is also a constitutional
isomer of propanal and propanone:

Further examples are shown below:

molecular formula: C5H10 molecular formula: C5H10O2 molecular formula: C5H12O

Figure 5. Further examples of functional group isomers. Note: ether consists of a C–O–C group

2.4 Deducing possible constitutional isomers

LO11.2(i): deduce the possible isomers for an organic molecule of known molecular formula

Here is a systematic way to draw all constitutional isomers with a given molecular formula:

1. From the molecular formula, identify likely functional group(s) and check if any double/triple bond
or ring present – see Section 2.4.1.
2. Using the number of carbon atoms, draw all possible carbon chains: start with straight chain first,
then gradually increase the branching to draw all possible branched chains.
3. For each carbon chain from step 2, draw structures with the functional group(s) placed at all possible
different positions on the carbon chain.
4. Repeat step 3 with other likely functional group(s), until all possibilities are exhausted.

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Hwa Chong Institution 2023 09 – Isomerism

2.4.1 Degrees of unsaturation (Useful Info)

We can find out how many double bonds, triple bonds or ring(s) are present in a compound by comparing
its molecular formula with the general formula of alkanes with same number of C atoms.

Recall aliphatic alkanes have the general formula, CnH2n+2. They are saturated and have zero degrees of
unsaturation e.g. butane or methylpropane is C4H10:

If a compound with n carbon atoms has fewer H atoms than 2n + 2, it must contain double/triple bonds
and/or ring(s).

How to tell how many double/triple bonds or rings?

• Every decrease of two H atoms from the alkane general formula contributes to 1o unsaturation.
• A 1o unsaturation indicates either one double bond or one ring present, hence e.g. C4H8 can be
butene or cyclobutane.

• A 2o unsaturation indicates the compound has either:

- 2 double bonds, or
- 2 ring structures, or
- 1 double bond plus 1 ring structure, or
- 1 triple bond.

The more degrees of unsaturation, the more possible combinations of double, triple bonds or rings.
Double bonds include C=C, C=O, C=N and triple bonds include CC, CN so this also provides clues on the
likely functional groups present.

What if the molecule contains atoms other than C and H?

• Halogen atoms do not affect the degree of unsaturation, e.g. C4H9Br has 0o unsaturation, just like
C4H10.

• O and S atoms do not affect the degree of unsaturation, e.g. C4H10O has 0o unsaturation, just like
C4H10.

• For every N atom present, there will be one additional H atom compared to the general saturated
formula e.g. C4H11N has one more H atom than C4H10 though both have 0o unsaturation.

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Hwa Chong Institution 2023 09 – Isomerism

Try this example!

A compound has molecular formula C5H7OF. How many double/triple bonds or ring(s) could it possibly
have?

n = 5, 2(5) + 2 = 12 so there should be twelve H atoms for 0o unsaturation.

The compound has one F atom, so no. of ‘H’ atoms is 8 (count halogens as H atoms).
O atoms have no impact.
=> 12 – 8 = 4 so there are four H atoms fewer  2o unsaturation (each decrease of two H atoms is 1o
unsaturation)
Hence the compound can have either 2 double bonds/2 rings/1 double bond plus 1 ring/1 triple bond.

Exercise 2.1
(a) (Worked Example) How many constitutional isomers are there in C4H10O? Draw their skeletal
formulae.
[Hint: These isomers are either alcohols (-OH) or ethers (C–O–C).]

One strategy: You can first try to draw all the possible alcohol constitutional isomers. Start with
isomers with 4 carbons in the longest carbon chain, followed by the isomers with 3 carbons in the
longest carbon chain.

Next, draw all the ether constitutional isomers. Start by drawing the ether group first, then
add in the rest of the 4 carbons (straight chains followed by branched chains).

Hence there are 7 constitutional isomers for C4H10O.

(b) Propanoic acid, CH3CH2CO2H, and hydroxypropanone, CH3COCH2OH, are isomers with molecular
formula C3H6O2.

(i) Draw the structures of another two isomers which are esters (contain group).

(ii) Draw the structures of another two isomers with both alcohol (OH) group and carbonyl
(C=O) group.

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Hwa Chong Institution 2023 09 – Isomerism

Exercise 2.2
(a) Draw the skeletal formulae of all constitutional isomers with molecular formula C3H6Br2.

(b) In general, how do constitutional isomers differ in their physical properties and chemical
reactivities? Circle the correct options below.

(i) Constitutional isomers with different carbon chains but same functional groups would
have similar/different physical properties and similar/different chemical reactivities.
(ii) Constitutional isomers with same functional groups in different positions of same carbon
chain would have similar/different physical properties and similar/different chemical
reactivities.
(iii) Constitutional isomers with different functional groups but same carbon chain would have
similar/different physical properties and similar/different chemical reactivities.
different, similar (ii) similar, similar (iii) different, different

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Hwa Chong Institution 2023 09 – Isomerism

3 STEREOISOMERISM

Stereoisomers are molecules with the same molecular formula and structural formula but different
arrangement in space. They contain the same atoms bonded to each other, the bonding and functional
groups are identical and differ only in the way the atoms are arranged in 3-D space.

3.1 Cis–trans isomerism

LO11.2(b): describe cis-trans isomerism in alkenes, and explain its origin in terms of restricted rotation due to the presence of π bonds [use
of E, Z nomenclature is not required]
LO11.2(j)part: identify cis-trans isomerism in a molecule of given structural formula

For a molecule to exhibit cis–trans isomerism, it must have:

1) a covalent bond with restricted rotation , e.g. presence of  bond or ring structure,
AND
2) non-identical groups attached to each end of this bond with restricted rotation

3.1.1 Alkenes
Unlike the case of the C–C single bond which rotates freely at room temperatures, it is not possible to rotate one
end of a double bond (e.g. C=C) with respect to the other end, without breaking the  bond:

Figure 6. Rotating a C=C bond in an ethene molecule

Breaking of the  bond requires much more energy than available at normal temperatures. Hence in alkenes,
there is restricted rotation about the C=C bond due to presence of the  bond.

Alkenes with two non-identical groups attached to each carbon of the C=C double bond will exhibit cis-trans
isomerism, e.g. but-2-ene:

Since the C=C bond cannot rotate freely, these two forms are not readily interconvertible by rotation,
hence they are distinct isomers – they have the same structural formula but different arrangements in
space i.e. stereoisomers.

The cis isomer has identical groups on the same side of the double bond while the trans isomer has
identical groups on the opposite sides of the double bond, e.g. but-2-ene:

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Hwa Chong Institution 2023 09 – Isomerism

The following alkenes, methylbut-2-ene and methylpropene, do not exhibit cis-trans isomerism because one
end, or both ends, of the double bond have identical groups attached.

Note that the two structures below are identical compounds (not distinct). They are not cis-trans isomers!

In summary, to deduce whether an alkene can exhibit cis-trans isomerism, look at each end of the C=C bond. If
each end has two non-identical groups attached like below, the alkene can exhibit cis-trans isomerism.

this end has 2 non-identical this end has 2 non-identical

groups attached: X ≠ Y groups attached: A ≠ B

If there are n such C=C double bonds in a molecule, the maximum number of cis-trans isomers will be 2n.

How do we name the cis-trans isomers if X, Y, A and B are all different groups?

The “cis-trans” nomenclature of isomers applies only when we have same groups on the same/opposite sides.
If we have four different groups in an alkene e.g.:

We will be able to tell A and B are cis-trans isomers but won’t be able to assign “cis” or “trans” as there are no
identical groups on same/opposite sides. The E/Z convention is used for such isomers and is not in the A Level
H2 syllabus.

• Cycloalkenes
Cycloalkenes with small rings such as cyclohexene and cyclopentene cannot exhibit cis-trans
isomerism as they exist only in the cis isomer form at room temperatures, even though each carbon
atom of the C=C bond may be attached to non-identical groups.

X unstable due to
ring strain

Figure 7. (a) cis-cyclopentene; (b) cis-cyclohexene; (c) unstable trans isomer of cyclohexene
(H atoms drawn to illustrate the cis and trans forms)

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Hwa Chong Institution 2023 09 – Isomerism

The trans isomer forms of cycloalkenes with smaller rings are not stable due to large ring strain. If
you make a model of this trans isomer, it would be quite impossible to close the ring while
maintaining the trans form and the trigonal planar geometry at the C=C double bond.

Larger rings, e.g. 8 or more atoms, are able to accommodate the trans form, so both their cis and
trans isomers are stable at room temperatures e.g. cyclodecene:

3.1.2 Ring structures (other examples of cis-trans isomers)

Cis-trans isomerism also occurs in ring structures. It is not possible for single bonds that form a ring to rotate
freely, without first breaking the ring. Hence there is restricted rotation about single bonds that form part of a
ring.

Ring structures with non-identical groups attached to two or more atoms in the ring will exhibit cis-trans
isomerism e.g. 1,2-dichlorocyclopentane:

There is restricted rotation about the C1–C2 single bond and C1 and C2 atoms are each attached to two
non-identical groups.

The cis isomer has identical groups on the same side of the plane of the ring, whereas the trans isomer has
identical groups on the opposite sides.

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Hwa Chong Institution 2023 09 – Isomerism

Exercise 3.1 (Worked Example)

Which of the following alkenes exhibit cis-trans isomerism? Draw the cis-trans isomers if any, and label
them cis or trans.

(a) ClCH=CHCl (b)

(a) There is presence of a covalent bond with restricted rotation, and 2 non-identical groups attached to
each end of the carbon-carbon double bond. Hence ClCH=CHCl can exhibit cis-trans isomerism.

(b) Cyclohexene cannot exhibit cis-trans isomerism whereas there are 2 identical groups attached to one end
of the carbon-carbon double bond in the alkyl side chain, thus this compound does not exist as cis-trans
isomers.

Exercise 3.2
Which molecules have isomers that exhibit cis-trans isomerism? (N2005/I/21)

C3H6BrI C3H5I C3H4I2 C3H4BrI

I II III IV

A I, II and III only

B II, III and IV only
C II and IV only
D III and IV only

Exercise 3.3
Linoleic acid is an essential fatty acid in human diet, with the following structural formula:
CH3(CH2)4CH=CHCH2CH=CH(CH2)7CO2H
In linoleic acid, both double bonds are in the cis configuration. Representing the formula by the
abbreviated structure A–CH=CH–CH2–CH=CH–B, draw the structure of:

(a) linoleic acid; and

(b) all its cis–trans isomers.

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Hwa Chong Institution 2023 09 – Isomerism

3.1.3 Cis–trans isomers in nature (Application)

• Retinal
Our sight is dependent on a compound known as retinal. When light enters the eye, retinal molecules bound to
opsin proteins in the eye are converted from the 11–cis isomer to the all–trans isomer within a few picoseconds.
Once formed, the trans-retinal diffuses away from the opsin protein and takes several minutes to be isomerized
back to the cis-isomer.

Figure 8. Conversion of 11-cis-retinal to trans-retinal upon absorption of light

Source: Lehninger, Principles of Biochemistry, 5th Edition

Retinal is usually produced by the biological system through consumption of beta-carotene present in foods such
as carrots, sweet potatoes and apricots.

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Hwa Chong Institution 2023 09 – Isomerism

3.2 Enantiomerism
LO11.2(d): deduce whether a given molecule is chiral based on the presence or absence of chiral centres and/or a plane of symmetry

For a molecule to exhibit enantiomerism (i.e. to be chiral, pronounced ‘kai-ral’), its mirror image must be
non-superimposable onto itself. These two non-superimposable mirror images are called enantiomers.

Molecules which exhibit enantiomerism:

1) often contain one or more chiral centres
2) do not possess any internal plane (or centre) of symmetry

3.2.1 Molecules with one chiral centre

LO11.2(c): explain what is meant by a chiral centre
LO11.2(j)part: identify chiral centres in a molecule of given structural formula

Consider molecule I below. The central carbon atom has four different groups attached to it in a tetrahedral
geometry. This carbon atom is referred to as a chiral centre. Any atom with a tetrahedral geometry
around it that is bonded to four different groups is known as a chiral centre. A chiral centre is denoted
with an asterisk(*) on the structure.

wedged bonds show the bond

pointing out of the paper
towards you
hashed bonds show the bond
pointing into the paper away
from you
these bonds show the arrangement of
atoms/groups in 3D space in
stereochemical formulae, particularly
important in this topic

Now consider molecule II, the mirror image of molecule I.

imagine turning
Molecule II about the
C–H bond to align the
C–Br bond to the
same position as in
Molecule I, you will
find that the Cl and F
atoms are still not
this Br atom is now superimposable onto
aligned with the one Molecule I.
in Molecule I

Molecule II also has a chiral centre attached to the same four groups that are present in molecule I. They
have the same structural formula. However, the two molecules differ in the spatial arrangement of these
groups around the chiral centre. Because of this different arrangement in space, these two molecules
that are non-superimposable mirror images of each other are called enantiomers.

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Hwa Chong Institution 2023 09 – Isomerism

Exercise 3.4 (Worked Example)

(a) Draw the enantiomers of butan-2-ol. Indicate the chiral centres (*).
Step 1. Identify the chiral carbon. Recall that any atom with a tetrahedral
geometry around it that is bonded to four
different groups is known as a chiral centre.

Step 2. Keep any 2 bonds on the plane of the paper, assign

them as ‘stick lines’.
For example, keep the bonds to –CH2CH3 and –OH on
the plane of the paper.

Step 3. Draw in the third group with a solid wedge or

a dashed wedge.

Step 4. Draw in the last group with the wedge not used in step 3,
in this example it is the dashed wedge.

Step 5. To draw the other enantiomer, simply draw a mirror image of the enantiomer you ended with
in Step 4.
Groups on the plane remain on the plane, and
groups pointing towards the mirror plane will
continue to point towards it. Similarly, groups
pointing away from the mirror plane will
continue to point away.

There are other acceptable presentations, please check with your tutors.

(b) Identify the chiral centres, if any, in the molecules below:

Recall that a chiral centre is any atom with a tetrahedral geometry and is bonded to 4 different groups.

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3.2.2 Molecules with more than one chiral centre

Molecules with more than one chiral centre can also exhibit enantiomerism (i.e. be chiral), if they do not
possess any internal plane of symmetry.

Consider molecule III below. It contains two chiral centres. Each chiral centre can have two ways of
arranging its four different groups in 3D space, giving two enantiomers. Hence there can be a total of 4
stereoisomers for molecule III, i.e. 2 pairs of enantiomers:

A and B are enantiomers because they are non-superimposable mirror images of each other. C and D are
also enantiomers.

Note that for A and C, however, the arrangement around one chiral centre (the carbon on the left-hand
side) is exactly the same, so A and C are not enantiomers, just stereoisomers. Similarly, B and D are not
enantiomers. Stereoisomers with at least one chiral centre of the same arrangement are called
“diastereomers” (usage of this term is not required for H2 Chemistry). The arrangement around all chiral
centres must be different in order for two stereoisomers to be considered enantiomers.

• Meso compounds
Consider molecule IV. It also contains two chiral centres. However, each chiral centre is bonded to the
same four groups: OH, H, CH3 and CH(OH)CH3. Again we may draw 4 possible stereoisomers:

Note that P and Q are equivalent structures, not

enantiomers!
P has an internal plane of symmetry, so its mirror
image is superimposable onto itself.
Hence, P is achiral (i.e. not chiral) even though it
has chiral centres, due to its internal plane of
symmetry.

A stereoisomer with two or more chiral centres but no optical activity due to an internal plane of
symmetry is called a meso compound.

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Hwa Chong Institution 2023 09 – Isomerism

Hence molecule IV has only three stereoisomers: enantiomers R and S, and meso compound labelled P
or Q.
If there are m chiral centres in a molecule, the maximum number of stereoisomers will be 2m.
The actual number of stereoisomers is determined by considering any internal plane of symmetry in the possible
structures.

Exercise 3.5

Identify the chiral centres in the pentane-2,4-diol molecule below. Draw the stereoisomers for
pentane-2,4-diol.

3.2.3 Molecules without chiral centres (other examples of chirality)

Enantiomerism can occur in molecules without chiral centres. Consider 1,3-dichloropropa-1,2-diene. It
has the allene functional group: C=C=C.

Due to the orientation of the overlapping p orbitals forming the two  bonds – see Figure 9(a), the H and
Cl atoms at one end do not lie in the same plane as the other end (they lie in perpendicular planes). There
is no internal plane of symmetry in the molecule. Its mirror image is non-superimposable onto itself,
hence it has two enantiomers, and is chiral.

(a) (b)
Figure 9. (a) orbital overlap of the two  bonds in allene functional group (b) enantiomers of 1,3-dichloropropa-1,2-diene

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3.2.4 Properties of Enantiomers

Enantiomers have mostly identical physical and chemical properties, since they have the same structural
formula. However, when placed in a chiral environment or interacting with chiral molecules, the
enantiomers will behave differently from each other.

• Physical properties
LO11.2(e): recognise that an optically active sample rotates plane-polarised light and contains chiral molecules
LO11.2(f): recognise that enantiomers have identical physical properties except in the direction in which they rotate plane-polarised light
[usage of the term diastereomers is not required]

Enantiomers have identical physical properties except in the direction in which they rotate plane-
polarised light.

Each enantiomer rotates plane-polarised light by the same angle but in opposite directions. A 50:50
mixture of the two enantiomers therefore does not rotate plane-polarised light, as the clockwise rotation
caused by one enantiomer is exactly cancelled by the anticlockwise rotation of the other enantiomer.
This mixture containing equal proportions of each enantiomer is called a racemic mixture. The direction
of rotation cannot be predicted from the structure of the enantiomer and is determined by direct
measurement using a polarimeter.

When a sample is able to rotate plane-polarised light, this sample is said to be optically active and contain
chiral molecules. Mixtures containing only achiral molecules, or a racemic mixture will have no effect on
plane-polarised light, and are therefore optically inactive.

The optical activity of a sample can be measured using a polarimeter.

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• Plane-polarised light (Background Info)

Light is an electromagnetic wave. It is made up of an electric field and a magnetic field oscillating
perpendicular to each other and to its direction of propagation. The oscillation of each light wave is
assigned along the plane of the electric field.

double-headed arrow
Direction of represents the
propagation oscillation of this
particular light wave

Figure 10. Direction of propagation and oscillation of a light wave

Unpolarised light emitted from common light sources consists of light waves oscillating in all directions.
By passing it through a polariser, only light waves oscillating in one particular plane are allowed to pass
through, resulting in plane-polarised light.

Unpolarised light Polariser Plane-polarised

light
Figure 11. Obtaining plane-polarised light using a polariser

• Measuring Optical Activity using a Polarimeter (Background Info)

In a polarimeter, plane-polarised light is allowed to pass through a sample solution. If the sample contains
chiral molecules of a pure enantiomer, the plane-polarised light would rotate by a certain angle
(depending on concentration) either clockwise or anticlockwise. The rotated plane-polarised light is
analysed by another polarizer and the angle of rotation measured.

Figure 12. How a polarimeter works to measure the angle of rotation of plane-polarised light

The enantiomer that rotates plane-polarised light in a clockwise direction is said to be dextrorotatory
(Latin dextro: “right”), and we add a (+) prefix to its name. The enantiomer that rotates plane-polarised
light in an anticlockwise direction is said to be laevorotatory (Latin laevo: “left”), and we add a (–) prefix
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to its name. The direction of rotation cannot be predicted from its structure and is determined by direct
measurement using a polarimeter.

To distinguish between enantiomers based on structure alone, chemists use a set of systematic rules to
assign each chiral centre to either an R or S configuration. This R/S convention is not in the A-level H2
syllabus.

Sunglasses (Application of polarized light)

Try this!
When buying sunglasses, some are claimed to have polarising effects. How do you know the claim is true?
Here is a simple way to check:
• If they are on the same rack with others, take two pairs and hold them such that you are looking
through both. Then slowly rotate one pair of glasses through 90o. You should see the lenses turn
darker and darker.

• Chemical properties
LO11.2(g): recognise that enantiomers have identical chemical properties except in their interactions with another chiral molecule
LO11.2(h): recognise that different stereoisomers exhibit different biological properties, for example in drug action

Enantiomers have identical chemical properties except in their interactions with another chiral
molecule.

Since the human body is a chiral environment, it responds differently depending on which enantiomer is
interacting with it. Hence enantiomers have different biological properties and this has particular
relevance in drug action.

Examples:
• (–)-carvone gives a spearmint taste, while (+)-
carvone gives an earthy taste of citrus and
pepper.
• Pure (+)-lactic acid is produced in our muscles
when we exercise anaerobically while a
racemic mixture of (+)-lactic acid and (–)-
lactic acid is often produced when milk is
fermented.
• (–)-epinephrine is a natural hormone also
known as adrenaline with a stimulating effect
while (+)-epinephrine cannot fit into the
enzyme active site and is mildly toxic.

Figure 13 shows how the two enantiomers of

epinephrine interact differently with the same Figure 13. Different interactions of (–)-epinephrine and (+)-
enzyme active site, due to the fixed spatial epinephrine with the same enzyme active site
arrangement within the active site.

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The story of thalidomide

In the late 50s, thalidomide was a drug prescribed to pregnant women for morning sickness. It seemed
to be a very successful, non-toxic sedative with no known side effects. Thousands of pregnant women
took the drug to relieve their symptoms. Soon there was a huge increase in birth defects, especially in
Europe and Canada. It was discovered that thalidomide was responsible for this, causing children to be
born with missing or extra limbs.

Figure 14. Photo by Leonard McCombe/Time Life Pictures/Getty Images)

Research showed that while (+)-thalidomide was an effective and safe sedative, (–)-thalidomide was the
culprit in damaging the fetus. Originally it was thought that the problem had been due to contamination
by the (–)isomer during production, but subsequent research showed that racemization of the pure
(+)isomer occurs rapidly as soon as it enters the bloodstream. Within 10 min, racemization is over 50%
complete. Hence even if the (+)isomer is administered, the terrible effects of the (–)isomer cannot be
avoided.

Figure 15. The two enantiomers of thalidomide

An important lesson
Following the thalidomide incident, there was increased fear in the safety of pharmaceutical drugs. It
brought on a change in drug testing and increased awareness of potential side effects of drugs. It led to
much stricter testing before drug licensing.

The biological impact of enantiomers also highlights the importance of enantiomeric purity in the medicinal
industry. This has to be achieved either through synthesis of only one particular enantiomer or the separation of
mixtures of enantiomers.

As enantiomers have mostly identical chemical and physical properties, it is very difficult to separate
them from a mixture. The only way is to involve other chiral compounds, since enantiomers interact
differently with chiral molecules. One method, kinetic resolution, makes use of the different reaction
rates of the enantiomers with a chiral reagent.

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• Kinetic Resolution (Method of separation of enantiomers)

In kinetic resolution, a mixture of enantiomers is reacted with a chiral reagent. The chiral reagent is
chosen such that it reacts quickly with one enantiomer but reacts very slowly with the other enantiomer.

For example, to separate an enantiomer of mandelic acid from its racemic mixture, we add a limited
amount of a pure sample of (–)-menthol (chiral reagent). Only one enantiomer of mandelic acid reacts
with the (–)-menthol to produce an ester. The other enantiomer of mandelic acid, due to difference in
rate of reaction, does not form an ester with the (–)-menthol.

The ester product now has different physical and chemical properties with the unreacted mandelic acid
and can be easily separated through conventional separation techniques. The desired enantiomer is then
recovered by hydrolysing the ester.

hydrolysis

racemic mixture (–)-menthol ester

mandelic acid pure (+)-mandelic acid
enantiomers

unreacted mixture of
(–)-mandelic acid and some
(+)-mandelic acid

Figure 16. Reaction scheme in the kinetic resolution of mandelic acid

3.3 Counting the total number of stereoisomers

LO11.2(i): deduce the possible isomers for an organic molecule of known molecular formula
LO11.2(j): identify chiral centres and/or cis-trans isomerism in a molecule of given structural formula

Stereoisomers include both cis–trans isomers and enantiomers.

If a molecule has m chiral centres and n double bonds that can give rise to cis–trans isomers, the
maximum number of stereoisomers it can have = 2m+n.

The actual number of stereoisomers is determined by considering any internal plane of symmetry in the
possible structures.

For example, in the methoprene molecule below, there is only one chiral centre, and both C=C double
bonds can give rise to cis-trans isomerism. As such, the maximum number of possible stereoisomers for
methoprene is 2(1+2) = 8. There is no internal plane of symmetry, so the actual total number is 8.

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Exercise 3.6
Consider a compound with structural formula CH3CH=CHCH(CH3)CH2CH3.
(a) (a) What is the total number of stereoisomers?

(b) Draw the structure of each stereoisomer.

Exercise 3.7
(a) What is the total number of stereoisomers for the following compound?

A 2 B 3 C 4 D 8

(b) The drug cortisone has the formula shown.

In addition to those chiral centres marked by an asterisk(*), how many other chiral centres are present
in the cortisone molecule?
A 0 B 1 C 2 D 3

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10 Alkanes
GUIDING QUESTIONS
● Why are alkanes generally unreactive, particularly towards polar reagents?
● Which class of reagents do alkanes react with and why?
● What type of reactions do alkanes undergo and why?
● How do alkanes react with halogens?
● What are the environmental concerns arising from the use of hydrocarbons?

LEARNING OUTCOMES
At the end of the chapter, you should be able to:
11.3 (a) explain the general unreactivity of alkanes, including towards polar reagents
11.3 (b) describe the chemistry of alkanes as exemplified by the following reactions of ethane:
(i) combustion
(ii) free-radical substitution by chlorine and by bromine
11.3 (c) describe the mechanism of free-radical substitution with particular reference to the
initiation, propagation and termination reactions
11.3 (n) 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
11.3 (o) recognise that petroleum, a chemical feedstock, is a finite resource and the
importance of recycling

REFERENCES
1. Peter Cann and Peter Hughes, Cambridge International AS and A level Chemistry, Hodder
Education, Chapter 13.
2. John McMurry, Organic Chemistry, 6th ed., Thomson/Brooks/Cole, Chapters 3, 5 and 10.
3. Jonathan Clayden, Nick Greeves and Stuart Warren, Organic Chemistry, 2nd Ed., Oxford
University Press, Chapter 37.

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1 INTRODUCTION

Alkanes are the simplest and least reactive of the homologous series found in organic chemistry.

● They are often described as saturated hydrocarbons:

Hydrocarbon – contains only carbon and hydrogen
Saturated – contains only single bonds (i.e. only C–C and C–H single bonds for alkanes), hence
each carbon has four bonds.

The chart below describes different types of hydrocarbons and some examples of them.

Hydrocarbons

Saturated hydrocarbons Unsaturated hydrocarbons Aromatic

hydrocarbons

Aliphatic Alicyclic Aliphatic alkenes Alicyclic Alkynes Arenes

alkanes, e.g., alkanes e.g., alkenes e.g., e.g.,
(cycloalkanes) (cycloalkenes)
e.g., e.g.,

● Alkanes contain only sp3 hybridised carbon atoms.

● Aliphatic alkanes contain open chains of carbon atoms which may be straight–chain or
branched.

In straight–chain alkanes, the carbon atoms are connected in a continuous line, whereas in
branched alkanes the carbon atoms may be connected to two or three other carbon atoms.

● Cycloalkanes contain closed rings of carbon atoms.

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2 NOMENCLATURE
LO11.1(a)(i)(part): interpret, and use the nomenclature, general formulae and displayed formulae of the following classes of
compound: (i) hydrocarbons (alkanes, alkenes and arenes)

2.1 Straight-chain alkanes

Straight–chain alkanes are named according to the number of carbon atoms in their chain with an
–ane suffix.

Examples

Number of Formula Number of Formula

Name Name
carbons (n) (CnH2n+2) carbons (n) (CnH2n+2)
1 Methane CH4 6 Hexane C6H14
2 Ethane C2H6 7 Heptane C7H16
3 Propane C3H8 8 Octane C8H18
4 Butane C4H10 9 Nonane C9H20
5 Pentane C5H12 10 Decane C10H22
Table 1. Names of straight-chain alkanes

2.2 Branched (or substituted) alkanes

1. Locate the longest continuous chain of carbon atoms; this chain determines the parent name
for the alkanes.
2. Number the longest chain beginning with the end of the chain nearer to the substituent, if any.
3. Use the numbers obtained by application of rule no. 2 to designate the location of the
substituent group.
4. When two or more substituents are present, give each substituent a number corresponding to
its location on the longest chain. Cite them in alphabetical order. The number prefixes di-, tri-,
tetra-, etc. are ignored in alphabetizing (refer to point 6).
5. When two substituents are present on the same carbon atom, use that number twice.
6. When two or more substituents are identical, indicate this by the use of the prefixes di-, tri-,
tetra- and so on.

Examples

4–ethyloctane 3–ethyl–2–methylhexane 4–ethyl–2,4–dimethylhexane

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In the case of a substituent also branching off, it is useful to treat the substituent separately.

The substituent is named as it follows:

4–(1–methylethyl)heptane
a (1–methylethyl) group
The carbon bonded to the parent chain is C1.

2.3 Cycloalkanes

To name a cycloalkane, add “cyclo-” as a prefix in front of the parent name of the corresponding
alkane.

Examples

cyclopropane (C3H6) cyclohexane (C6H12)

Substituted cycloalkanes are named by rules similar to those used for open–chain alkanes.

Examples

methylcyclopentane 1–ethyl–2–methylcyclopentane 1,1,3–trimethylcyclohexane

If there is just one substituent, no numbering is needed.

Exercise 2.1

(a) Write the general formula of aliphatic alkanes and cycloalkanes.

(b) Which class of compounds is isomeric with cycloalkanes?

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3 ISOMERISM
LO11.2(a): describe constitutional (structural) isomerism
LO11.2(d): deduce whether a given molecule is chiral based on the presence or absence of chiral centres and/or a plane of
symmetry
LO11.2(i): deduce the possible isomers for an organic molecule of known molecular formula

3.1 Constitutional (structural) Isomerism

Alkanes can exhibit constitutional isomerism.

The number of constitutional isomers increases dramatically as the number of carbon atoms
increases. For example, C10H22 has 75 and C20H42 has 366,319 constitutional isomers respectively.

Exercise 3.1 (Includes Worked Example)

Draw the skeletal formulae of all the alkanes with the molecular formula of
(a) C5H12 (Worked Example)

With five C and twelve H atoms, the molecule will consist of single bonds only, just like a
saturated (aliphatic) alkane with a general formula of CnH2n+2. Thus, we start with the straight
chain pentane with five C atoms. Then, we rearrange the carbon chain by shortening it one
carbon at a time and re-attaching this –CH3 group to other non-terminal carbon atoms to form
the various constitutional isomers with branched chains.

Answer

Note: Remember to draw the skeletal formulae as specified in the question.

(b) C5H10

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3.2 Enantiomerism

Apart from exhibiting constitutional isomerism, some alkanes can also exhibit enantiomerism.

Exercise 3.2 (Worked Example)

Draw the structural formula of the alkane with the lowest Mr that can exhibit enantiomerism. Draw the
mirror images of the enantiomers.
[J95/1/9(a) modified]

Answers
To exhibit enantiomerism, the molecule should have a central C atom as a chiral centre with four
different groups attached to it. To obtain an alkane with the lowest Mr, start by drawing a hydrogen
atom to the central C atom and increase the number of C atoms for each new group attached. Check
that all four groups attached to the central C atom are different.

Next, draw the stereochemical formula of the molecule and its mirror image. The molecule and its
mirror image are not superimposable on each other and are enantiomers.

Enantiomers:

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4 PHYSICAL PROPERTIES
LO2(m): describe, interpret and/or predict the effect of different types of structure and bonding on the physical properties of
substances
LO2(n): suggest the type of structure and bonding present in a substance from given information

The electronegativity of carbon and hydrogen are 2.55 and 2.20 respectively. The C–H bond thus has
a very small dipole moment (considered as a non-polar bond). The molecules of alkanes are therefore
non–polar and are held together mainly by weak dispersion forces.

4.1 Physical state

At room temperature and pressure, the lower alkanes, from methane to butane are gases.
The C5–C17 straight–chain alkanes are liquids while those with 18 or more carbon atoms are solids.

State Melting Boiling Density

Formula Name Mr Remarks (FYI only)
(at r.t.p) point /oC point /oC /g cm–3
major component of
CH4 methane gas 16 –182 –162 –
natural gas

C2H6 ethane gas 30 –183 –89 – component of natural gas

component of liquefied
C3H8 propane gas 44 –188 –42 – petroleum gas (LPG),
bottled gas
component of LPG,
C4H10 butane gas 58 –138 0 –
cigarette lighters
C5H12 pentane liquid 72 –130 36 0.63
C6H14 hexane liquid 86 –95 69 0.66 component of petrol
C7H16 heptane liquid 100 –91 98 0.68
major component of
C8H18 octane liquid 114 –57 126 0.70
petrol
Table 2. Physical properties of some alkanes

4.2 Boiling point

Straight
chain
alkanes

Branched–chain
alkanes

Figure 1. Boiling points of straight-chain and branched-chain alkanes

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The boiling point of alkanes increases regularly with increasing number of carbon atoms in the chain.

As the number of carbon atoms increases, the number of electrons in the molecule increases, hence
size of the electron cloud increases leading to stronger dispersion forces between the molecules.
Thus, more energy is required to overcome the stronger dispersion forces between the molecules.
Branched–chain alkanes have lower boiling points than the straight–chain alkanes with the same
number of carbon atoms. Recall what you have learned in Topic 2 Chemical Bonding that explains this
observation.
H H H H H CH3

H C C C C C H H3C C CH3

H H H H H CH3
pentane 2,2–dimethylpropane
b.p. = 36 oC b.p. = 9.5 oC

4.3 Melting point

The increase in melting point of alkanes is not as regular as that observed for their boiling points; this
is because the dispersion forces between the molecules in a crystal depend not only on the size of the
molecules but also on the arrangement of molecules in a solid crystal lattice. The table below
illustrates the effect of structure on the melting point of four different C6H14 isomers.

IUPAC Name Structure Boiling point / oC Melting point / oC

Hexane 69 –95

2-methylpentane 60 –154

2,3-dimethylbutane 58 –135

2,2-dimethylbutane 50 –98

Table 3. Boiling and melting points of C6H14 isomers

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4.4 Solubility

In order for dissolution to occur, the solute molecules and the solvent molecules should have
favourable intermolecular forces of attraction.
Alkanes can form favourable dispersion forces with non-polar solvents such as benzene and
tetrachloromethane. Hence they are soluble in non-polar solvents.

Alkanes can only form permanent dipole-induced dipole intermolecular forces with water, which are
much weaker than the hydrogen bonding between water molecules themselves (as well as the
dispersion forces between alkane molecules). Hence they are insoluble in water.

4.5 Density

Liquid alkanes are less dense than water and form an immiscible layer above water.

Their densities increase slightly with increasing number of carbon atoms present. This is because the
increase in the strength of dispersion forces causes the alkane molecules to attract more closely
together, resulting in a slightly smaller volume of the liquid. Since ρ = m/V, with a larger relative
molecular mass, the density of the liquid increases.

4.6 Viscosity

Viscosity describes a fluid's internal resistance to flow and may be thought of as a measure of fluid
friction. The viscosity of liquid alkanes increases with increasing number of carbon atoms present as
the dispersion forces between the molecules increases. In addition, longer-chain alkanes have higher
viscosity as the long molecules tend to “tangle up” with one another.

Exercise 4.1

The following are boiling points of various alkanes given in oC and at atmospheric pressure.

Butane Pentane Hexane

0.5 oC 36 oC 69 oC

(a) Explain why the boiling point of butane is lower than that of pentane.
(b) Draw the structure of 2,2-dimethylbutane and predict whether it would have a higher
or lower boiling point than hexane.

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5 CHEMICAL PROPERTIES
LO11.3(a): explain the general unreactivity of alkanes, including towards polar reagents

The only two types of bonds contained in alkanes, C–C and C–H, are strong and non-polar. The C–C
and C–H bonds are essentially non-polar due to similarity in electronegativities of the C and H atoms.
Hence, alkane molecules do not contain any significant amount of positive or negative charge, and are
unreactive towards polar reagents.

The net result is that alkanes have a fairly restricted set of reactions, namely: combustion and free
radical substitution.

5.1 Combustion of alkanes

LO11.3(b): describe the chemistry of alkanes as exemplified by the following reactions of ethane: (i) combustion

Alkanes react with excess oxygen (complete combustion) to give carbon dioxide and water. The
reaction is a highly exothermic process.

General equation

Example CH4(g) + 2O2(g) →

 CO2(g) + 2H2O(l) ∆Hc = −890
890 kJ mol-11
 20CO2(g) + 21H2O(l)
C20H42(s) + 30½ O2(g) → ∆Hc = −13368
13368 kJ mol-11

Although the combustion of alkanes is highly exothermic, it also has a high activation energy. For
example, a mixture of methane and oxygen is stable unless ignited by a spark. The reaction, once
started, accelerates explosively due to large amount of heat liberated.

Alkanes only burn in the gaseous state. Liquid and solid alkanes must be vapourised before they will
burn.

When they are burnt in a limited supply of oxygen (incomplete combustion), carbon (soot) and carbon
monoxide are also formed and these have adverse environmental consequences.

Example 2CH4 + 3O2 → 2CO + 4H2O

CH4 + O2 → C + 2H2O

Exercise 5.1

The complete combustion of alkanes to produce

carbon dioxide and water is an important exothermic
reaction. Which line on the graph shows the
relationship between the number of carbon atoms in
the alkane and the number of moles of oxygen gas
needed for complete combustion of the alkane?
[J2003/I/23]

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5.2 Free radical substitution

LO11.3(b): describe the chemistry of alkanes as exemplified by the following reactions of ethane: (ii) free-radical substitution
by chlorine and by bromine

Alkanes react with halogens (Cl2 and Br2) in the presence of ultraviolet light or heat to form
halogenoalkanes (or alkyl halides). This type of reaction is known as free radical substitution, an
example of non-polar reactions.

When initiated (started off) by the absorption of UV light or sunlight, the reaction is called a
photochemical reaction. Nevertheless, remember that the free radical substitution can also be
initiated if sufficient heat is supplied. In the reaction, one or more of the hydrogen atoms in the alkane
can be substituted by the halogen atom(s).

Reagent and conditions: Cl2(g) or Br2(l); UV light or heat

Observations: Greenish–yellow Cl2(g) decolourised

or Reddish–brown Br2(l) decolourised

5.2.1 Mechanism of the free radical substitution of methane by chlorine

LO11.3(c): describe the mechanism of free-radical substitution with particular reference to the initiation, propagation and
termination reactions

Step 1. Initiation

The Cl−Cl bond is homolytically broken to give chlorine free radicals (Cl•). The energy required
comes from the light absorbed or the heat supplied.
UV
Cl Cl 2Cl•

Exercise 5.2 (Worked Example)

Why are the C−H bonds in CH4 unaffected during the initiation step?

Answer
The energy is insufficient to break the stronger C−H bond.
(From the Data Booklet, Bond Energy (Cl−Cl) = 242 kJ mol−1; Bond Energy (C−H) = 410 kJ mol−1)

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Step 2. Propagation

The highly reactive chlorine radical collides with a methane molecule and abstracts a hydrogen atom
to produce HCl and a methyl radical (•CH3).

Cl• + CH4 → HCl + •CH3 (1)

(Note: ΔH(1) = B.E.(C–H) – B.E.(HCl) = 413 – 431 = –18 kJmol–1 which explains why HCl and •CH3 are formed
instead of C–Cl and •H)

This methyl radical then reacts further with another molecule of Cl2 in a second propagation step to
yield the product chloromethane and regenerate a new chlorine radical.

•CH3 + Cl2 → CH3Cl + Cl• (2)

The chlorine radical formed can again react with another methane molecule as in step (1) and so on,
making the radical a homogeneous catalyst. Thus, once the reaction has been initiated, it becomes a
self–sustaining cycle of repeating steps (1) and (2), making the overall process a chain reaction.

Exercise 5.3

(a) Why is the free radical reaction known as a chain reaction?

(b) Explain why the reaction of alkanes with halogens requires only a flash of ultraviolet light
rather than prolonged radiation. [J88/II/2(c) modified]

Step 3. Termination
Two radicals collide and combine to form a stable product in this stage. The possible products are:

Cl• + C• → Cl2
Cl• + •CH3 → CH3Cl
•CH3 + •CH3 → CH3CH3

When these reactions occur, radicals needed for the propagation steps are consumed. The reaction
cycle is broken and the chain reaction is terminated.

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Exercise 5.4

(a) State the conditions used for the reaction between ethane and bromine.
C2H6 + Br2 → C2H5Br + HBr
(b) Why is this described as a free–radical substitution reaction?
(c) Write equations to show the mechanism for the above reaction.
[N2006/III/6(a) modified]

5.2.2 Formation of by–products

Halogenation of alkanes via free radical substitution may seem like a good method of obtaining
halogenoalkanes at first, but in reality, the extent and the position of substitution is difficult to control.

A free radical is highly reactive and can react with almost any C–H bond present in the reaction
mixture. In the presence of excess halogen, further substitutions of the product may occur resulting
in a mixture of multi–substituted halogenoalkanes.

For example, chloromethane formed may further react with a chlorine radical to form
dichloromethane:
CH3Cl + Cl• → •CH2Cl + HCl

•CH2Cl + Cl2 → CH2Cl 2 + Cl•

dichloromethane

Similarly, CH2Cl2 can undergo further chlorination to give CHCl3 and CCl4.

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Exercise 5.5 (Includes Worked Example)

Suggest suitable reaction conditions for the substitution of methane by chlorine in UV light, so
as to favour the production of
(a) chloromethane (Worked Example)

Answer
Excess methane and limited amount of chlorine.

In this way, further substitution of the monochlorinated methane is limited as the

probability of chlorine radicals reacting with a methane molecule is higher than the
probability of chlorine radicals reacting with a monochlorinated methane molecule.

(b) tetrachloromethane.

5.2.3 Ratios of products formed when an alkane has non-equivalent hydrogen atoms

As all hydrogen atoms are susceptible to substitution, when an alkane contains 3 or more carbon
atoms, isomeric products are formed depending on which H atom is substituted. The proportion of
the isomers depends on the probability of the intermediates formed and the relative stability of the
intermediates.
Let’s look at the chlorination of propane: two monochlorinated products are possible and their
experimental yields are shown in the equation below. How can we explain their ratios?

Before we examine their ratios, let’s look at the classification of hydrogen atoms in alkanes and the
stability of alkyl radicals.

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Classification of carbon and hydrogen atoms

Carbon atoms are classified depending on the number of other carbon atoms attached to it. Hydrogen
atom is classified according to the carbon atom to which it is attached. For example, a hydrogen atom
attached to a primary carbon atom is called a primary hydrogen (Table 4). In the following topics, we
will use the same classification for radicals, carbocations, alcohols, amines, and so on.

No. of alkyl groups attached 1 2 3

Type of carbon atom Primary (1) Secondary (2) Tertiary (3)
Type of hydrogen atom Primary (1) Secondary (2) Tertiary (3)
Table 4. Classification of carbon and hydrogen atoms

Stability of alkyl radicals

The alkyl groups attached to the carbon radical play a role in the stability of that carbon radical. The
more alkyl groups attached to the carbon radical – the more stable the radical is and hence more
easily it will be formed.

R' R' H H
R C R C R C H C
R" H H H

Stability : 3o radical > 2o radical > 1o radical > methyl radical

Reason: Alkyl groups are weakly electron-donating and can hence compensate for the electron
deficiency experienced by carbon radicals (or carbocations, see Alkenes).

We can now use the abovementioned concepts to explain the experimentally observed ratio of the
two monochlorination products formed from propane. There are two factors which affect the
proportion of products formed:

1. Ratio of different types of hydrogen atoms present in the alkane

In the case of propane, the ratio of primary ( ) hydrogens to secondary ( ) hydrogens is
6:2. Therefore, based on probability only, there should be two types of monochlorinated
products formed, 1–chloropropane and 2–chloropropane, and their ratio should be 6:2, or 3:1.
(see next page)

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2. Stability of each type of carbon radical intermediate present

Propyl radical ( CH2CH2CH3), formed by the abstraction of a primary hydrogen atom, is however
a primary radical and less stable than the secondary isopropyl radical CH3CHCH3, and hence it is
less likely to form. So, formation of 1-chloropropane is less favoured.

Figure 2. The formation of carbon radical intermediate and its subsequent chlorination

Hence, the actual ratio of 1–chloropropane:2–chloropropane cannot be 6:2. In fact, it is found to be

45:55 (or nearly 1:1), which is due to both factors playing a role in the mechanism of the reaction.

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Exercise 5.6 (Includes Worked Example)

1. Pentane was reacted with limited chlorine in the presence of uv light. Assuming that only
mono-chlorination takes place and the reaction occurs at the same rate at all carbon atoms,
predict the ratio of the products obtained.
[HCI Prelim 2008/I/20]

1-chloropentane : 2-chloropentane : 3-chloropentane

A 3 : 2 : 1
B 1 : 2 : 3
C 1 : 3 : 2
D 3 : 1 : 2

2. Worked Example
2-methylbutane, CH3CH2CH(CH3)2, undergoes free radical substitution with Cl2 to give 4
mono-substituted products A, B, C, and D.

Type of Hydrogen Relative Reactivity

Primary, 1o 1
Secondary, 2o 3.5
Tertiary, 3o 5

The following information will allow you to determine the structures of A, B, C and D.
• The ratio of the four products formed can be found by multiplying the relative reactivity
of the hydrogen responsible for the formation of the product to the number of
hydrogen atoms in the compound that can form that product.
• There is twice as much of C as compared to A in the product mixture.
• B and C are both optically active.

(i) Draw the structures of the 4 monochlorinated products and label each structure (A, B, C or
D). Explain your answer.

(ii) Predict the ratio of the four monochlorinated products by considering the above
information.
[HCI Promo 2014/II/5]

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Answer
(i) Structure Explanation
• Since B and C are optically active,
they can only be:
A

or .
B
• Since there is twice the amount of C
as compared to A, the hydrogen
atoms responsible for their
formation should be from the -CH3
C groups.

A must be and C

D must be

• As a check, ratio of product A : C

= 3 x 1o H : 6 x 1 o H = 3 : 6

(ii) Ratio A : B : C : D = 1  3 : 3.5  2 : 1  6 : 5  1 = 3 : 7 : 6 : 5

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5.2.4 Reactivity of halogens with alkanes

The reactivity of halogens in the free radical substitution of alkanes decreases in the following order:
F2 > Cl2 > Br2 > I2.

Reaction of methane with halogens

Fluorine gas Reacts vigorously, even in the dark and at room temperature.
Dangerously exothermic because of the low F–F bond energy and the high C–F
bond energy.
Chlorine gas Requires UV light or heat. Reaction is exothermic.
Bromine liquid Requires UV light or heat. Reaction is slower than with chlorine.
Iodine solid No reaction.

The ∆H of the reactions of methane with the halogens are shown below:
CH4 + X2 → CH3X + HX ∆Hr

Halogen (X) ∆Hr / H–X bond energy / C–X bond energy / X–X bond energy /
kJ mol–1 kJ mol–1 kJ mol–1 kJ mol–1
F –478 562 484 158
Cl –117 431 340 244
Br –43 366 280 193
I +22 299 240 151
Table 5. Bond energies for calculation of ∆Hr

From the table, the trend in reactivity matches the trend in ∆Hr, which is calculated as the overall
enthalpy change for both propagation steps. Recall Topic 5 Chemical Energetics for the calculation of
∆Hr by the use of bond energies of the bonds broken and formed.
The C–H bond is broken in the first propagation step (Step 1), whereas H–X is formed. The X–X bond
is broken in the second propagation step (Step 2) and C–X bond is formed.

Step 1: CH3–H + X• → •CH3 + H–X ∆H1 = BE(C–H) – BE(H–X)

Step 2: •CH3 + X–X → CH3–X + X• ∆H2 = BE(X–X) – BE(C–X)
Overall reaction: CH4 + X2 → CH3X + HX ∆Hr = ∆H1 + ∆H2

Exercise 5.7 (Worked Example)

Chloroalkanes and bromoalkanes can be made by the reaction of the corresponding halogen with
alkanes, for example:
C2H6 + Cl2 → C2H5Cl + HCl

Suggest why it is not possible to make iodoalkanes by this method. [N2010/III/1(c)]

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Answer
Propagation: I• + CH3CH3 → HI + •CH2CH3
•CH2CH3 + I2 → CH3CH2I + I•

The H–I bond formed in the first propagation step is very weak, such that this step becomes highly
endothermic. H1 = BE(C–H) – BE(H–I) = 410 – 299 = +111 kJ mol–1. For the second step,
H2 = BE(X–X) – BE(C–I) = 151 – 240 = -89 kJ mol–1. Hence, this final step is insufficiently exothermic
to make up for the endothermic formation of the alkyl radical in the first step.

Note: recall from Chemical Energetics that H = BE(Broken) – BE(Formed)

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6 ALKANES AS FUELS

Alkanes are found in crude oil and their main use is as fuels. A huge fraction of the energy we use
comes from the combustion of alkanes. The gas in cookers, the petrol in cars, aviation fuel and diesel
oil for powering ships and electric generators are all mixtures of alkanes.

6.1 Processing of crude oil

Fractional distillation (Background info)

● Crude oil is a mixture of many hundreds of hydrocarbons. It also contains some compounds
containing sulfur and nitrogen. It is an important source of aliphatic and aromatic hydrocarbons.
● The first stage in the processing of crude oil is fractional distillation, carried out at atmospheric
pressure.

Figure 3. Model of a fractional

distillation tower Figure 4. Fractional distillation of crude oil

No. of C Boiling point % in

Fraction Uses
atoms range / oC crude oil
Petroleum gas 1–4 < 40 2 Fuel, petrochemical feedstock
Fuel for petrol engines, petrochemical
Gasoline 5 – 12 40 – 200 20
feedstock
Airplane fuel, can be cracked to give
Kerosene 12 – 16 175 – 275 13
more gasoline
Fuel for diesel engines, can be cracked
Gas oil 15 – 18 250 – 400 20
to give more gasoline
Lubricating oil, power station fuel,
Residue > 20 > 350 45 bitumen for roads, can be cracked to
give more gasoline
Table 6. Fractions of crude oil and their uses

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LO 11.3(o): recognise that petroleum, a chemical feedstock, is a finite resource and the importance of recycling

Petroleum, a fraction of crude oil, is an important energy source. However, it is a finite resource (a
resource that does not renew itself at a sufficient rate for sustainable economic extraction in
meaningful human time-frames). The world has a limited supply of petroleum, and current
estimations tell us that within the next few decades mankind will have completely depleted this
valuable natural resource.

6.2 Importance of recycling

Recycling is a process to convert waste materials into new products to

prevent waste of potentially useful materials, reduce the consumption
of fresh raw materials, reduce energy usage, reduce air pollution (from
incineration) and water pollution (from landfilling) by reducing the need
for "conventional" waste disposal and lower greenhouse gas emissions
as compared to plastic production. Recycling is a key component of
modern waste reduction and is the third component of the "Reduce,
Reuse and Recycle" waste hierarchy.

Recycling is very important as waste has a huge negative impact on the natural environment.
● Harmful chemicals and greenhouse gases are released from rubbish in landfill sites. Recycling
helps to reduce the pollution caused by waste.
● Habitat destruction and global warming are some the effects caused by deforestation. Recycling
reduces the need for raw materials so that the rainforests can be preserved.
● Huge amounts of energy are used when making products from raw materials. Recycling helps to
preserve natural resources.
Recycling is essential to cities around the world and to the people living in them.
● No space for waste. Landfill sites are filling up fast.
● Reduce financial expenditure in the economy. Making products from raw materials costs much
more than if they were made from recycled products.
● Preserve natural resources for future generations. Recycling reduces the need for raw materials;
therefore preserving natural resources for the future.

6.3 Environmental consequences of the use of hydrocarbons

LO 11.3(n)(part): recognise the environmental consequence of: (i) carbon monoxide, oxides of nitrogen and unburnt
hydrocarbons arising from the internal combustion engine and of their catalytic removal

6.3.1 Carbon monoxides and unburnt hydrocarbons

Carbon monoxide and unburnt hydrocarbons arise due to incomplete combustion of the fuel, which
may be caused by various factors such as short reaction time in the internal combustion engine, poor
maintenance of the engine and a lack of oxygen supply in the engine.

Carbon monoxide is a dangerous pollutant as it binds irreversibly with hemoglobin in blood by forming
a stable complex and reduces the capacity of hemoglobin to transport oxygen. This causes drowsiness,
headaches and is fatal above 2000 ppm. Being odorless, it gives no warning of its presence.

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Unburnt hydrocarbons by themselves cause little damage, but in the presence of sunlight, they react
with oxygen, ozone and oxides of nitrogen to form photochemical smog (read Section 6.3.2 below).

6.3.2 Oxides of nitrogen

NO and NO2, collectively known as NOx, are formed inside the combustion chambers of motor vehicles.
At the high temperature of combustion, atmospheric nitrogen and oxygen combine to form NO which
is further oxidised to NO2.
N2(g) + O2(g) → 2NO(g)
2NO(g) + O2(g) → 2NO2(g)

Oxides of nitrogen irritate lungs, cause bronchitis and pneumonia and lower resistance to respiratory
infections. They often result in the formation of photochemical smog where the strong sunlight
interacts with pollutant gas causing a complex series of photochemical reactions which produce a
choking mixture of ozone, NOx and other gases. Photochemical smog has a harmful effect on plants.
It may also result in chest pains and breathing difficulties in children.

NO2 dissolves in water to give a mixture of nitrous (HNO2) and nitric (HNO3) acids:

2NO2(g) + H2O(l) → HNO2(aq) + HNO3(aq)

NO2 also catalyses the formation of SO3 from SO2. SO3 then dissolves in water to form H2SO4.

SO2(g) + NO2(g) → SO3(g) + NO(g)

HNO3 and H2SO4 are strongly acidic. When they are present in rainwater, they produce acid rain. Acid
rain renders farm land unsuitable for cultivation (due to the acidity of the soil), causes corrosion of
buildings and other man–made structures, and adversely affects marine lives (due to increased acidity
of water). In addition, NO2 can be easily regenerated by atmospheric oxygen:

NO(g) + ½ O2(g) → NO2(g)

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6.3.3 Catalytic converter

Typical location of catalytic converter

Figure 5. Expanded view of a catalytic converter

A catalytic converter removes pollutant gases from the exhaust by oxidising or reducing them. The
exhaust gases pass through a converter containing an alloy of platinum or rhodium. The mechanism
of the reaction is that of a heterogeneous catalyst reaction (recall Topic 6 Reaction Kinetics for the
mechanism). The harmful gases are adsorbed onto the surface on the metals, go through a reaction
and then the harmless gas products desorb from the surface.

Three main pollutants (CO, NOx and unburnt hydrocarbons) are removed from exhaust gases by the
catalytic converter. According to the following equations, these harmful gases are converted into less
harmful CO2, N2 and water vapour.

2NO(g) + 2CO(g) → N2(g) + 2CO2(g)

2CO(g) + O2(g) →2CO2(g)

However, catalytic converters only work with unleaded petrol because lead ‘poisons’ the catalyst in
the converter (i.e. destroy their catalytic action).

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Exercise 6.1 (Includes Worked Example)

1. How are oxides of nitrogen formed in a car engine?

A oxidation of nitrogen by ethanol in petrol
B reaction of nitrogen with oxygen
C oxidation of nitrogen by carbon dioxide
D reaction of nitrogen compounds in petrol with oxygen [N2001/III/19]

2. Worked example
The three-way catalytic systems which are fitted to the exhaust systems of cars remove nitrogen
oxides, carbon monoxide and unburnt hydrocarbons. Oxidation and reduction are both involved.
(a) State whether the catalysis is homogeneous or heterogeneous.
(b) What reaction or reactions are catalysed by the reduction catalyst?
(c) What reaction or reactions are catalysed by the oxidation catalyst?
(d) Name a substance which poisons the catalyst and suggest a remedy for this poisoning.

Answer
(a) Heterogeneous catalysis. The nitrogen oxides, carbon monoxide and unburnt hydrocarbons
are in the gaseous state while the catalyst is in the solid state.
(b) 2NO(g) + 2CO(g) → N2(g) + 2CO2(g)
NO(g) is reduced to N2(g).
(c) 2CO(g) + O2(g) → 2CO2(g)
 y y
CxHy(g) +  x +  O2(g) → xCO2(g) + H2O(g)
 4 2
CO(g) and the unburnt hydrocarbons CxHy(g) are oxidised to CO2(g).
(d) Lead poisons the catalyst. Use unleaded petrol instead to remedy this poisoning.

6.3.4 Enhanced greenhouse effect

LO 11.3(n)(part): recognise the environmental consequence of: (ii) gases that contribute to the enhanced greenhouse effect

The "greenhouse effect" is the heating of the Earth due to the presence of greenhouse gases. It is
named this way because of a similar effect produced by the glass panes of a greenhouse. Increase in
the amount of greenhouse gases in the Earth's atmosphere enhances the greenhouse effect.

As concentration of greenhouse gases increases, there will be a greater proportion of radiation

trapped in the atmosphere, resulting in an increase in global temperatures.

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Figure 6. Illustration of greenhouse effect

What are greenhouse gases? http://www.ncdc.noaa.gov/oa/climate/gases.html

Many chemical compounds present in Earth's atmosphere behave as 'greenhouse gases'. These are
gases which allow direct sunlight (relative shortwave energy) to reach the Earth's surface
unobstructed. As the shortwave energy (that is in the visible and ultraviolet portion of the spectra)
heats the surface, longer–wave (infrared) energy (heat) is re–radiated to the atmosphere. Greenhouse
gases absorb this energy, thereby allowing less heat to escape back to space, and 'trapping' it in the
lower atmosphere.

Many greenhouse gases occur naturally in the atmosphere, such as carbon dioxide, methane, water
vapour, and nitrous oxide, while others are synthetic. Those that are man–made include the
chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs) and perfluorocarbons (PFCs), as well as sulfur
hexafluoride (SF6). Atmospheric concentrations of both the natural and man–made gases have been
rising over the last few centuries due to the industrial revolution. As the global population has
increased and our reliance on fossil fuels (such as coal, oil and natural gas) has been firmly solidified,
so emissions of these gases have risen. While gases such as carbon dioxide occur naturally in the
atmosphere, through our interference with the carbon cycle (through burning forest lands, or mining
and burning coal), we artificially move carbon from solid storage to its gaseous state, thereby
increasing atmospheric concentrations, making carbon dioxide a major greenhouse gas.

Figure 7. U.S. greenhouse gas emissions by gas, 2009

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6.3.5 Impact of Methane on the Environment

Methane is one of literally millions of compounds in the carbon cycle, but one of the most abundant.
It is formed when carbon-containing compounds decompose in the absence of air (anaerobic
conditions). The organisms that bring this about are called methanogens. Each year an estimated
5 × 1014 g of biologically produced methane is released into the atmosphere. This vast amounts of
methane produced in the biosphere have been touted as a renewable, carbon neutral energy source.
However, this also carries particular significance to the global climate because methane is a highly
potent greenhouse gas, with a greenhouse factor 30. Although present at much lower
concentrations in the atmosphere than CO2, methane currently accounts for 20% of the radiative
forcing of all greenhouse gases.

Exercise 6.2 (Worked Example)

Methane is burnt in power plants to produce heat which is used to generate electricity. This process
produces an exhaust gas which contains CO2(g), CO(g), steam and nitrogen oxides, (NOx(g)). When
CO2(g) is released into the atmosphere it causes an enhanced greenhouse effect.

(a) Describe what is meant by the term enhanced greenhouse effect.

(b) Name one environmental consequence which occurs when nitrogen oxides are released into
the atmosphere. Ignore the effect of nitrogen oxides on human health.
[N2022/II/6(a),(b)]

Answer
(a) It refers to the increased temperatures on Earth’s surface due to release of greenhouse gases
from human activities, in addition to the natural greenhouse effect Earth has.
(b) Acid rain (which makes farm land unsuitable for cultivation / affects marine life).
Note: The question states to ignore effect on human health, so formation of photochemical
smog which causes breathing difficulties is not the answer here.

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11 Alkenes

GUIDING QUESTIONS
• Which classes of reagents does alkenes react with and why? What types of reactions do alkenes
undergo and why?
• How do alkenes react with electrophiles?
• What is the major product obtained when an unsymmetrical alkene reacts with hydrogen halide
and why?

LEARNING OUTCOMES
Students should be able to:
11.3(d) explain the general reactivity of alkenes towards electrophilic reagents/electrophile
11.3(e) describe the chemistry of alkenes as exemplified, where relevant, by the following reactions
of ethene:
(i) electrophilic addition of water/steam, hydrogen halides and halogens
(ii) reduction via catalytic hydrogenation (catalytic addition of hydrogen)
(iii) oxidation by cold, alkaline solution of manganate(VII) ions to form the diol
(iv) oxidation by hot, acidified solution of 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
11.3(f) describe the mechanism of electrophilic addition in alkenes, using bromine/ethene as an
example
11.3(g) apply Markonikov’s rule to the addition of hydrogen halides to unsymmetrical alkenes and
explain the composition of products in terms of the stability of carbocation intermediates

REFERENCES
1. L. G. Wade, Jr (2012), Organic Chemistry, 8th Ed., Chapters 7 and 8.
2. Cann & Hughes (2015), Chemistry, Chapter 24.
3. J. McMurry (2010), Organic Chemistry, 8th Ed., Chapter 6 and 7.

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1 INTRODUCTION

Alkenes are unsaturated hydrocarbons that contain at least one carbon-carbon double bond, C=C.
Alkenes are said to be unsaturated because they have fewer than the maximum possible number of
hydrogen atoms.

Alkenes occur abundantly in nature. Examples include:

• ethene, a gas responsible for the ripening of fruits;
• -pinene, a major component of turpentine which is commonly used as paint solvent;
• cholesterol, a precursor for the synthesis of steroid hormones and vitamin D;
• -carotene, the orange pigment responsible for the colour of carrots.

H H H

C C
H H
H H
HO
ethene -pinene cholesterol

-carotene

1.1 Nomenclature

Aliphatic alkenes containing only one carbon-carbon double bond have the general formula CnH2n,
where n is the number of carbon atoms in the molecule. Do note that this general formula is not
applicable for aliphatic alkenes containing more than one carbon-carbon double bond and alicyclic
alkenes.
n Name Molecular Formula Structural Formula

2 Ethene C2H4

3 Propene C3H6

4 But-1-ene C4H8

Table 1. Table showing some examples of alkenes

The number “1” in but-1-ene is used because the carbon-carbon double bond is on C1 and C2. What
do you think is the structure of but-2-ene?

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The IUPAC rules for naming alkenes are similar to those for alkanes.

1. Find the longest parent chain containing the double bond and name the compound accordingly
using the suffix -ene.

2. Number the double bond from the end of the chain nearest to the double bond. If the double
bond is equidistant from the two ends, begin at the end nearer the first branch point. The number,
followed by a hyphen, precedes the name of the parent chain.

CH3CH2CH=CH2 CH3CH2CH2CH=CHCH3 CH3CH(CH3)CH=CHCH2CH3

but-1-ene hex-2-ene 2-methylhex-3-ene

3. Number the substituents according to their position in the chain and list them alphabetically.

4. If more than one double bond is present, indicate the position of each and use the suffixes -diene,
-triene, -tetraene, and so on.

CH3CH2CH=CHCH=CH2 CH2=C(CH3)CH=CHCH3 (CH3)2C=CHCH(CH3)CH=CHCH=CH2

hexa-1,3-diene 2-methylpenta-1,3-diene 5,7-dimethylocta-1,3,6-triene

5. Stereochemical descriptors, such as cis and trans, are placed in front of the prefix, followed by a
hyphen.

trans-hexa-1,3-diene cis-hexa-1,3-diene trans-5,7-dimethylocta-1,3,6-triene

Note: When drawing the stereochemical formula of cis-trans isomers, the geometry around each
carbon of the C=C bond should be shown to be trigonal planar.

6. Cycloalkenes are named in a similar way. Number the cycloalkene so that the double bond is
between C1 and C2 and the first substituent has as low a number as possible.

3-methylcyclohexene cyclohexa-1,4-diene 3,5-dimethylcyclopentene

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Exercise 1.1 (Worked Example)

Draw the structural formulae of
(a) 2,3-dimethylocta-1,4,6-triene
(b) 2-ethyl-3-methylcyclohepta-1,4-diene.

Answer:

(a)
After drawing the main carbon chain with 8 carbon atoms, insert C=C between carbons 1 and 2, 4 and
5, as well as 6 and 7. Add the two dimethyl carbons on carbon 2 and carbon 3 as the last step.

(b)
A 7 membered ring must be established first before inserting C=C between carbons 1 and 2, as well as
4 and 5 on the ring. Add one ethyl group on carbon 2 and one methyl group on carbon 3 as stated by
the locants.

1.2 Electronic structure of ethene

In Topic 2 Chemical Bonding, you have learnt the hybridisation, shape and bonding of ethene.

• The ethene molecule is trigonal planar with respect to each carbon atom.

• The carbon-carbon double bond in ethene is made up of one σ bond and one  bond. The carbons
are sp2-hybridised and have three equivalent sp2 hybrid orbitals that lie in a plane at angles of 120°
to one another. The carbons form a σ bond with each other by head-on overlap of sp2 orbitals, as
well as a  bond by side-on overlap of unhybridised p orbitals orientated perpendicular to the sp2
plane. The -electron cloud lies above and below the plane of the atoms.

• The C-H bonds are σ bonds formed by head-on overlap of sp2 orbital of C and s orbital of H.

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1.3 Cis-trans isomerism in alkenes

In Topic 9 Isomerism, you have learnt that cis-trans isomerism arises in alkenes due to restricted
rotation about the C=C bond and 2 different groups attached to each C=C carbon atom.

But-2-ene can exist as cis-but-2-ene and trans-but-2-ene as shown below. Cis-but-2-ene has the same
groups on the same side of the double bond, whereas trans-but-2-ene has the same groups on the
opposite sides of the double bond.

Cis-trans isomerism cannot exist if any one of the C=C carbons carries two identical groups.
2-methylpropene is an example of a constitutional isomer of cis-but-2-ene and trans-but-2-ene.

Cycloalkenes with up to 7 carbon atoms exist only as the “cis isomers”. Cycloalkenes with 8 or more
carbon atoms can exist as cis-trans isomers.

Exercise 1.2 (Worked Example)

Draw the cis-trans isomers of (Cl)CH=C(CH3)Br.
Answer:
The shape and bond angles of 120° of sp2 hybridised
carbon atoms of alkene must be clearly shown in your
drawing. In your syllabus, there is no need to assign
which is the cis or trans isomer for alkenes with no same
groups on each C of C=C.

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2 PHYSICAL PROPERTIES OF ALKENES

2.1 Boiling and melting points within the homologous series

The trend in the boiling and melting points within the homologous series indicate that as the number
of carbon atoms increases, the boiling points increase correspondingly. This is due to the increase in
number of electrons and hence the size of the electron cloud, leading to stronger dispersion forces
between the molecules.

The trend in melting points is not as clear as the trend in boiling points as melting point also depends
on how the molecules are packed in the solid lattice.

Boiling point (oC) Melting point (oC)

Ethene –104 –169

Propene –47 –185

But-1-ene –6 –138
Pent-1-ene 30 –165
Table 2. Boiling and melting points of a few alkenes.

2.2 Physical properties of cis-trans isomers

Boiling point of cis-trans isomers

There can be differences in the boiling and melting points between the cis and trans isomers of alkenes
e.g. 1,2-dichloroethene

Isomer Boiling point (oC) Melting point (oC)

cis-1,2-dichloroethene 60.3 –81

trans-1,2-dichloroethene 47.5 –50

Table 3. Boiling and melting points of cis- and trans- isomers of 1,2-dichloroethene

You will notice that:

• the cis-isomer has the higher boiling point;
• the trans-isomer has the higher melting point.

Between the cis and the trans isomer of disubstituted alkenes, the cis isomer tend to have higher
boiling points. The reason for this is that cis isomers tend to be more polar. We shall use
1,2-dichloroethene as an example below:
• In the cis isomer, the polar C–Cl bonds result in dipole moments that do not cancel out, hence
producing an overall dipole moment for the molecule. Thus, the cis isomer is polar and permanent
dipole-permanent dipole interactions (on top of dispersion forces) exist between molecules.

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• In the trans isomer, the two dipole moments cancel out such that the overall dipole moment for
the molecule is zero. Hence, the trans isomer is non-polar and only dispersion forces exist between
molecules.
• Hence, more energy is required to overcome the stronger forces of attraction between cis isomers,
leading to a higher boiling point.

This effect is less noticeable for some alkenes, for example:

Isomer Boiling Point (oC)

cis-but-2-ene 4
trans-but-2-ene 1
cis-pent-2-ene 37
trans-pent-2-ene 36
Table 4. Table showing the boiling points of some cis-trans isomers

Their similar boiling points can be understood from the fact that both isomers (in the case of cis-but-
2-ene and trans-but-2-ene) contain the methyl group as a substituent and this is a relatively non-polar
group such that the cis isomer is not much more polar than the trans isomer. The same reasoning can
be applied to cis-pent-2-ene and trans-pent-2-ene.

Exercise 2.1 (Worked Example)

Which of the following compounds has the highest boiling point?

A B

C D

Answer: C
C-H bonds are generally considered non-polar due to small difference in electronegativity between the
two atoms. Since D is a trans isomer, there is no net dipole moment. Being a cis isomer with polar
C-Cl bond, C has a net dipole moment and permanent dipole-permanent dipole interactions between
molecules, in addition to dispersion forces. Hence, C has the highest boiling point.

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Melting point of cis-trans isomers

Between the cis and the trans isomer of alkenes, the trans isomer tend to have higher melting point.

In order for the intermolecular forces of attraction to work well in a solid, the molecules must be able
to pack together efficiently in the solid state.

• The trans isomer pack better than the cis isomer due to the higher symmetry of the trans isomer.
The “U” shape of the cis isomer does not pack well compared to the straighter shape of the trans
isomer.
• The better packing of the trans isomer in the solid state means that the dispersion forces work
more effectively in holding the molecules together when compared to the cis isomer.
• Hence more energy is required to overcome the forces of attraction between trans isomer, leading
to a higher melting point.

cis trans

2.3 Solubility

In order for dissolution to occur, the solute molecules and the solvent molecules should have
favourable intermolecular forces of attraction.

Non-substituted alkenes can form favourable dispersion forces with non-polar solvents such as
benzene and tetrachloromethane. Hence they are soluble in non-polar solvents.

Non-substituted alkenes can only form permanent dipole-induced dipole intermolecular forces with
water, which are much weaker than the hydrogen bonding between water molecules themselves (as
well as the dispersion forces between non-substituted alkene molecules). Hence they are insoluble in
water.

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2.4 Density

Liquid alkenes are less dense than water and form an immiscible layer above water.

Their densities increase slightly with increasing number of carbon atoms present. This is because the
increase in the strength of intermolecular dispersion forces causes the alkene molecules to attract
more closely together, resulting in a slightly smaller volume of the liquid. Since ρ = m/V, with a larger
relative molecular mass, the density of the liquid increases.

2.5 Viscosity

The viscosity of liquid alkenes increases with increasing number of carbon atoms present as the
strength of dispersion forces between the molecules increases. In addition, straight-chain alkenes
have higher viscosity as compared to branched alkenes.

3 PREPARATION OF ALKENES

Alkenes can be prepared by the following reactions:

• Elimination of hydrogen halide from halogenoalkanes (to be covered in Topic 15 Halogen

Derivatives)

• Dehydration of alcohol (to be covered in Topic 16 Hydroxy Compounds)

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4 REACTIONS OF ALKENES

Reactivity of alkenes towards electrophilic reagents

LO11.3(d): explain the general reactivity of alkenes towards electrophilic reagents/electrophile

Even though C=C bond is stronger than C–C bond, alkenes are more reactive than alkanes. This is due
to the electron-rich C=C. The  bond (electron cloud), which lies on the surface of the molecules,
attracts electrophiles.

During reaction, the weaker  bond is broken instead of the σ bond in the C=C bond. In place, two
strong bonds (C–A and C–B) are formed in the product, leaving the carbon atoms joined by a single
bond. This typical reaction of alkenes is known as electrophilic addition.

The overall reaction for electrophilic addition of alkenes can be represented as:

Examples of electrophiles that react with alkenes include hydrogen halides and halogens.

4.1 Electrophilic addition

4.1.1 General mechanism of electrophilic addition

Step 1: Initial attack by the  electrons of the C=C bond on the electrophile, forming a positively-
charged carbocation intermediate.

Step 2: Subsequent attack of the unstable carbocation intermediate by nucleophile to generate a

stable product.

4.1.2 Carbocation intermediate

In electrophilic addition to alkenes, the carbocation is an important intermediate. Before studying the
reactions of alkenes, we need to learn more about the structure and factors affecting the stability of
carbocations.

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Structure

The central carbon atom is positively charged and sp2 hybridised. The 3 substituents are arranged in a
trigonal planar geometry around the central carbon atom. As the carbon atom has lost an electron,
the unhybridised p orbital is empty.

Due to the positive charge on the carbon atom, the carbon atom is electron-deficient and strongly
attracts any nucleophile towards it. And because the geometry around the carbon atom is planar, the
nucleophiles may attack from either side of the plane.

Stability

In general, organic species with a charge on it are less stable. Therefore, anything that disperses the
charge would stabilise the species as a whole. Conversely, anything that intensifies the charge on it
would destabilise it.

As mentioned earlier, the central carbon atom of the carbocation is positively charged. The 3
substituents bonded to it can affect the stability of the carbocation as a whole depending on whether
they are electron donating or electron withdrawing.

Alkyl groups e.g. methyl (-CH3) are considered electron donating groups. Therefore, the more alkyl
substituents the carbocation has, the more stable it would be, as the electron donating groups
disperse the positive charge on the central carbon atom.

Conversely, electron withdrawing substituents like halogens would destabilise the carbocation as
they intensify the positive charge on the central carbon atom.

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4.1.3 Electrophilic addition of hydrogen halides (H-X)

LO11.3(e)(part): describe the chemistry of alkenes as exemplified, where relevant, by the following reactions of ethene:
(i) electrophilic addition of water/steam, hydrogen halides and halogens

Reagents and conditions: Gaseous HCl, HBr or HI, room temperature

The general reaction mechanism of electrophilic addition applied to the reaction between ethene and
HBr is illustrated as follows:

• This is the rate-determining step (involves breaking of the  bond).

• As the polar HBr molecule approaches the  electron cloud of ethene in the correct orientation,
the high electron density of the  electron cloud “attacks” the electron deficient H atom on the
HBr molecule. (*Note: arrow must show the direction of electron movement.)

• The  bond in the C=C bond breaks, forming a new C–H bond. The H–Br bond undergoes heterolytic
fission producing a carbocation intermediate and a bromide ion.

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• In the next step, the bromide anion acts as a nucleophile and attacks the unstable carbocation
intermediate quickly as the negatively charged bromide ion is attracted to the positively charged
carbon, forming a new C–Br bond. A stable product, bromoethane is formed.

The energy profile diagram of the electrophilic addition of hydrogen halide to ethene is as follows:
Energy/kJ mol-1

Ea,1
Ea,2

∆H

progress of reaction
Exercise 4.1 (Worked Example)
Hydrogen bromide reacts with ethene to form bromoethane. What is the best description of the
organic intermediate in this reaction?

A It contains carbon, hydrogen and bromine.

B It has a negative charge.
C It is an electrophile.
D It is a free radical. N97/III/Q23

Answer: C
The organic intermediate formed is a carbocation. It is an electrophile because it has 6 electrons
around the carbon atom, which is electron deficient.

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Addition to an unsymmetrical alkene

LO11.3(g): apply Markonikov’s rule to the addition of hydrogen halides to unsymmetrical alkenes and explain the composition
of products in terms of the stability of carbocation intermediates

When a hydrogen halide adds across the double bond of an unsymmetrical alkene, there are two
possible products. One of them is preferred over the other. Why is this so?

(unsymmetrical alkene) (major product) (minor product)

To explain this observation, we need to look at the 2 possible intermediates that generate each
product.

Markovnikov's rule

The Markovnikov’s rule states that in the addition of HX to an alkene, the H atom adds to the C atom
of the double bond that holds the greater number of H atoms. Reactions that follow this rule are said
to follow Markovnikov orientation and give the Markovnikov product.

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This observation is due to the stability of the carbocation intermediate formed. Since alkyl groups are
electron-donating, they tend to disperse the positive charge on a cation, and thus stabilise it. The

secondary carbocation is more stable than as the secondary

carbocation has 2 electron-donating groups while the primary carbocation only has one. The more
stable the carbocation, the lower the energy of the transition state that precedes it.

In an electrophilic addition to an alkene, the electrophile adds in such a way so as to generate the
most stable carbocation intermediate. In short, in an electrophilic addition to an alkene, the
electrophile adds to the less-substituted end of the double bond to give the more substituted (and
therefore more stable) carbocation.

However, we are often interested in adding electrophiles other than H to the double bonds of alkenes.
Markovnikov's rule can be extended to include a variety of other additions, based on the addition of
the electrophile in such a way as to produce the most stable carbocation.

Exercise 4.2 (Worked Example)

Identify the major product of the following reaction:

Answer:
There are two possible carbocations that can be formed:

The carbocation on the left will be formed more preferably because there are
three electron-donating alkyl groups attached to the electron deficient carbon.
Thus, the major product will be formed from the more stable carbocation.

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Formation of a racemic mixture

When a hydrogen halide adds across the double bond of an alkene that produces an intermediate
carbocation with 3 different groups attached to it, it produces equal amounts of 2 enantiomers,
forming a racemic mixture.

This occurs because the geometry about the positively charged carbon is planar, hence it has equal
chances of being attacked from the top or bottom by the bromide ion in the second step, thereby
producing the two enantiomers in equimolar ratio.

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4.1.4 Electrophilic addition of halogens (X2)

LO11.3(e)(part): describe the chemistry of alkenes as exemplified, where relevant, by the following reactions of ethene:
(i) electrophilic addition of water/steam, hydrogen halides and halogens
LO11.3(f): describe the mechanism of electrophilic addition in alkenes, using bromine/ethene as an example

Alkenes also readily react with chlorine or bromine to form halogenoalkanes with two atoms of
halogens attached to adjacent carbon atoms. The reaction with fluorine is very violent while iodine
does not react with most alkenes.

Reagents and conditions: Cl2(g) / Br2(l) or Cl2 / Br2 dissolved in CCl4

Room temperature
Observations: Greenish yellow Cl2 / reddish brown Br2 decolourised

Electrophilic addition of halogens can occur in the presence of UV light but the reaction is usually
carried out in the absence of UV light to prevent free radical substitution of the alkyl substituents on
the alkene or of the product.

For the mechanism, we will use the electrophilic addition of Br2 to ethene as an example. The
mechanism takes place in two steps.

• As the non-polar Br2 molecule approaches the  electron cloud of ethene, the high electron density
of the  electron cloud polarises the electron cloud of the Br2 molecule.

• The Br-Br bond undergoes heterolytic fission resulting in a bromide anion with the other bromine
atom bonded to the alkene to form a positively charged carbocation intermediate.

• This is the rate-determining step as it involves breaking the  bond in ethene and Br-Br bond.

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• In this step, the bromide anion acts as a nucleophile to attack the carbocation intermediate to form
the product, 1,2-dibromoethane.

• This step is fast as it involves the reaction between oppositely charged species. The mutual
electrostatic attraction results in the easy formation of the stable 1,2-dibromoethane.

For your information

Although the mechanism Section 4.1.4 is reasonable and follows that of the alkene reaction with
hydrogen halides, studies have shown that it is not completely consistent with some observations.

For instance, it was observed in the reaction of bromine with cyclopentene, that only the trans product
is formed rather than an expected mixture of cis and trans products if a planar carbocation
intermediate was involved.

Hence, it was proposed that the intermediate in the mechanism was a cyclic three-membered
bromonium ion during electrophilic addition of bromine on alkene.

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This cyclic bromonium ion as an intermediate could explain the above observation because the
second step of the mechanism (shown below) will then involve an SN2 attack by bromide anion from
the opposite side of the C–Br bond to be broken. The consequence of this SN2 attack is the formation
of a trans product in which the two Br atoms are on the opposite faces of the double bond. We shall
look at SN2 mechanism in greater detail in Topic 15 Halogen Derivatives.

4.1.5 Electrophilic addition of bromine water

LO11.3(e)(part): describe the chemistry of alkenes as exemplified, where relevant, by the following reactions of ethene:
(i) electrophilic addition of water/steam, hydrogen halides and halogens

Reagents and conditions: Br2(aq), room temperature

Observations: Yellow-orange Br2(aq) decolourised (*distinguishing test)

Alkenes react with bromine water to form bromoalcohol (or bromohydrin) as the major product
instead of the dibromo compound.

This is because the carbocation intermediate is susceptible to attack by any nucleophile present in the
reaction mixture.

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In the case of bromine water, after forming the carbocation intermediate in the rate-determining step,
the carbocation intermediate can be attacked by any nucleophile in the reaction mixture. So, both
water and bromide ion can act as nucleophiles to attack the carbocation. The major product generally
depends on which nucleophile is present in excess.

Scenario 1: Nucleophilic attack by water

Scenario 2: Nucleophilic attack by bromide ion

Water is present in a much higher concentration compared to the bromide ion and therefore attacks
the intermediate preferentially in the second step of the reaction.

Exercise 4.3 (Worked Example)

Predict the products formed when propene reacts with bromine water that is contaminated by
aqueous sodium chloride. Explain why it is not possible to obtain 1,2-dichloropropane.

Answer:

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The first slow step of the reaction involves the electrophilic attack of Br2. Thus the product will
always have the addition of at least one Br atom. Also, there is no Cl+ electrophile and hence the
products cannot contain 2 Cl atoms.

Note that the only electrophile present is Br2, in the presence of propene, bromine, water and
sodium chloride.

4.1.6 Electrophilic addition of water/steam

LO11.3(e)(part): describe the chemistry of alkenes as exemplified, where relevant, by the following reactions of ethene:
(i) electrophilic addition of water/steam, hydrogen halides and halogens

Alkenes react with steam (H2O) to form alcohols. The addition of steam to alkenes is similar to that of
hydrogen halides. Phosphoric acid is added as a catalyst.

Industrial method
Reagents and conditions: steam; H3PO4 catalyst
High temperatures and high pressures
Lab method
Reagents and conditions: 1. concentrated H2SO4, cold
2. H2O

(Refer to Appendix for the mechanism)

Exercise 4.4 (Worked Example)

What alkenes would you start with to prepare the following compounds?

(a) (b)

Answer:
(a)

OR

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By eliminating a bromine atom with a hydrogen atom on an adjacent C atom and establishing a C=C
bond, two possible alkenes are possible starting reactants. Using HBr, the most stable carbocation
intermediate would be preferably formed. In either cases, they result in the tertiary carbocation as
the most stable intermediate, thus producing the compound as the major product.

(b)

Eliminate the OH group with a hydrogen atom on an adjacent C atom (not attached to methyl group)

to establish two C=C bonds as shown in the answer. Note that would give a major product

of instead as it forms a stable tertiary carbocation as the intermediate.

4.2 Reduction
LO11.3(e)(part): describe the chemistry of alkenes as exemplified, where relevant, by the following reactions of ethene:
(ii) reduction via catalytic hydrogenation (catalytic addition of hydrogen)

Reduction via catalytic hydrogenation is often used to convert unsaturated alkenes to saturated
alkanes. This process is commonly used in the food industry to produce margarine by converting
unsaturated plant oil into the saturated soft margarine.

This is a form of heterogeneous catalysis. See Topic 6 Reaction Kinetics for the mechanism.

Reagents and conditions: H2 gas; Ni catalyst

Room temperature and high pressure
Note: Platinum/Palladium catalyst at room temperature and pressure can also be used for this
reduction.

H2 gas with nickel catalyst is also able to reduce other functional groups and these reactions will be
discussed in the later organic chemistry topics.

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4.3 Oxidation

4.3.1 Mild oxidation

LO11.3(e)(part): describe the chemistry of alkenes as exemplified, where relevant, by the following reactions of ethene:
(iii) oxidation by cold, alkaline solution of manganate(VII) ions to form the diol

Cold alkaline potassium manganate(VII) can oxidise alkenes into the corresponding diols. The
formation of diols from alkenes is considered as a type of mild oxidation.

Reagents and conditions: KMnO4, dilute NaOH, cold

Observations: Purple KMnO4 is decolourised and a brown precipitate of MnO2

is formed. (*distinguishing test)

4.3.2 Oxidative cleavage

LO11.3(e)(part): describe the chemistry of alkenes as exemplified, where relevant, by the following reactions of ethene:
(iv) oxidation by hot, acidified solution of 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

Hot acidic potassium manganate(VII) can cleave the carbon-carbon double bond in alkenes to give
carbonyl compounds and/or carboxylic acids as products. This oxidative cleavage of alkenes is
considered as a type of strong oxidation.

Reagents and conditions: KMnO4, dilute H2SO4, heat

Observations: Purple KMnO4 is decolourised. Note that effervescence of
carbon dioxide is possible for selected alkenes as mentioned
below.
(*distinguishing test)

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NOTE:
• Oxidation of alkenes CANNOT be carried out with potassium dichromate(VI).

Different substituents on the C=C carbon atoms give rise to different products upon oxidative cleavage.
The table next page summarises the possible products arising from a different number of hydrogen
atoms attached directly to the C=C carbon atoms.

No. of hydrogen atoms Products after oxidative

Structure
on carbon cleavage

2 CO2 + H2O

Special case of oxidative cleavage:

The special case of oxidative cleavage illustrated above should not be surprising as you have learnt
about the redox titration of ethanedioic acid and potassium manganate(VII) under Topic 4 Reactions
and Stoichiometry (try balancing the redox equation).

Usefulness of oxidative cleavage:

• Oxidative cleavage is a useful tool to establish the location of the alkene double bond in a
hydrocarbon chain or ring.

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• Oxidative cleavage using hot acidified KMnO4 can be used as a test to distinguish between alkenes
with terminal C=C double bonds (=CH2) and those without. Alkenes with terminal C=C double
bonds would, upon oxidation, evolve carbon dioxide gas. This distinguishes between the alkenes.

Exercise 4.5 (Worked Example)

Write down the products of the following compounds undergoing oxidative cleavage.
(a) (CH3)2C=CHCH=CH2 (b)

(c) (d)

Answer:
(a) (b)

(c)

(d)

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Generic procedure for distinguishing test for alkenes

(a) Using acidified potassium manganate(VII), KMnO4

1. To prepare acidified KMnO4 solution, add 5 drops of KMnO4(aq) to 1 cm3 of dilute H2SO4 in a test
tube.

2. To 1 cm3 of the unknown, add 2 – 3 drops of the acidified KMnO4 dropwise.

3. Shake well.
4. Warm in a water bath.

(b) Using aqueous bromine (bromine water)

1. To 1 cm3 of the unknown in a test tube, add aqueous bromine dropwise.
2. Shake well.

Exercise 4.6 (Worked Example)

Refer to the above distinguishing test and answer the following questions.
(a) Why should the KMnO4 be added dropwise?
(b) Why should the aqueous Br2 be added dropwise?

Answer:
(a) If excess KMnO4 is added, the decolourisation cannot be observed. Instead, the solution will
remain purple.
(b) If excess aqueous Br2 is added, the decolourisation cannot be observed. Instead, the solution will
remain yellow-orange.

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Summary of reactions
Write the reagents and conditions needed for the conversions on the arrows below.

Ethanolic KOH
heat

Excess concentrated H2SO4

heat

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APPENDIX

Electrophilic addition of water/steam mechanism:

Using ethene as an example, the mechanism for the acid-catalysed hydration of ethene is as follows:

Step 1: Protonation of the double bond to form a carbocation.

Step 2: Nucleophilic attack by –OSO3H on carbocation to produce a hydrogensulfate.

The hydrogensulfate is then added to cold water. Water acts as a nucleophile to attack the
hydrogensulfate. The –OSO3H group is substituted with –OH group, producing the alcohol and
regenerating the sulfuric acid catalyst.

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12 Arenes

GUIDING QUESTIONS
• What determines the shape of benzene?
• How does the reactivity of benzene compare to that of alkene and why?
• Which class of reagents does benzene react with and why? What types of reactions does benzene
undergo and why? How does benzene react with an electrophile?
• What types of reactions do the alkyl side-chains of arenes undergo and why?
• How does the substituent on mono-substituted arenes determine the reactivity towards, and the
substitution position of an incoming electrophile?

LEARNING OUTCOMES
At the end of the chapter, you should be able to:
11.1(d) describe sp3 hybridisation, as in ethane molecule, sp2 hybridisation, as in ethene and
benzene molecules, and sp hybridisation, as in ethyne molecule.
11.1(e) explain the shapes of, and bond angles in, the ethane, ethene, benzene, and ethyne molecules
in relation to σ and π carbon-carbon bonds
11.1(f) predict the shapes of, and bond angles in, molecules analogous to the ethane, ethene,
benzene, and ethyne molecules
11.3(h) explain, in terms of delocalisation of π electrons, the difference between benzene and
alkene
(i) reactivity towards electrophiles
(ii) preference of benzene to undergo substitution rather than addition reaction
11.3(i) describe the chemistry of the benzene ring as exemplified by the following reactions of
benzene and methylbenzene:
(i) electrophilic substitution reactions with chlorine and with bromine
(recognise the use of Lewis acid as catalysts)
(ii) nitration with concentrated nitric acid
(recognise concentrated sulfuric acid as a Bronsted-Lowry acid catalyst)
(iii) Friedel-Crafts alkylation with halogenoalkanes
(recognise the use of Lewis acid as catalysts)
11.3(j) (i) describe the mechanism of electrophilic substitution in arenes, using the mono-
bromination of benzene as an example
(ii) describe the effect of the delocalisation of electrons in arenes in such reactions
11.3(k) describe the chemistry of the alkyl side-chain of benzene ring as exemplified by the
following reactions of methylbenzene:
(i) free-radical substitution by chlorine and by bromine
(ii) complete oxidation to give benzoic acid
11.3(l) predict whether halogenation will occur in the side-chain or aromatic nucleus in arenes
depending on reaction conditions
11.3(m) apply the knowledge of positions of substitution in the electrophilic substitution reactions
of mono-substituted arenes

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REFERENCES

1. P. Cann & P. Hughes (2015), Chemistry, Chapter 25.

2. J. McMurry (2010), Organic Chemistry, Chapters 15-16.
3. M. B. Smith, J. March (2007), March’s Advanced Organic Chemistry, Chapter 19.

1 INTRODUCTION (Background info)

Arenes are aromatic hydrocarbons that contain one or more benzene rings. The name “aromatic”
originally referred to certain compounds that possessed pleasant smells, such as benzaldehyde (from
cherries, peaches and almonds) and methylbenzene (from Tolu balsam). As chemists discovered more
aromatic hydrocarbons, they found that other members of the group possess unpleasant smells and
are extremely carcinogenic. Today, aromaticity is used to describe the extra stability of benzene and
its structural relatives due to the delocalisation of electrons.

Figure 1. Examples of aromatic compounds.

Many compounds from natural sources as well as many synthetic drugs are aromatic in part. Similarly,
each of the three aromatic amino acids phenylalanine, tryptophan, and tyrosine, also serve as the
basic building blocks of proteins.

Figure 2. Examples of compounds containing aromatic rings.

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1.1 Nomenclature
LO 11.1(a)(i)part: interpret, and use the nomenclature of hydrocarbons (alkanes, alkenes and arenes)

1.1.1 Benzene

Benzene has a molecular formula of C6H6. The benzene ring is often represented using the skeletal
formula as shown below.

1.1.2 Mono-substituted benzenes

When one H atom of benzene is replaced by another atom or group of atoms comprising 6 carbon
atoms or less, the benzene ring is considered the parent and a suffix – benzene is employed in naming.

Some mono-substituted benzenes are more common such that their conventional names are used
instead.

When the substituent is an alkyl group of more than 6 carbon atoms, or when it is too complex to be
named conveniently as a prefix, benzene is considered as a substituent and named as a prefix – phenyl.

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1.1.3 Multi-substituted benzenes

Multi-substituted benzenes are named by numbering the position of each substituent so that the
lowest possible numbers are used.

E.g.

If the substituents are different, one of them is deemed the principal functional group (at position 1),
in the order of precedence –CO2H > –OH > –CH3 > –halogen > –NO2. The rest of the substituents are
named in alphabetical order.

Exercise 1.1 (Worked Example)

Draw the structure for each of the following compounds:
a) 4-bromo-2-nitromethylbenzene b) 3-methyl-2-phenylpentane

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2 PHYSICAL PROPERTIES AND USES OF BENZENE

Physical properties

Benzene is a colourless liquid at rtp. It is toxic and carcinogenic and should therefore be handled
cautiously if used in the laboratory. It is highly volatile and flammable.

Melting and boiling points

Melting point: 5.5 oC; boiling point: 80 oC

Being a non-polar molecule, only a small amount of energy is required to overcome the weak
dispersion forces between molecules; hence benzene has low melting and boiling points.

Solubility

Being a non-polar molecule, benzene is insoluble in (or immiscible with) polar solvents (e.g. water),
but soluble in non-polar solvents (e.g. hexane, CCl4). It could be used as a non-polar solvent.

Uses

Prior to the 1920's, benzene was frequently used as an industrial solvent, especially for degreasing
metal. As its toxicity became obvious, other solvents such as methylbenzene replaced benzene in most
applications. By far, the largest use of benzene is as an intermediate to make other chemicals. The
most widely produced derivatives of benzene are styrene (phenylethene), which is used to make
polymers and plastics, phenol for resins and adhesives (via cumene i.e. isopropylbenzene), and
cyclohexane, which is used in the manufacture of nylon.

Health effects

The major effect of benzene from chronic (long term) exposure is to the blood. Benzene causes
harmful effects on the bone marrow and can cause a decrease in red blood cells leading to anaemia.
Benzene is a known carcinogen to human beings. Long-term exposure to high levels of benzene in the
air can cause leukaemia, cancer of the blood-forming organs.

Exercise 2.1 (Worked Example)

a) Explain the difference in the boiling point of phenol, (bp 182 °C) with that of benzene,

(bp 80 °C).

b) Explain, in terms of intermolecular forces and energy, why benzene is insoluble in water. (You may
refer to Topic 2 Chemical Bonding for the discussion on solubility.)

(a) Phenol has stronger intermolecular hydrogen bonding (on top of dispersion forces) while benzene
has weaker dispersion forces between the molecules.
More energy is needed to overcome the stronger intermolecular hydrogen bonding in phenol,
resulting in a higher boiling point.

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(b) The energy released from the weaker permanent dipole-induced dipole interactions between
water and benzene molecules is not sufficient to overcome the stronger hydrogen bonding between
water molecules, and dispersion forces between benzene molecules.

3 BENZENE

3.1 Structure of benzene

LO 11.1(d)part: describe sp2 hybridisation, as in benzene
LO 11.1(e)part: explain the shapes of, and bond angles in benzene in relation to  and π carbon-carbon bonds
LO 11.1(f)part: predict the shapes of, and bond angles in, molecules analogous to benzene

In benzene, each carbon is bonded to two other carbons and one hydrogen. The geometry around
each carbon atom in benzene is trigonal planar with C–C–C bond angle of 120°. Recall from Topic 2
Chemical Bonding where you learnt about the hybridisation of atomic orbitals. Each carbon atom in
benzene is sp2 hybridised. The mixing of one s orbital and two p orbitals gives three sp2 hybrid orbitals
oriented at 120 to one another for each carbon atom. One p orbital remains unhybridised, and this p
orbital is arranged perpendicular to the three sp2 hybrid orbitals as shown in Figure 3.

Figure 3. Arrangement of sp2 hybrid orbitals and unhybridised p orbital around each carbon in benzene.

Overall, there are six C-C sigma () bonds in benzene, each of which is formed from the head-on
overlap of one sp2 hybrid orbital of one carbon atom with one sp2 hybrid orbital of the adjacent carbon
atom. There are also six C-H single bonds, each of which is an s–sp2  bond formed from head-on
overlap of the 1s atomic orbital of H and the sp2 hybrid orbital of C.

Figure 4. σ bonds between two carbon atoms and between carbon and hydrogen atoms in benzene.

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The remaining unhybridised p orbitals of the six carbon atoms are all parallel to one another due to
the planarity of the benzene molecule. These p orbitals could overlap side-on as shown in Figure 5a to
produce three  bonds between atoms 1 and 2, 3 and 4 and 5 and 6 of the ring, or just as likely, overlap
as shown in Figure 5b to produce  bonds between atoms 2 and 3, 4 and 5 and 6 and 1 of the ring. In
reality, all six unhybridised p orbitals overlap side-on with each other equally to produce two
continuous rings of π electrons above and below the plane of the benzene ring, known as the
delocalised π electron cloud, as shown in Figure 5c. The six electrons found in this delocalised π
electron cloud are free to move throughout the entire π electron cloud, so the electrons are said to
be delocalised.

Figure 5. (a) and (b) Alternative views of bonding between carbon pairs in benzene. (c) The delocalised bonding in benzene.

3.2 Implications of  electron cloud delocalisation

The delocalised π electron cloud is responsible for the following physical and chemical properties of
benzene:
i. It causes all carbon-carbon bond lengths to be equal, creating a planar, regular hexagonal
shape.
ii. It prevents benzene from undergoing any of the typical addition reactions that alkenes show.

i. Carbon-carbon bond lengths and bond energies in benzene

Instead of three C=C double bonds and three C-C single bonds, X-ray measurements showed that all
six carbon-carbon bonds of benzene are identical in length and intermediate between a C-C single
bond length and a C=C double bond length. The carbon-carbon bond energy in benzene is also
between that of a C-C single bond and a C=C double bond. (Note: When quoting the carbon-carbon

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bond energy for benzene from the Data Booklet, do refer to the specific bond energy between carbon
atoms for benzene.)

carbon-carbon bond bond length / nm bond energy / kJ mol−1

C–C bond 0.154 350
carbon-carbon bond in benzene 0.139 520
C=C bond 0.134 610
Table 1. Different types of carbon-carbon bond lengths and bond energies.

ii. Difference in reactivities of benzene versus alkenes

LO11.3(h): explain, in terms of delocalisation of π electrons, the difference between benzene and alkene: (i) reactivity towards
electrophiles, (ii) preference of benzene to undergo substitution rather than addition reaction

Similar to electron-rich alkenes, the π electron cloud in benzene attracts electrophiles (electron-
deficient species). However, the delocalisation of electrons in the π electron cloud in benzene results
in extra stability of benzene (which is also known as resonance-stabilisation). As a result, the π
electron cloud in benzene is less susceptible to attack by electrophiles compared to the C=C double
bonds in alkenes. Hence, benzene requires stronger electrophiles to react as compared to alkenes. In
addition, benzene undergoes electrophilic substitution rather than electrophilic addition reactions
because electrophilic addition destroys the delocalised  electron cloud and this requires a significant
amount of energy, which is highly unfavourable. Benzene preferentially undergoes electrophilic
substitution reactions (where one or more hydrogen atoms is substituted by electrophiles) which
preserve its aromaticity.

The following shows an example of the electrophilic addition in alkenes, and the electrophilic
substitution in arenes. While electrophilic addition of cyclohexene using liquid bromine can be carried
out at room temperature and without a catalyst, electrophilic substitution of benzene with liquid
bromine requires warming, and FeBr3 as a Lewis acid catalyst to generate strong electrophile Br+ (to
be discussed in Section 4.2).

rt FeBr3 (s) Br
absence of UV Br warm
+ Br2 (l) + Br2 (l) + HBr (g)
electrophilic addition Br electrophilic substitution

The stabilisation energy of benzene (Application example)

We can get a quantitative idea of benzene’s stability from the comparison of various enthalpy change
of hydrogenation. The experimentally determined enthalpy change of hydrogenation of cyclohexene
is −118 kJ mol–1. The experimentally determined enthalpy change of hydrogenation of
cyclohexa-1,4-diene is −232 kJ mol–1, which is approximately twice of the experimentally determined
enthalpy change of hydrogenation of cyclohexene. Hence the theoretical prediction for benzene’s
enthalpy change of hydrogenation, based on the model of 3 alternating C–C and C=C bonds (i.e.
hypothetical cyclohexatriene), is –354 kJ mol–1 (−118 kJ mol–1 × 3). However, the experimentally
determined enthalpy change of hydrogenation of benzene was found to be –205 kJ mol–1. Hence,
benzene is estimated to be more stable than the hypothetical cyclohexatriene by about 354 – 205 =
149 kJ mol–1. The difference of 149 kJ mol–1 is known as the stabilisation energy.

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Figure 6. Energy level diagram for hydrogenation of cyclohexene, cyclohexa-1,4-diene, the hypothetical cyclohexatriene and
actual benzene.

Exercise 3.1 (Worked Examples)

(a) Consider cyclohexane, cyclohexene and methylbenzene, is methylbenzene the only
compound that contains sp2 hybridised carbon atoms? Explain your answer.
[Modified from PromoHCI09/I/16]

(b) Which property does benzene have as a consequence of the delocalised electrons present
in the molecule?
A. It is a good conductor of electricity.
B. It is susceptible to attack by nucleophilic reagents.
C. Addition reactions of benzene take place more readily than substitution.
D. The carbon-carbon bond length is between that of a C‒C bond and a C=C bond.
[PromoHCI09/I/19]

(c) Naphthalene is an aromatic compound with the following structure.

(i) How many π electrons does naphthalene have?

(ii) Is naphthalene a planar molecule? Explain your answer.
(iii) Draw all the hydrogen atoms on naphthalene.
[Modified from PrelimRI12/I/21]

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(a) No. Both cyclohexene and methylbenzene contain sp2 hybridised carbon atoms.

(b) Answer: D (Refer to Section 3.2); Teaching solutions: Benzene does not conduct electricity
(The delocalised  electrons in benzene is “localised” in the  electron cloud within each
benzene molecule, they are not free to move as charge carriers). Electron-rich benzene
reacts with electrophiles (electron-deficient species), and not with nucleophiles (electron-
rich species). Benzene undergoes substitution more readily than addition.

c(i) 10 π electrons

c(ii) Yes, all carbon atoms that make up the rings are sp2 hybridised, and the geometry around
each carbon atom in napthalene is trigonal planar with C–C–C bond angle of 120°.
c(iii)

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4 REACTIONS OF BENZENE

4.1 Electrophilic substitution reaction

Aromatic compounds like benzene undergo electrophilic substitution reactions where a hydrogen
atom bonded to the benzene ring is substituted by an electrophile.

The overall reaction for an electrophilic substitution can be represented as:

Examples of electrophiles that can react with benzene include Br+, NO2+ and R+ (R = alkyl group). Unlike
alkenes, the electrophiles that react with benzene are all positively charged, with a strong electron-
attracting tendency.

4.1.1 General Mechanism

LO11.3(j)(i): describe the mechanism of electrophilic substitution in arenes, using the mono-bromination of benzene as an
example
LO11.3(j)(ii): describe the effect of the delocalisation of electrons in arenes in such reactions

Step 1:

• Initial attack by the  electrons of the aromatic system on the electrophile forms a carbocation
intermediate with a positive charge delocalised across five carbon atoms. Two of the six  electrons
are used to form the bond to the electrophile, leaving only four  electrons delocalised across the
five carbon atoms.
• The movement of two  electrons means that the stability conferred by the delocalisation of the
six  electrons of the ring is disrupted, so this process has high activation energy. Hence, this is the
slow step i.e. rate-determining step.

Step 2:

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• Unlike in alkenes where an anion ‘adds on’ to the carbocation intermediate, the proton i.e. H+ on
the carbon-1 of the benzene intermediate is removed by a Bronsted base, so as to reform the
delocalised  system. A stable substitution product results, and aromaticity is restored.

4.1.2 Shape of molecule and intermediate

The hybridisation and shape of the reacting carbon changes in each step of the mechanism.

4.2 Electrophilic substitution with chlorine or bromine (chlorination or bromination)

LO11.3(i)part: describe the chemistry of the benzene ring as exemplified by the following reactions of benzene: (i) electrophilic
substitution reactions with chlorine and with bromine (recognise the use of Lewis acid as catalyst)

X = Cl X = Br
Reagents & Conditions: Reagents & Conditions:
Cl2(g), FeCl3(s) as Lewis acid catalyst, warm Br2(l), FeBr3(s) as Lewis acid catalyst, warm
OR OR
Cl2(g), Fe(s), warm Br2(l), Fe(s), warm
Observations: Observations:
decolourisation of greenish-yellow Cl2(g) decolourisation of reddish-brown Br2(l)
and white fumes of HCl(g) and white fumes of HBr(g)
Note
• Fe(s) is not the Lewis acid catalyst for electrophilic substitution (see Note 5 below).
• Aluminium analogues such as AlCl3 (s), AlBr3 (s), and Al (s) can also be used in place of their
respective iron counterparts.

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LO11.3(j)(i): describe the mechanism of electrophilic substitution in arenes, using the mono-bromination of benzene as an
example

Mechanism: Electrophilic substitution

Formation of electrophile Br+

(Reaction between FeBr3(s) and Br2(l) generates a strong electrophile Br+.)

Step 1: Delocalised π electron cloud attacks the electrophile.

(The delocalised π system is disrupted in this step thus it has fairly high activation energy.
Notice that EA1 is larger than EA2 in Figure 7 as step 1 is the slow step.)

Step 2: The intermediate loses a proton and aromaticity is restored.

([FeBr4]− acts as a Bronsted base and deprotonates the carbocation intermediate, producing
the product bromobenzene, by-product HBr, and regenerating the Lewis acid catalyst FeBr3.)

The energy profile diagram of bromination of benzene via electrophilic substitution is as follows:

Figure 7. Energy profile diagram of bromination of benzene via electrophilic substitution.

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Note

1. Fe in FeX3(s) or Al in AlX3(s) are electron deficient and can accept a lone pair of electrons from
the halogen X2. Hence FeX3(s) or AlX3(s) are called the Lewis acid (electron pair acceptors)
catalysts.
2. FeX3(s) or AlX3(s) catalyses the electrophilic substitution because they react with halogen X2
(where X = Cl or Br) to generate a strong (positively charged) electrophile (Cl+ or Br+).

3. In the absence of the Lewis acid catalyst, reaction between benzene and halogen cannot take
place. This is because halogen molecule Cl2(g) or Br2(l) is a weak electrophile, unable to react
with the resonance-stabilised benzene ring.

4. The reaction conditions must be anhydrous. This is because in the presence of water, FeX3(s) or
AlX3(s) will accept lone pair of electrons from water and undergo hydrolysis instead, and hence
can no longer accept lone pair of electrons from halogen X2 to generate the strong electrophile
X +.

5. Fe(s) can also be used instead of FeX3(s). This is because when Fe(s) comes into contact with X2,
Lewis acid catalyst FeX3(s) is generated in situ according to the redox reaction shown below.

4.3 Electrophilic substitution with concentrated nitric acid (nitration)

LO11.3(i)part: describe the chemistry of the benzene ring as exemplified by the following reactions of benzene: (ii) nitration
with concentrated nitric acid (recognise concentrated sulfuric acid as a Brønsted-Lowry acid catalyst)

Reagent: concentrated HNO3

Conditions: concentrated H2SO4 as Bronsted-Lowry acid catalyst,
maintained at 55 oC
Observation : pale yellow oily liquid formed

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Mechanism

Note
1. Sulfuric acid is a stronger Bronsted-Lowry acid than nitric acid hence sulfuric acid protonates nitric
acid, eventually generating strong electrophile nitronium ion NO2+.

Steps for generating NO2+ electrophile (background info)

Sulfuric acid protonates nitric acid
H2SO4 + HNO3 → HSO4− + H2NO3+
The protonated nitric acid loses a water molecule to give nitronium ion
H2NO3+ → H2O + NO2+
The water molecule lost is protonated by another molecule of sulfuric acid to give hydronium ion
H2SO4 + H2O → HSO4− + H3O+
Overall equation is therefore 2H2SO4 + HNO3 → 2HSO4− + H3O+ + NO2+

2. The reaction does not occur in the absence of concentrated sulfuric acid.

3. Under more rigorous conditions (e.g. higher temperature or prolonged heating), nitrobenzene can
be further nitrated to give 1,3-dinitrobenzene or 1,3,5-trinitrobenzene. This is not ideal if the
desired product is nitrobenzene.

4. Nitration of benzene is an important first step on the way to a variety of compounds in organic
synthesis. For example:

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Exercise 4.1 (Worked Example)

1. Which set of conditions will bring about the transformation shown below?

A Cl2(g) in the presence of UV

B Cl2(g) in the presence of AlCl3(aq)
C Cl2(g) in the presence of Fe(s)
D Concentrated HCl with heat
[Modified from PrelimRI12/I/20]

Ans C.
Option A is incorrect. While the free radical substitution results in the hydrogen atom in benzene
being substituted by the chlorine atoms, the C-H bond between a sp2-hybridised carbon and a
hydrogen in stronger in benzene than that of a sp3-hybridised carbon in alkane. This will require
an even more drastic condition for the reaction to occur.

Option B is incorrect as reaction conditions must be anhydrous (in the absence of moisture or
water). Lewis acid catalyst FeCl3(s) is generated in situ from Cl2(g) and Fe(s).

A catalyst is required to be present in order to generate a positively charged electrophile for the
stable benzene to react in Option D.

2. What is the main reason for adding concentrated sulfuric acid to concentrated nitric acid in the
preparation of nitrobenzene?
C6H6(l) + HNO3(l) → C6H5NO2(l) + H2O(l)

A It acts as an inert solvent for the benzene and nitric acid.

B It removes protons from nitric acid, thus forming NO3– ions.
C It donates protons to the nitric acid, thus forming NO2+ ions.
D It removes the water, thus preventing equilibrium being established.
[J99/3/23]
Ans C. Conc. H2SO4 acts as a Bronsted-Lowry acid to protonate HNO3 to generate strong
electrophile NO2+ for electrophilic substitution to occur.

3. Will benzene decolourise liquid bromine when warmed in the presence of anhydrous iron(III)
chloride? Explain your answer.
[Modified from PrelimVJC12/I/37]
+
Yes. Electrophilic substitution will occur. Electrophile Br is generated from Br2(l) and FeCl3(s) as
shown below.

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4. Draw the organic product when benzene is warmed with BrCl and anhydrous iron(III) chloride.
[Modified from PrelimTJC12/I/21]

Exercise 4.2 (Worked Example)

The bromination of benzene in the presence of AlBr3 can be represented by the following
mechanism. The enthalpy change of reaction for the bromination of benzene is −43 kJ mol-1.
AlBr3
C6H6 + Br2 C6H6Br+ + AlBr4- C6H5Br + HBr + AlBr3

Which of the following reaction profiles correctly represents this mechanism?

A B C D

Option D is an energy profile diagram for an exothermic reaction. There are two steps in the
electrophilic substitution mechanism hence we eliminate C because it has only one peak which
implies that reaction is one step only. Activation energy for the first step is higher than the second
step as aromaticity of the benzene ring is destroyed when the  electrons attack the electrophile.

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4.4 Electrophilic substitution with halogenoalkanes (Friedel-Crafts alkylation)

LO11.3(i)part: describe the chemistry of the benzene ring as exemplified by the following reactions of benzene: (iii) Friedel-
Crafts alkylation with halogenoalkanes (recognise the use of Lewis acid as catalysts)

Reagent: chloroalkane
Conditions: AlCl3(s) as Lewis acid catalyst, warm
Observation : white fumes of HCl(g)

Mechanism

Note

1. Similar to electrophilic substitution using halogens, AlCl3(s) acts as the Lewis acid catalyst.

2. Friedel-Crafts alkylation only works with alkyl halides as reagents, such as chloroalkane,
bromoalkane and iodoalkane, and not aryl halides (e.g. chlorobenzene) as reagents. In Topic 15
Halogen Derivatives, you will learn that the C–X bond in aryl halides cannot be broken easily.

Exercise 4.3

Describe the mechanism for the following reaction scheme.

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5 METHYLBENZENE AND OTHER SUBSTITUTED BENZENES

5.1 Structure and physical properties of methylbenzene

Methylbenzene (commonly known as toluene) is obtained when a methyl group (–CH3) replaces one
of the hydrogen atoms in benzene. It has the molecular formula C7H8.

Methylbenzene is a colourless liquid which is insoluble in water. It is relatively less toxic than benzene.

5.2 Overview of reactions of methylbenzene

(view section 5.6)

5.3 Electrophilic substitutions of methylbenzene

5.3.1 Electrophilic substitution with chlorine or bromine
LO11.3(i)part: describe the chemistry of the benzene ring as exemplified by the following reactions of methylbenzene: (i)
electrophilic substitution reactions with chlorine and with bromine (recognise the use of Lewis acid as catalyst)

LO11.3(l): predict whether halogenation will occur in the side-chain or aromatic nucleus in arenes depending on reaction
conditions

X = Cl X = Br
Reagents & Conditions: Reagents & Conditions:
Cl2(g), FeCl3(s) as Lewis acid catalyst, rt and Br2(l), FeBr3(s) as Lewis acid catalyst, rt and
absence of UV absence of UV
Observations: Observations:
decolourisation of greenish-yellow Cl2(g) decolourisation of reddish-brown Br2(l)
and white fumes of HCl (g) and white fumes of HBr (g)
Note: Room temperature and absence of UV prevent free radical substitution on alkyl side chain.

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Section 5.5 will explain why the major products below are obtained.

5.3.2 Electrophilic substitution with concentrated nitric acid

LO11.3(i)part: describe the chemistry of the benzene ring as exemplified by the following reactions of methylbenzene: (ii)
nitration with concentrated nitric acid (recognise concentrated sulfuric acid as a Brønsted-Lowry acid catalyst)

Reagent: Concentrated HNO3

Conditions: Concentrated H2SO4 as Bronsted-Lowry acid catalyst, maintained at 30 oC
Observation: Yellow oily liquid formed

5.3.3 Electrophilic substitution with halogenoalkanes (Friedal-Crafts alkylation)

LO11.3(i)part: describe the chemistry of the benzene ring as exemplified by the following reactions of methylbenzene: (iii)
Friedel-Crafts alkylation with halogenoalkanes (recognise the use of Lewis acid as catalysts)

Reagent: chloroalkane
Conditions: AlCl3(s) as Lewis acid catalyst, rt
Observation: white fumes of HCl(g)

Notice that the reaction conditions and possible products in the electrophilic substitution of
methylbenzene are slightly different from benzene. This is because the methyl group has changed the
reactivity of the benzene ring and it also determines the substitution of the incoming group.

Sections 5.4 and 5.5 explain the effects of substituents on the benzene ring.

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5.4 Substituent effect on the reactivity of the benzene ring towards electrophilic substitution
LO11.1(c)part: interpret, and use the following terminology associated with organic reactivities: (i) delocalisation (ii)
electronic effect (electron-donating and electron-withdrawing effect)

Electron-donating groups increase the electron density in the benzene ring. On the other hand,
electron-withdrawing groups decrease the electron density in the benzene ring

From Topic 8 Introduction to Organic Chemistry, electron-donating and electron-withdrawing effects

can occur through:
(i)  bonds via inductive effect
(ii) a  electron cloud via delocalisation

Inductive effect
The inductive effect arises from the polarisation of electron density in a bond due to the
electronegativity of nearby atoms.

• Electron-withdrawing groups via inductive effect

These groups, e.g. –OH, –NH2, –Cl, inductively withdraw electron density from the benzene ring
via the  bond, because O, N and the halogens are more electronegative than the C atom in the
benzene ring:

Other examples include: –OR, –NHR, –NR2, –CHO, –COR, ‒CO2H, –CO2R, ‒NO2, and ‒CN etc.

• Electron-donating groups via inductive effect

Alkyl groups (e.g. –CH3, –CH2CH3) inductively donate electron density into the benzene ring via
the  bond. The reason is due to hyperconjugation which will not be covered here.

Delocalisation
Delocalisation occurs when p orbitals on 3 or more adjacent atoms overlap, forming a π electron
cloud. For substituents with a p orbital on the atom joined to the benzene ring, the p orbital can
overlap with the  electron cloud of the ring.

• Electron-donating groups via delocalisation

These groups have a lone pair of electrons in the p orbital of the atom directly joined to the
benzene ring, and can therefore donate the lone pair of electrons into the benzene ring via
delocalisation. Examples include: –OH, –OR, –NH2, –NR2, –Cl, –Br, and –I.

In phenol below, the p orbital on the O atom joined to the benzene ring can overlap with the 
electron cloud of the ring, enabling the lone pair of electrons on O to be donated into the  system.

Figure 8. Delocalisation of the lone pair of electrons on O atom into the benzene ring in phenol.

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• Electron-withdrawing groups via delocalisation

In these groups, the atom directly joined to the benzene ring forms double/triple bonds to
electronegative atoms like O or N. Hence electron density in the benzene ring is drawn away by
these electronegative atoms via delocalisation. Examples include: –CHO, –COCH3, ‒CO2H,
–CO2CH3, ‒NO2, ‒CN etc.

In benzaldehyde below, the carbon directly bonded to benzene ring forms a double bond with an
electronegative O atom. The p orbitals on C and O of the aldehyde group overlap with the 
electron cloud of the benzene ring. The O atom draws electron density away from the aldehyde
carbon as well as from the  electron cloud of the benzene ring.

Figure 9. Electron density in the  electron cloud of benzene drawn away by electronegative O atom of –CHO group.

Overall effect on reactivity of benzene ring

Inductive effect and delocalisation do not necessarily act in the same direction. When two effects are
opposing e.g. –OH group is electron-withdrawing via inductive effect but electron-donating via
delocalisation, the stronger effect dominates.

• Substituents that are overall electron-donating towards the benzene ring will increase the
electron density of the benzene ring, making it more reactive towards electrophilic attack. We
call them activating groups.

• Substituents that are overall electron-withdrawing from the benzene ring will decrease the
electron density of the benzene ring, making it less reactive towards electrophilic attack. We call
them deactivating groups.

Table 2 summarises the overall electron-donating or electron-withdrawing effect of substituents on

the reactivity of the benzene ring in the A-Level syllabus.

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substituent via inductive effect via delocalisation overall effect on benzene ring
–OH, –OR weakly withdrawing strongly donating strongly electron-donating
–NH2, –NHR, –NR2 ⇒ strongly activating
–NHCOR
–alkyl weakly donating – weakly electron-donating ⇒
weakly activating
–Cl, –Br, –I strongly withdrawing weakly donating* electron-withdrawing
⇒ deactivating
–CHO, –COR, strongly withdrawing strongly withdrawing strongly electron-withdrawing
‒CO2H, ‒CO2R, ⇒ strongly deactivating
‒NO2, ‒CN, –NH3+
Table 2. Effect of substituents via inductive effect and delocalisation, and their overall effect on reactivity of the benzene ring.

*The electron-donating effect of –Cl via delocalisation of lone pair of electrons is not significant
because the overlap between the 3p orbital of Cl atom with the 2p orbitals of the carbon atoms in the
benzene ring is not effective due to large difference in size of the 3p and 2p orbitals. Hence the
halogens are overall electron-withdrawing (mainly due to inductive effect) and deactivating when
attached to the benzene ring.

In contrast, the 2p–2p overlap between O or N atoms with carbon atom is much more effective so the
electron-donating effect of –OH and –NH groups via delocalisation of lone pair of electrons is much
stronger. Hence –OH and –NH groups are overall electron-donating (mainly due to delocalisation) and
activating when attached to the benzene ring.

Activating groups present on the benzene ring means milder conditions (e.g. lower temperatures, no
need for catalysts, dilute concentrations etc.) are required for electrophilic substitution to take place,
compared to benzene. Deactivating groups, on the other hand, will require more vigorous conditions.

Compare the reaction conditions required for benzene and methylbenzene to undergo electrophilic
substitution in Table 3.

Reaction Benzene Methylbenzene

conditions

Bromination Br2(l), FeBr3(s), warm Br2(l), FeBr3(s), r.t.

Nitration conc. HNO3, conc. H2SO4 conc. HNO3, conc. H2SO4
maintained at 55 °C maintained at 30 °C
Alkylation chloroalkane, AlCl3(s), warm chloroalkane, AlCl3(s), r.t.
Table 3. Reaction conditions required for electrophilic substitution of benzene, methylbenzene.

Since the –CH3 group is activating, the conditions required for it to undergo electrophilic substitution
are milder compared to those for benzene. If higher temperatures are used, more than one
substitution could occur, resulting in multi-substituted products and reducing the yield of the desired
monosubstituted product.

In later topics, we will also learn the different conditions required for phenol and phenylamines to
undergo electrophilic substitution.

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5.5 Substituent effect on the position of the incoming electrophile of monosubstituted arenes
LO11.3(m): apply the knowledge of positions of substitution in the electrophilic substitution reactions of monosubstituted
arenes

When methylbenzene undergoes electrophilic substitution with E+ (electrophile), three possible

mono-substituted compounds could be formed:

Figure 10. Three possible mono-substituted products: 2-and 4-substitution is favoured in this case (major products).

The position of the incoming group, E, is determined by the nature of the substituent or group already
bonded to the ring (i.e. –CH3 in this case), and not by the nature of E.

Activating groups (like –CH3) favour 2- and 4- substitution, we call them 2,4-directing groups.
Deactivating groups favour 3-substitution, we call them 3-directing groups. An exception is the
halogens. The reasons are explained at the end of the chapter (not in syllabus). Table 4 summarises
the effects on both reactivity and position of substitution by the group already on the benzene ring in
the A-Level syllabus (also in the Data Booklet).

Substituent on –alkyl –CHO, –COR

benzene ring –OH, –OR ‒CO2H, ‒CO2R
–Cl, –Br, –I
–NH2, –NHR, –NR2 –NH3+
Effect on –NHCOR ‒NO2, ‒CN
Reactivity of ring
activated deactivated deactivated
compared to benzene
Position of incoming
2- and/or 4- 2- and/or 4- 3-
group E
Table 4. Effects on reactivity and position of incoming electrophile by substituents.

What happens if there are two groups already bonded to the benzene ring?
• If both groups direct to the same position on the ring, then substitution will occur at that position.
• If each group directs the incoming electrophile to a different position, the major product follows
the directing effect of the more strongly activating group.
• Further substitution rarely occurs between the two groups in 1,3-disubstituted benzene rings as
this site is too sterically hindered.

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Other combinations may result in a mixture of products with no clear major product. This situation is
not ideal as the reaction will give poor yields of the desired product.

Exercise 5.1 (Worked Examples)

1. Draw the structures of the major organic products in each of the following reactions.

(a) mononitration of 4-methylbenzaldehyde

(b) monobromination of 4-methylphenol

(c) mononitration of 4-bromophenol

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2. In the mononitration of 1,2-dimethylbenzene, a mixture of several products is obtained. Draw

these products and explain why there is no one major product.

1,2-dimethylbenzene has two similarly activating groups which direct the incoming group to all 4
different positions on the benzene ring. Hence there is no clear major product.

Exercise 5.2
Draw the structures of the major organic products in each of the following reactions:

1. monochlorination of nitrobenzene 2. mononitration of bromobenzene

3. monobromination of 4-hydroxybenzoic acid 4. mononitration of 4-aminomethylbenzene

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5.6 Side-chain reactions of methylbenzene

LO11.3(k): describe the chemistry of the alkyl side-chain of benzene ring as exemplified by the following reactions of
methylbenzene: (i) free-radical substitution by chlorine and by bromine, (ii) complete oxidation to give benzoic acid

5.6.1 Free Radical Substitution

LO11.3(l): predict whether halogenation will occur in the side-chain or aromatic nucleus in arenes depending on reaction
conditions

During the side-chain halogenation, methylbenzene and other alkylbenzenes undergo free-radical
substitution with chlorine or bromine in the presence of UV light or heat. The alkyl side chain reacts
like an alkane (Recall from Topic 10 Alkanes).

X = Cl X = Br
Reagents and conditions: Reagents and conditions:
Cl2(g), UV light or heat Br2(l), UV light or heat
Observation: Observation:
greenish-yellow Cl2(g) decolourises slowly reddish brown Br2(l) decolourises slowly
Note: To preferably obtain product of monohalogenation on the alkyl side chain, limited Cl2(g) or
excess alkylbenzene is usually employed.

More than one chlorine or bromine atom can be incorporated onto the alkyl side chain if excess Cl2(g)
or Br2(l) is used. For example:

Exercise 5.3 (Worked Examples)

a) Why must the synthesis of 2-bromomethylbenzene from methylbenzene be carried out in the
absence of light and without heat?

b) Chlorine was passed into methylbenzene under reflux in the presence of aluminium chloride.

Cl CH2Cl
The compound was found to be present in the product. How is the mechanism
for the formation of this product best described?

A electrophilic and free-radical substitution

B electrophilic and nucleophilic substitution
C nucleophilic and free-radical substitution
D nucleophilic substitution only
[N94/4/19]

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(a) To prevent free radical substitution on the alkyl side-chain of methylbenzene which occurs
in the presence of light or heat.
(b) Ans: A. AlCl3 is present as Lewis acid catalyst for methylbenzene to undergo electrophilic
substitution with chlorine. Under reflux conditions, the methyl side-chain may undergo free
radical substitution with chlorine too.

5.6.2 Side-Chain Oxidation

When particular alkylbenzenes are heated with aqueous potassium manganate(VII) in the presence
of dilute H2SO4 or dilute NaOH, oxidation of the side chain occurs. Depending on whether acidic or
alkaline conditions are used, the alkyl side-chain may be oxidised to benzoic acid or a benzoate salt.

Reagents and conditions: Reagents and conditions:

KMnO4(aq), dilute H2SO4, heat KMnO4(aq), dilute NaOH, heat
Observations: Observations:
purple KMnO4(aq) decolourises and white purple KMnO4(aq) decolourises and brown
precipitate of benzoic acid is formed precipitate of manganese dioxide, MnO2(s) is
formed
Note: To write the balanced equation using [O], balance the H atoms using H2O first, then O atoms
using [O].

For an alkyl side-chain of benzene ring to undergo oxidation, the carbon atom just next to the benzene
ring must possess at least one hydrogen atom as shown below.

Regardless of the length of the alkyl side-chain, the carbon next to the benzene ring will be oxidised
to –CO2H in acidic medium or –CO2− in alkaline medium if it bears at least one H atom.

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For example, ethylbenzene undergoes side-chain oxidation in acidic medium producing benzoic acid.
The second carbon in the side-chain is oxidised to CO2(g).

If the side-chain consists of a propyl group, the products after oxidation in acidic medium will consist
of benzoic acid and the rest of the side-chain gets oxidised to a carboxylic acid.

When there are three alkyl substituents attached to the C atom beside the benzene ring, the
alkylbenzene will not undergo side-chain oxidation. For example, tert-butylbenzene does not react
with hot acidified KMnO4 as the C atom adjacent to the benzene ring does not possess any H atom.

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OTHER CASES OF SIDE-CHAIN OXIDATION (Application examples)

[2009/P2/4c and 2003/P3/7]

Exercise 5.4

1. Write a balanced equation for the side-chain oxidation of in acidic medium.

2. Write a balanced equation for the side-chain oxidation of in acidic medium.

3. Write a balanced equation for the side-chain oxidation of in dilute NaOH.

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6 DISTINGUISHING TESTS

Bromine in tetrachloromethane can be used as a distinguishing test to differentiate between alkenes

and arenes. For example: 1-methylcyclohexene and benzene.

Procedure for distinguishing test between 1-methylcyclohexene and benzene as example

1. Add bromine in tetrachloromethane dropwise with shaking to 1 cm3 of each compound in

separate test tubes.

Observations
Benzene: Br2 in CCl4 remains reddish-brown
1-methylcyclohexene: Reddish-brown Br2 in CCl4 decolourises

Note
• Bromine in tetrachloromethane is usually employed instead of liquid bromine because it is
easier to handle than liquid bromine which is a volatile liquid at rtp that constantly gives rise to
toxic bromine gas.
• In the presence of light, both electrophilic addition and free radical substitution occur to
1-methylcyclohexene. However, free radical substitution is not usually used as a distinguishing
test.

Aqueous bromine can also be used as a distinguishing test to differentiate between alkenes and
arenes. For example: 1-methylcyclohexene and benzene.

Procedure for distinguishing test between 1-methylcyclohexene and benzene as example

1. Add aqueous bromine dropwise with shaking to 1 cm3 of each compound in separate test tubes.

Observations
Benzene: Br2(aq) remains yellow-orange
1-methylcyclohexene: Yellow-orange Br2(aq) decolourises

Note:
The difference between aqueous bromine and bromine in tetrachloromethane is that in the presence
of light, free radical substitution does not occur with the use of aqueous bromine.

Heating with aqueous potassium manganate(VII) and dilute H2SO4 can be used as a distinguishing
test to differentiate between certain alkenes and certain alkylbenzenes, and between certain
alkylbenzenes. For example: hexene and methylbenzene, and methylbenzene and tert-butylbenzene.

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Hexene Methylbenzene
Structure

Physical Colourless liquid Colourless liquid

appearance at rtp
Reagents and KMnO4(aq) KMnO4(aq)
conditions Dilute H2SO4 Dilute H2SO4
Heat Heat
Type of reaction Oxidative cleavage Side chain oxidation
Organic product

Observations Effervescence of CO2(g) and Purple KMnO4(aq) decolourises, and white ppt
purple KMnO4(aq) decolourises of benzoic acid
No white ppt No effervescence

Observations: KMnO4(aq)
remains purple. No white
ppt.

Procedure for distinguishing test between methylbenzene and tert-butylbenzene as example

1. Add 5 drops of KMnO4(aq) to 1 cm3 of dilute H2SO4 in a test tube.

2. To 1 cm3 of each compound in separate test tubes, add 2‒3 drops of the KMnO4(aq)/H2SO4(aq)
mixture dropwise with shaking. Warm this test tube in a water bath for a few minutes.

Observations
Methylbenzene: Purple KMnO4(aq) decolourises, and white ppt of benzoic acid forms
tert-butylbenzene: KMnO4(aq) remains purple. No white ppt.

Exercise 6.1
Suggest a simple chemical test to distinguish between each of the following pairs of compounds.
State the reagents and conditions required, and expected observations for each compound.

a) 1-methylcyclohexene and methylbenzene, both appears as colourless liquid

b) Benzene and methylbenzene, both appears as colourless liquid

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Summary of reactions of benzene

Fill in the boxes with the correct compounds.

benzene

Type of reaction: electrophilic substitution

Cl2(g) Conc. HNO3 CH3Cl

FeCl3(s) Conc. H2SO4 AlCl3(s)
warm maintained at 55 oC warm

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Summary of reactions of methylbenzene

Fill in the boxes with the correct compounds.

CH3Cl major organic products:

AlCl3(s)
rt

Cl2(g)
major organic products:
FeCl3(s)
rt
absence of UV
methylbenzene
Reactions at the
benzene ring

Type of reaction:
electrophilic
substitution
major organic products:
Conc. HNO3
Conc. H2SO4
maintained at 30 oC

Reactions at the
alkyl side-chain

excess Cl2(g)
KMnO4(aq), dilute H2SO4, heat
UV light
Type of reaction: side-chain oxidation
Type of reaction: free-radical substitution

All possible organic products: major organic product:

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Reasons for directing effects of substituents (Background Info)

2,4-directing groups

Activating groups and halogens are 2,4-directing. The reason can be explained by the stability of the
carbocation intermediates. The fundamental principle is that “A more stable carbocation is formed
faster than a less stable one”.

Consider the nitration of methylbenzene in the following example. NO2+ can be added to
methylbenzene at 2-, 3- or 4-position to give three carbocation intermediates as shown in the
following figure. The carbocation intermediates formed from 2- and 4-substitution are stabilised more
than the intermediate formed from 3-substitution. This is because carbocation intermediates formed
from 2- and 4-substitution each have resonance structures where the positive charge is on the methyl-
substituted carbon. These carbocation intermediates are stable tertiary carbocations that are
stabilised by the electron-donating methyl substituent by inductive effect (see the box). The
carbocation intermediates formed from 2- and 4-substitution are therefore more stable and form
faster, giving rise to higher product yields of 2-nitromethylbenzene and 4-nitromethylbenzene than 3-
nitromethylbenzene.

Figure 11. Carbocation intermediates in the nitration of methylbenzene. Note: It is more convenient to use one of the
resonance structures of toluene for illustration.

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Consider the nitration of phenol in the following example. The carbocation intermediates formed from
2- and 4-substitution are more stable than the intermediate formed from 3-substitution. This is
because carbocation intermediates formed from 2- and 4-substitution each have resonance structures
where the positive charge is dispersed by the OH substituent via delocalisation of lone pair of electrons
from O atom.

Figure 12. Carbocation intermediates in the nitration of phenol. Note: It is more convenient to use one of the resonance
structures of phenol for illustration.

Consider the nitration of chlorobenzene in the following example. The carbocation intermediates
formed from 2- and 4-substitution are more stabilised than the intermediate formed from 3-
substitution. This is because carbocation intermediates formed from 2- and 4-substitution each have
resonance structures where the positive charge is dispersed by the Cl substituent via delocalisation of
lone pair of electrons from Cl atom.

Figure 13. Carbocation intermediates in the nitration of chlorobenzene. Note: It is more convenient to use one of the
resonance structures of chlorobenzene for illustration.

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3-directing groups
Deactivating groups (with the exception of halogens) are 3-directing. Consider the nitration of
benzaldehyde in the following example. The carbocation intermediates formed from 3-substitution is
more stable than the intermediate formed from 2- and 4-substitution. This is because carbocation
intermediates formed from 2- and 4-substitution each have resonance structures where the positive
charge is on the carbon bearing the deactivating group. These carbocation intermediates will be
destabilised by the electron-withdrawing deactivators by inductive effect and delocalisation. (See the
box)

Figure 14. Carbocation intermediates in the nitration of benzaldehyde. Note: It is more convenient to use one of the
resonance structures of benzaldehyde for illustration.

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Chemistry of the Aqueous Solution:

13 Solubility Equilibria
GUIDING QUESTIONS
• What is a saturated solution?
• What is solubility and solubility product? How are they related?
• What and why does precipitation take place?

LEARNING OUTCOMES
Students should be able to:
10.2(a) show understanding of, and apply, the concept of solubility product, Ksp
10.2(b) calculate Ksp from concentrations and vice versa
10.2(c) discuss the effects on the solubility of ionic salts by the following:
(i) common ion effect
(ii) formation of complex ion, as exemplified by the reactions of halide ions with
aqueous silver ions followed by aqueous ammonia

REFERENCES
1. Martin S. Silberberg, Chemistry: The molecular nature of Matter and Change. 3rd Edition, McGraw
Hill, Chapter 18
2. Graham C. Hill and John S. Holman, Chemistry in Context, second Edition, ELBS, Chapter 22

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1 INTRODUCTION

LOOKING BACK
In Topic 7 Chemical Equilibrium, we learnt the concept of dynamic equilibrium and the Le Chatelier’s
principle. In this topic, we will apply this knowledge to the dynamic equilibrium that exists between
an undissolved solute and its dissolved ions in solution, when the rate of precipitation and dissolution
is equal, and use the Le Chatelier’s principle to explain the factors that affect the solubility of a salt.

Equilibria involving ions in aqueous solution are important in industrial, analytical and biological
processes. The dissolving and precipitating of ionic compounds in aqueous solution are phenomena
that occur both within us and around us. For example, the dissolving of enamel on teeth in acidic
solutions causes tooth decay; the precipitation of certain salts in our kidneys produces kidney stones;
the precipitation of calcium carbonate from underground water forms stalactites and stalagmites
inside caves. The principles and characteristics of these heterogeneous equilibria in aqueous solutions
are very similar to those in other systems in chemical equilibria.

In this extension topic, we will explore the solubility equilibria of sparingly soluble ionic compounds.

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2 SOLUBILITY AND SATURATED SOLUTIONS

DEFINITION

Solubility of a salt is the number of moles (or mass) of solute (salt) that can be dissolved in 1 dm3
of a given solvent (e.g. water) to form a saturated solution at a given temperature.

For example, the solubility of NaCl in water at 25 °C is 357 g dm−3 or 6.102 mol dm−3.
This is the maximum amount of NaCl that can be dissolved in water to give a saturated solution at that
temperature.

• Units of solubility: mol dm−3 (molar solubility) or g dm−3

Ionic compounds with low solubility are said to be sparingly soluble. The table below summarises
some ionic compounds with very high solubility (‘soluble’) and very low solubility (‘insoluble’).

Ions Solubility
NO3− All nitrates are soluble
Cl , Br , I
− − −
All halides are soluble except Ag+ and Pb2+
SO42− All sulfates are soluble except Pb2+, Ba2+ and Ca2+
CO32− All carbonates are insoluble except Na+, K+ and NH4+
O2− All oxides are insoluble except Na+ and K+
OH− All hydroxides are insoluble except Na+ and K+

As a solute begins to dissolve in a solvent, the concentration of the solute particles in the solution
increases. But this cannot occur infinitely, most solutes have a finite (limited) solubility in a particular
solvent at a particular temperature. For the sparingly soluble salts, they reach equilibrium with
relatively little solute dissolved.

When this upper limit is reached, the solution is said to be saturated at that temperature, and no
more solute will dissolve in the saturated solution.

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3 SOLUBILITY EQUILIBRIA AND SOLUBILITY PRODUCT, Ksp

LO 10.2(a): show understanding of, and apply, the concept of solubility product, K sp

When increasing quantities of a sparingly soluble ionic salt are added to water, a saturated solution
will eventually be formed. Upon addition of excess solute, a dynamic equilibrium is set up, in which
there is simultaneous dissolution of the excess undissolved solute and precipitation of the solute from
the ions in the solution. These two processes take place at the same rate. Ions in the saturated solution
are at equilibrium with the excess undissolved solute:

MX(s) ⇌ M+(aq) + X−(aq)

Now, consider a mixture containing a saturated aqueous solution of silver chloride and some
undissolved silver chloride. The system is at equilibrium:

AgCl(s) ⇌ Ag+(aq) + Cl−(aq)

We can write:
[Ag+][Cl-]
Kc =
[AgCl]

However, [AgCl] represents the ‘concentration’ of a pure solid, and is therefore a constant.

Therefore, Kc × [AgCl] = [Ag+][Cl−]

⇒ Ksp = [Ag+][Cl−]

The new constant, Ksp, is called the solubility product of AgCl.

Units of Ksp of AgCl: mol2 dm−6

DEFINITION

Solubility product, Ksp, of a sparingly soluble salt is the product of the molar concentrations of the
constituent ions in a saturated solution, raised to the appropriate powers at a given temperature.

Note: Appropriate power refers to the stoichiometric coefficient of the substance in the balanced
equation for the reaction.

• The concept of solubility product is valid only for sparingly soluble salts. For soluble salts such
as NaCl, CuSO4 and AgNO3, the use of the Ksp concept is inappropriate.

• As such, for sparingly soluble salts, the numerical value of Ksp is always very small, rarely
exceeding 10−4 and can be as low as 10−40.

• Like other equilibrium constants, the value of Ksp changes only with temperature.

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• Using the general formula AxBy for a sparingly soluble salt, the solubility equilibrium is:

AxBy(s) ⇌ xAy+(aq) + yBx−(aq)

and the general expression for solubility product is given by:

Ksp = [Ay+]x [Bx−]y

where [Ay+] and [Bx−] are concentrations of ions(in mol dm−3) in a saturated solution.

Exercise 3.1 (Worked Example)

Write an expression for the solubility product of each of the following salts and state its units:
(a) PbI2 (b) Ag2CO3 K (c) Ca3(PO4)2 = [Ca2+]3[PO43−]2 mol5 dm−15

(a) Ksp = [Pb2+][I−]2 mol3 dm−9

(b) Ksp = [Ag+]2[CO32−] mol3 dm−9
(c) Ksp = [Ca2+]3[PO43−]2 mol5 dm−15

Exercise 3.2
Write an expression for the solubility product of each of the following salts and state its units:
(a) FeCO3 (b) SrF2 (c) Hg2SO4 mol3 dm−9

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An experimental investigation on the solubility product of AgBrO3 at 16 °C

AgBrO3(s) ⇌ Ag+(aq) + BrO3−(aq)

Different initial volumes of AgNO3(aq) and KBrO3(aq), both of initial concentrations of

0.10 mol dm−3, were added to 200 cm3 of distilled water at 16 °C. The [Ag+] and [BrO3−] at
equilibrium were determined and shown in the table below:

Initial vol. of Initial vol. of [Ag+] [BrO3−] [Ag+]eqm × [BrO3−]eqm /

0.10 mol dm−3 0.10 mol dm−3 at equilibrium at equilibrium mol2 dm−6
AgNO3 / cm3 KBrO3 / cm3 / mol dm−3 / mol dm−3
40 10 0.0144 0.0024 3.45 × 10−5
30 20 0.0081 0.0041 3.32 × 10−5
25 25 0.0058 0.0058 3.36 × 10−5
20 30 0.0042 0.0082 3.44 × 10−5
10 40 0.0033 0.0102 3.37 × 10−5

It is important to note that the product of the equilibrium concentrations of Ag+(aq) and
BrO3−(aq) in all 5 sets of experiments were almost constant.

[Ag+][BrO3−] = constant at a given temperature = 3.39 × 10−5 mol2 dm−6 at 16 °C

This value of [Ag+][BrO3−] is the solubility product of AgBrO3 at 16 °C.

In other words, this value of Ksp of AgBrO3 at 16 °C is independent of the amount of Ag+ and
BrO3− added to the solution, provided that a saturated solution is obtained. (i.e. some
undissolved AgBrO3 is in contact with the solution.)

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4 SOLUBILITY VS SOLUBILITY PRODUCT

LO 10.2(b): calculate Ksp from concentrations and vice versa

Solubility of Solubility of Molar

compound compound concentration of Ksp
in g dm−3 in mol dm−3 ions

• Solubility and solubility product are different.

• Ksp can be calculated from the solubility of the salt and vice versa.

4.1 Calculation of Ksp from solubility

Exercise 4.1 (Worked Example)

The solubility of silver chloride is 1.46 × 10−3 g dm−3 at 18 °C. What is the solubility product of silver
chloride at this temperature? (Mr of AgCl is 143.5)

Molar solubility of AgCl = (1.46 × 10−3) ÷ 143.5 = 1.0174 × 10−5 mol dm−3

AgCl (s) ⇌ Ag+(aq) + Cl− (aq)

−3 −5
[ ]eqm /mol dm 1.017 × 10 1.017 × 10−5

Ksp = [Ag+][Cl−] = (1.017 × 10−5)2 = 1.04 × 10−10 mol2 dm−6

4.2 Calculation of solubility from Ksp

Exercise 4.2
A suspension of solid Mg(OH)2 in water is sold as "milk of magnesia" to alleviate minor stomach
disorders by neutralising stomach acid. The [OH−] is too low to harm the mouth and throat, but the
suspension dissolves in the acidic stomach juices.

Find the solubility of Mg(OH)2 in mol dm−3 and in g dm−3, given the numerical value of Ksp of Mg(OH)2
is 6.30 × 10−10. (Mr of Mg(OH)2 is 58.3)

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Determining the solubility product of a sparingly soluble compound

Scenario:
To plan an experiment to determine a value of the solubility product Ksp of a sparingly soluble salt, and
to investigate how the solubility will be affected by the presence of a common ion (see section 6.1).
Approach:
This experiment is in two parts: part 1, preparing the saturated solution(s), and part 2, determining
the amount of dissolved solid (usually by titration).
Part 1: To prepare a saturated solution of the sparingly soluble compound, take into consideration the
following characteristics of heterogeneous equilibria:

MX (s) M+ (aq) + X– (aq).

• To establish an equilibrium, the saturated solution must also contain excess (undissolved) solid. If
you are not required to determine the mass of the dissolved solid gravimetrically, there is no need
to weigh the amount of solid added accurately, so long as there is undissolved solid in the
saturated solution. At this stage, this is called a suspension because it contains undissolved solid.
• Like all reversible reactions, it takes time to reach equilibrium. Therefore the suspension is shaken
in stoppered bottles / conical flasks, or stirred in beakers with a glass rod, and then allowed to
stand for a while (about 5 – 10 min), at the end of which, the excess solid settles to the bottom.
• Solubility and Ksp values are dependent on temperature, so the temperature of the suspension
must be maintained (usually by a water bath or thermostat), and be recorded.
• To investigate the effect of a common ion (see section 6.1), you may be required to set up several
(usually five) different saturated solutions with different starting concentrations of the common
ion.

Part 2: To determine the amount of dissolved solid, a titration procedure is often carried out. For
example, standard hydrochloric acid will be used to titrate the saturated solution if X– is OH─. However,
before this titration is carried out, the suspension must be filtered to remove the undissolved solid.
To prevent the introduction of water which will dilute the saturated solution, it is critical that the
filtration is carried out using dry filter funnel, dry filter paper, and the filtrate is collected in a dry
conical flask.

Generic procedure for determining solubility

1. Measure _(volume)__ of __(solvent)___ into a conical flask, using a measuring cylinder.
2. Add _(solid)_ to the conical flask and swirl. Continue adding _(solid)_ until no more can dissolve.
3. Stopper the flask and shake.
4. Leave the flask to stand in a water bath maintained at 25 oC for (a suitable time) .
5. Filter the suspension into a dry conical flask, using dry filter funnel and dry filter paper.
6. Pipette 25 cm3 of the filtrate (saturated solution) into another conical flask.
7. (titration procedure).

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5 IONIC PRODUCT

DEFINITION

The ionic product (IP) of a sparingly soluble salt is the product of the molar concentrations of the
constituent ions in the solution, raised to the appropriate powers.

For example AgCl(s) ⇌ Ag+(aq) + Cl−(aq)

The ionic product of AgCl is therefore given by: IP of AgCl = [Ag+][Cl−]

• IP has the same mathematical expression as Ksp.

• IP can take on any value and is only numerically equal to Ksp in saturated solutions.

• Unlike Ksp which applies only in saturated solutions and at equilibrium, IP is applicable in
unsaturated solutions as well as in theoretical terms at the instant of mixing (or the instant
before precipitation occurs). Refer to the following exercises.

Exercise 5.1 (Worked Example)

1.00 × 10−3 mol dm−3 solution of Ca2+ is mixed with an equal volume of 1.00 × 10−3 mol dm−3 solution
of SO42− at 25.0 °C. No precipitation of CaSO4 occurs. Calculate the ionic product of CaSO4 in the
resulting solution.

After mixing, the concentration of each ion is halved since final volume has doubled
[Ca2+] = [SO42−] = (1.00 × 10−3) ÷ 2 = 5.00 × 10−4 mol dm−3
IP = [Ca2+][SO42−] = (5.00 × 10−4)2 = 2.50 × 10−7 mol2 dm−6
(note: Ksp value of CaSO4 is 4.93 x 10–5)

5.1 Using Ksp and IP to predict the occurrence of precipitation

• The value of IP indicates the direction in which the solubility reaction will occur. The idea of IP
and Ksp is analogous to that of Qc and Kc.

• When IP < Ksp, the forward reaction (dissolution of the salt) occurs. When IP > Ksp, the
backward reaction (precipitation of the salt) occurs. Relate this to what you learnt in Topic 7
Chemical Equilibria about Qc and Kc.

• Hence, the value of IP allows us to predict if precipitation would occur when two solutions are
mixed.

• When two solutions are mixed, precipitation may or may not occur depending on:
(a) concentration of ions after mixing
(b) Ksp of the salt present

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Consider the sparingly soluble salt BaSO4, BaSO4(s) ⇌ Ba2+(aq) + SO42−(aq)

IP = [Ba2+][SO42−]

Adding solid BaSO4 in small amounts into Mixing a solution of Ba2+(aq) and a
Context
pure water. solution of SO42–(aq)
When does the solution become
IP vs Ksp Will there be precipitation?
saturated?
The solution is not saturated. No precipitation occurs.
IP < Ksp
Forward BaSO4(s) ⇌ Ba2+(aq) + SO42−(aq)
reaction More BaSO4 can dissolve in the solution
occurs. until IP = Ksp.

The solution is saturated. The first trace of precipitate just

appears.
IP = Ksp No more BaSO4 can dissolve. (or is just about to appear)
At The solution contains the maximum
equilibrium amount of Ba2+ and SO42−.
Upon further addition of solid, IP remains
equal to Ksp. Undissolved solid is present in
equilibrium with the saturated solution.
IP > Ksp Precipitation of BaSO4 occurs.
Backward BaSO4(s) ⇌ Ba2+(aq) + SO42−(aq)
reaction Equilibrium shifts to the left, forming
occurs. the precipitate until IP = Ksp.

Exercise 5.2 (Worked Example)

Will a precipitate form when 0.100 dm3 of 3.00 × 10−3 mol dm−3 Pb(NO3)2(aq) is added to 0.400 dm3
of 5.00 × 10−3 mol dm−3 Na2SO4(aq)? (numerical value of Ksp of PbSO4 is 1.60 × 10−8)

The insoluble salt that may be produced is PbSO4.

[Pb2+] = 3.00 × 10−3 × (0.1 ÷ 0.5) = 6.00 × 10−4 mol dm−3
[SO42−] = 5.00 × 10−3 × (0.4 ÷ 0.5) = 4.00 × 10−3 mol dm−3
Ionic Product of PbSO4 = [Pb2+][SO42−] = (6.00 × 10−4)(4.00 × 10−3)
= 2.40 × 10−6 mol2 dm−6 > 1.60 × 10−8 mol2 dm−6
Since IP > Ksp, precipitation occurs and white precipitate of PbSO4 forms.

Exercise 5.3
Ca(NO3)2(s) is added to a 2.00 × 10−4 mol dm−3 solution of MgSO4. What is the minimum [Ca2+] before
a precipitate of CaSO4 can be formed? (numerical value of Ksp of CaSO4 is 2.40 × 10−5)

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5.2 Selective Precipitation of Ions

• Selective precipitation is the separation of ions in an aqueous solution by using a reagent that
forms a precipitate with one or a few of the other ions but not all.

• Ions can be separated from each other based on the different solubilities of their salts.

Exercise 5.4
In a solution, [Ag+] = 1.00 × 10−2 mol dm−3 and [Pb2+] = 2.00 × 10−2 mol dm−3. NaCl(s) is added to this
solution.
(numerical value of Ksp of AgCl is 1.80 × 10−10, numerical value of Ksp of PbCl2 is 1.60 × 10−5)

(i) What is the minimum concentration of Cl− necessary for each salt to be precipitated?

(ii) Which salt precipitates first? AgCl

(iii) How can Ag+ be separated from Pb2+? Find the % of Ag+ left in the solution. Is the separation
effective?

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6 FACTORS AFFECTING SOLUBILITY

6.1 Common Ion Effect

LO 10.2(c)(i): discuss the common ion effect on the solubility of ionic salts

Consider a mixture of solid calcium fluoride and its aqueous ions in a saturated solution:

CaF2(s) ⇌ Ca2+(aq) + 2 F−(aq)

If a water-soluble solute containing the common ion Ca2+ or F− is added, e.g. adding CaCl2(aq) or
NaF(aq), by Le Chatelier’s Principle, the position of equilibrium will shift to the left to decrease [Ca2+]
or [F−]. Less CaF2 will dissolve, reducing the solubility of CaF2.

Exercise 6.1
The numerical value of Ksp of AgCl is 2.00 × 10−10 at 25 °C.

(i) What is the solubility of AgCl?

(ii) Calculate the solubility of AgCl in 0.100 mol dm3 NaCl (aq).
be the solubility of AgCl in 0.100 mol dm−3 NaCl

Comments on the data:

• When a saturated solution is obtained by dissolving the pure salt in water, the concentrations
of the ions are in the ratio determined by the stoichiometry of the salt.

• Solubility of AgCl decreases in the presence of Cl−, the common ion

(2.00 × 10−9 mol dm−3 in (ii) < 1.40 × 10−5 mol dm−3 in (i)). This is known as the common ion
effect.

• In other words, the solubility of a sparingly soluble salt decreases in the presence of a second
solute that contains a common ion.

6.2 Formation of complex ion:

LO 10.2(c)(ii): discuss the effects on the solubility of ionic salts by formation of complex ions, as exemplified by the reactions
of halide ions with aqueous silver ions followed by aqueous ammonia

Some metal ions can accept electron pairs from neutral molecules or anions to form complex ions.

Example 1:
When NaOH(aq) is added to a solution containing Al3+, a white precipitate of Al(OH)3 is formed. This
precipitate dissolves in excess NaOH to form the complex ion [Al(OH)4]−. Such complex ions are soluble
in water.

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Explanation:
Initially, when NaOH(aq) is added to a solution containing Al3+, since Ksp of Al(OH)3 is very low, IP easily
exceeds Ksp.

Precipitate starts forming when IP = Ksp and equilibrium exists between some Al(OH)3(s) and its ions.

Al(OH)3(s) ⇌ Al3+(aq) + 3OH−(aq) ------------(1)

In excess NaOH, the complex ions [Al(OH)4]− are formed.

Al3+(aq) + 4OH−(aq) ⇌ [Al(OH)4]−(aq) ------------(2)

• Formation of the complex ions removes Al3+ from the solution, hence [Al3+] decreases.

• This shifts the position of equilibrium in (1) to the right to produce more Al3+, and the white
precipitate of Al(OH)3 dissolves.

• Complex ion formation increases the solubility of a sparingly soluble salt.

Example 2:
When AgNO3(aq) is added to a solution containing halide ions, (X−), silver halide (other than silver
fluoride), is precipitated. When this reaction is followed up by adding NH3(aq), AgCl dissolves in both
dilute and concentrated NH3, AgBr does not dissolve in dilute aqueous NH3, but dissolves in
concentrated NH3, while AgI does not dissolve in both dilute and concentrated NH3.

The table below summarises the reaction of the halide ions with aqueous silver nitrate and the
subsequent solubility of the silver halides in dilute and concentrated ammonia.

Halide ion F− (aq) Cl− (aq) Br− (aq) I− (aq)

Reaction with AgNO3 (aq) No ppt White ppt Cream ppt Yellow ppt
Partially
Solubility (i) in dilute NH3 − Soluble Insoluble
soluble
of AgX
(ii) in conc. NH3 − Soluble Soluble Insoluble

Ksp of AgX/ mol2 dm−6 − 1.80 × 10−10 5.40 × 10−13 8.50 × 10−17

Explanation:

Initially, when AgNO3(aq) is added to a solution containing halide ion (X−), since the numerical values
of the Ksp of AgX are very low, IP easily exceeds Ksp, hence AgX is formed.

Precipitates starts forming and equilibrium exists between the AgX and its ions.

AgX (s) ⇌ Ag+ (aq) + X− (aq) ------------------------ (1)

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The subsequent addition of ammonia results in the formation of the stable

diammine silver(I) complex, [Ag(NH3)2]+.

Ag+ (aq) + 2NH3 (aq) ⇌ [Ag(NH3)2]+ (aq) --------- (2)

Addition of NH3 shifts the position of equilibrium (2) to the right, causing [Ag+] to decrease (and the
value of ionic product, [Ag+][X−], to decrease). The decrease in [Ag+] causes the position of equilibrium
(1) to shift to the right, hence increasing the solubility of AgX. The solubility of the silver halides in
ammonia depends on the Ksp of the silver halides. For the AgX solid to dissolve completely in ammonia,
the ionic product must decrease to ≤ Ksp.

The Ksp values of silver halides decrease in the order: AgCl > AgBr > AgI.

For AgCl, when dilute NH3 is added, the precipitate dissolves completely because the addition of dilute
NH3 is sufficient to lower [Ag+] such that the ionic product becomes smaller than Ksp of AgCl.

For AgBr, Ksp is lower, so the addition of dilute NH3 is not sufficient to lower [Ag+] till the ionic product
becomes smaller than Ksp of AgBr. Hence, AgBr does not dissolve completely in dilute NH3. However,
when concentrated NH3 is used, it will sufficiently lower [Ag+] such that the ionic product becomes
smaller than Ksp and the precipitate dissolves completely.
For AgI, the value of Ksp is extremely low, thus the addition of either dilute or concentrated NH3 is not
sufficient to lower [Ag+] such that the ionic product becomes smaller than Ksp of AgI. Hence AgI
precipitate remains when dilute or concentrated NH3 is added.

Exercise 6.2 (Worked Example)

Explain why the solubility of PbCl2 decreases in dilute HCl but increases in concentrated HCl.

PbCl (s) ⇌ Pb (aq) + 2Cl (aq) ------------(1)

2
2+ −

In dilute HCl, the common ion [Cl ] causes the position of equilibrium in (1) to shift to the left to
−

lower [Cl ], hence less PbCl dissolves.

−
2

Pb (aq) + 4Cl (aq) ⇌ [PbCl ] (aq) ------------(2)

2+ −
4
2−

In concentrated HCl, Pb will form a water soluble complex, [PbCl ] , with excess Cl .
2+
4
2− −

Formation of the complex ion removes Pb from solution.2+

The position of equilibrium in (1) shifts to the right to produce more Pb , and PbCl dissolves (i.e.
2+
2

solubility of PbCl increases).

2

6.3 Effects of pH

Changes to the pH of a solution may affect the solubility of a sparingly soluble salt containing either
Brønsted acids or bases. A Brønsted acid is a proton donor whereas a Brønsted base is a proton
acceptor. The Brønsted acid-base theory was introduced briefly in Topic 4 Reactions & Stoichiometry.

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DEFINITIONS
The pH of a solution is the negative logarithm to base ten of the molar concentration of hydrogen ion,
i.e. pH = − lg [H+]

The pOH of a solution is the negative logarithm to base ten of the molar concentration of hydroxide
ion, i.e. pOH = − lg [OH−]

i.e. [H+] = 10−pH and [OH−] = 10−pOH

Also, at 25 oC, pH + pOH = 14 (refer to Topic 14 Acid-base Equilibria).

For example, a sparingly soluble salt, magnesium hydroxide, Mg(OH)2, dissolves in aqueous solution
according to the equation below.
Mg(OH)2(s) ⇌ Mg2+(aq) + 2OH−(aq)

Addition of a strong Brønsted acid like HCl (which will decrease pH) will neutralise the OH− to form
water. The removal of OH− lowers [OH–]. According to the Le Chatelier’s Principle, the position of the
above equilibrium will shift to the right to offset the decreased [OH−], more Mg(OH)2 dissolves.

Thus, the solubility of Mg(OH)2 increases when the pH of the solution decreases.
Therefore, the solubility of a sparingly soluble salt containing basic anions increases as [H+] increases
(i.e. pH decreases).

Exercise 6.3
A saturated solution of Mg(OH)2 has a pH of 10.52.
(The numerical value of Ksp of Mg(OH)2 is 1.80 × 10−11)
(i) Calculate the solubility of Mg(OH)2 in this solution. (1.64 × 10−4 mol dm−3)
(ii) Calculate the solubility of Mg(OH)2 if the saturated solution in (i) is mixed with a solution
maintained (i.e. buffered) at pH 9.00. (0.180 mol dm−3)

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7 APPLICATION AND RELEVANCE TO REAL-LIFE CONTEXTS

The following examples illustrate the relevance of the Ksp concept to a range of phenomena and
contexts.

• Daily life
In regions with hard water (that contains calcium and magnesium ions), mineral deposits can
sometimes be seen on cooking dishes or in bathtubs. These deposits are caused by the
precipitates of calcium/magnesium ions in the hard water. These deposits can make hard
water unsuitable for many uses. Thus, variety of ways can be used to reduce the hardness of
water, for example, by the addition of sodium carbonate.

• Health
Kidney stones are a biological example of how the concept of solubility is experienced in our
lives. A kidney stone is usually made up of a salt of calcium, commonly ethanedioate or
phosphate. Thus people who are prone to kidney stones have to limit or avoid eating foods
with high ethanedioate content (e.g. spinach, peanuts and sweet potatoes). A possible
approach to treating kidney stones is to drink a large amount of water so as to flush out the
kidney stones from the urinary tract.

Looking ahead:
The concepts learnt about the dynamic equilibrium of a saturated solution will be useful when we
explore the chemistry of inorganic compounds in further topics (such as in Inorganic Qualitative
Analysis experiments and Topic 22 Chemistry of the Transition Elements). For example, the Le
Chatelier’s principle, common ion effect and the formation of metal complex ions will be applied to
explain the precipitation and dissolution of metal salts in inorganic reactions.

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Chemistry of Aqueous Solutions:

14 Acid-Base Equilibria

GUIDING QUESTIONS:
• What is a strong or weak acid/base?
• How can the strength of acids and bases be represented and determined?
• What is the relationship between concentration of acid (base), pH (pOH) and strength of acid
(base)?
• What are buffers? How do buffers work? How can the pH of buffers be determined?
• What are the changes in pH during acid-base titrations? How can these pH changes be
explained?

LEARNING OUTCOMES
Students should be able to:
4(b) show understanding of, and apply the BrØnsted-Lowry theory of acids and bases, including the
concept of conjugate acids and conjugate bases (Refer to Topic 4 Reactions and Stoichiometry for
the BrØnsted-Lowry theory of acids and bases)
5(e)(v) describe and explain the reactions of the chlorides with water (for NaCl; MgCl2; AlCl3; SiCl4; PCl5)
(Refer to Topic 21 Chemical Periodicity for the reactions of NaCl, MgCl2, SiCl4, PCl5 with water)
10.1(a) explain qualitatively the differences in behaviour between strong and weak acids and bases in
terms of the extent of dissociation
10.1(b) explain the terms pH; Ka; pKa; Kb; pKb; Kw and apply them in calculations, including the relationship
Kw = KaKb
10.1(c) calculate [H+(aq)] and pH values for strong acids, weak monobasic (monoprotic) acids, strong
bases, and weak monoacidic bases [Calculations involving weak acids/bases will not require solving
of quadratic equations]
10.1(d) describe the changes in pH during acid-base titrations and explain these changes in terms of the
strengths of the acids and bases
10.1(e) explain the choice of suitable indicators for acid-base titrations, given appropriate data
10.1(f) (i) explain how buffer solutions control pH
(ii) describe and explain their uses, including the role of H2CO3/HCO3– in controlling pH in
blood
10.1(g) calculate the pH of buffer solutions, given appropriate data

REFERENCES
1. Peter Cann & Peter Hughes, Cambridge International AS and A Level Chemistry, Hodder
Education, Chapters 6 & 22
2. Martin S. Silberberg, Chemistry – The Molecular Nature of Matter & Change, McGraw Hill,
Chapter 18 & 19

LOOKING BACK
In Topic 4 Reactions and Stoichiometry, we learnt to define acids and bases according to three models:
Arrhenius Theory, BrØnsted-Lowry Theory and Lewis Theory of acids and bases. In this topic, we shall
use the BrØnsted-Lowry Theory in our understanding of acids and bases and apply the concept of
equilibrium learnt from Topic 7 Chemical Equilibria specifically to acid–base systems.

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1 INTRODUCTION

Acids and bases are important in many chemical processes that occur around us, from industrial
processes to biological ones and from reactions in the laboratory to those in our environment. In this
topic, we will examine equilibria involving acids and bases and study the pH of solutions containing
strong acids and bases, weak acids and bases, salts and buffers.

Recall from Topic 4 Reactions and Stoichiometry that, according to the BrØnsted-Lowry Theory of
acids and bases:
• An acid is a proton-donor and a base is a proton-acceptor.
• An acid-base reaction therefore involves a transfer of a proton from an acid to a base.

1.1 Conjugate Acid-Base pair

LO 4(b): show understanding of, and apply the Brønsted-Lowry theory of acids and bases, including the concept of conjugate
acids and conjugate bases

Consider the following acid-base reaction:

CH3CO2H + H2O ⇌ CH3CO2– + H3O+

acid base conjugate base conjugate acid

In the forward reaction:

CH3CO2H acts as a BrØnsted acid, donating a proton to the BrØnsted base, H2O.

In the reverse reaction:

CH3CO2– acts as a BrØnsted base, accepting a proton from the BrØnsted acid, H3O+, to re-form the
BrØnsted acid, CH3CO2H.

• CH3CO2H and CH3CO2– form a conjugate acid-base pair;

• H2O and H3O+ form another conjugate acid-base pair.

In general, conjugate acid-base pair

acid 1 + base 2 ⇌ base 1 + acid 2

conjugate acid-base pair

• A conjugate acid-base pair constitutes two species which differ from each other by one proton.
• An acid after donating a proton forms its conjugate base.
• A base after accepting a proton forms its conjugate acid.
• In any acid-base reaction, there are two conjugate acid-base pairs.

Exercise 1.1
Identify the conjugate acid-base pairs in each of the following reactions:
1. (worked example) HNO3 + NH3 → NO3– + NH4+
HNO3 (acid) / NO3− (conjugate base) & NH3 (base) / NH4+ (conjugate acid)
2. NH3 + H2O ⇌ NH4+ + OH–

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1.2 Strong and Weak Acids and Bases

LO 10.1(a): explain qualitatively the differences in behaviour between strong and weak acids and bases in terms of the extent of
dissociation

A strong BrØnsted acid is a proton-donor that dissociates or ionises completely in water to give H3O+.
It donates a proton more readily compared to the H3O+ ion.

e.g. HCl + H2O → Cl– + H3O+

strong acid conjugate base

• The conjugate base of a strong acid has a very low tendency to accept a proton.
• The reverse reaction is negligible  single–headed arrow (→).
• Other examples of strong acids: HNO3, HBr, HI, HClO3, HClO4, H2SO4

A weak BrØnsted acid is a proton-donor that dissociates partially in water to give H3O+. It donates a
proton less readily compared to the H3O+ ion.

e.g. CH3CO2H + H2O ⇌ CH3CO2– + H3O+

weak acid conjugate base

• The conjugate base of a weak acid (CH3CO2– ) has a tendency to accept a proton.
• CH3CO2H and CH3CO2– is a conjugate acid-base pair that differ by one proton.
• The reverse reaction occurs to some extent  double–headed arrow (⇌).
• A mixture of mainly undissociated CH3CO2H molecules and the ions exists in solution.
• Other examples of weak acids: H2SO3, HNO2, H2CO3, H2S, HF, HCN, most organic acids

A strong BrØnsted base is a proton-acceptor that dissociates or ionises completely in water to give
OH−.

e.g. NaOH → Na+ + OH−

• Other examples of strong bases: KOH, Ba(OH)2

A weak BrØnsted base is a proton-acceptor that dissociates or ionises partially in water to give OH−.

e.g. NH3 + H2O ⇌ NH4+ + OH−

• Other examples of weak bases: hydrazine N2H4, amines such as CH3NH2, C6H5NH2

The strength of an acid (or base) is different from the concentration of the acid (or base).
Strength of an acid (or base) refers to the extent of its dissociation at equilibrium.
Concentration of an acid (or base) refers to the no. of moles of acid (or base) dissolved in 1 dm3 of
solution.

Exercise 1.2
Match each acid on the left with the correct description on the right.

0.001 mol dm–3 HNO3 • • concentrated but weak acid

4.0 mol dm–3 CH3CO2H • • dilute but strong acid
0.001 mol dm–3 CH3CH2CO2H • • dilute and weak acid

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2 CALCULATIONS INVOLVING ACIDS AND BASES

LO 10.1(b)part: explain the terms pH; Kw and apply them in calculations

2.1 Definition of pH and pOH

The concentration of H+ and OH– in an aqueous solution is usually quite small. Hence it is more
convenient to express the concentration of H+(aq) in terms of its negative logarithm to base 10.

pH = −lg [H+(aq)]
where symbol ‘p’ means ‘–log10’

Hence, [H+(aq)] = 10−pH

E.g. for 0.01 mol dm–3 HCl, [H+(aq)] = 10–2 mol dm–3 and pH = 2.

Note:
pH is a measure of the (total) concentration of H+ in a solution. It is not a measure of the strength of
the acid unless the two acids being compared have the same initial concentration (see Section 2.8).

Similarly, the concentration of OH–(aq) is commonly expressed in terms of its negative logarithm to
base 10.

pOH = −lg [OH–(aq)]

and [OH−(aq)] = 10−pOH

E.g. for 0.01 mol dm–3 NaOH, [OH–(aq)] = 10–2 mol dm–3 and pOH = 2.

2.2 Ionic product of water, Kw

Pure water conducts electricity slightly, due to the very slight self-ionisation or autoionisation of water
which produces trace concentrations of ions.

H2O(l) + H2O(l) ⇌ H3O+(aq) + OH–(aq)

A simpler way of representing the equilibrium is:

H2O(l) ⇌ H+(aq) + OH–(aq)

The equilibrium constant, Kc, for the reaction is given by:

[H+][OH–]
Kc =
[H2O]

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[H2O] = 55.6 mol dm–3 (water has density 1.00 g cm–3, so 1 dm3 of water has mass of 1000 g. Since
molar mass of water is 18.0 g mol−1, therefore 1000 g (1 dm3) of water contains 1000/18.0 = 55.6 mol
of water.)

The extent of self-ionisation of water is very small compared to the concentration of water
(55.6 mol dm–3), hence [H2O] is almost constant.

Therefore, Kc  [H2O] = [H+][OH–]

or Kw = [H+][OH–]

where Kw is known as the ionic product of water. The value of Kw depends only on temperature. It is
always a constant at constant temperature.

Taking –lg on both sides of equation:

–lg Kw = (–lg [H+]) + (–lg [OH–])

pKw = pH + pOH * remember the symbol ‘p’ means ‘–log10’

Hence, we can determine the value of pH, given Kw value at the specified temperature and the pOH
value, and vice versa.

2.3 Relationship between [H+(aq)], [OH–(aq)] and pH

In pure water as well as any aqueous solution, the following equilibrium exists:

H2O(l) ⇌ H+(aq) + OH–(aq)

where Kw always = [H+][OH–] and pKw = pH + pOH.

When [H+(aq)] = [OH–(aq)] ➔ neutral solution

[H+(aq)] > [OH–(aq)] ➔ acidic solution
[H+(aq)] < [OH–(aq)] ➔ alkaline solution

At 25oC, Kw = 1.00  10–14 mol2 dm–6 (value is given in the Data Booklet)

And so pKw = pH + pOH = 14

Hence at 25o C, the pH of acidic, basic and neutral solutions can be calculated as follows:
Table 1. Summary of [H+], [OH–], pH and pOH of acidic, basic and neutral solution at 25 oC

Type of solution [H+] / mol dm–3 [OH–] / mol dm–3 pH pOH

Neutral = 1.0  10 –7 = 1.0  10 –7 = 7.00 = 7.00
Acidic > 1.0  10–7 < 1.0  10 –7 < 7.00 > 7.00
Basic < 1.0  10 –7 > 1.0  10 –7 > 7.00 < 7.00

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Like other equilibrium constants, the value of Kw depends only on temperature:

Table 2. Kw values and [H+] of water at different temperatures

Temperature / oC Kw / mol2 dm–6 [H+] = [OH–] = √Kw / mol dm–3
0 1.5  10–15 3.9  10–8
10 3.0  10–15 5.5  10–8
25 1.0  10–14 1.0  10–7
40 3.0  10–14 1.7  10–7
60 9.5  10–14 3.1  10–7

Exercise 2.1
With reference to the above data in Table 2, state whether the following statements are true or
false.
(i) The ionic dissociation of water, H2O(l) ⇌ H+(aq) + OH–(aq), is an endothermic process.

(ii) When water is heated, the concentration of H+(aq) increases.

(iii) When water is heated, the concentration of OH–(aq) increases.
(iv) In pure water, the concentration of H+(aq) is higher than that of OH–(aq) at 60 oC.
(v) Water remains a neutral liquid at 60 oC.
(vi) The pH of pure water at temperatures greater than 25 oC is greater than 7.

2.4 pH of Strong Acid / Strong base solutions

LO 10.1(c)part: calculate [H+(aq)] and pH values for strong acids, strong bases

Strong acids and strong bases are fully dissociated, hence

[H+] = [strong monobasic acid] and [H+] = 2  [strong dibasic acid]
Similarly, [OH−] = [strong monoacidic base] and [OH−] = 2  [strong diacidic base]

Note: If the concentration of the acid or base is 10–7 mol dm–3 or lower, the contribution of H+ or OH–
from auto-ionisation of H2O becomes significant. We should then take into consideration the
contribution of H+ or OH– from auto-ionisation of H2O in the calculation (See Exercise 2.2 Q3).

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Exercise 2.2 (Worked Example)

1. An aqueous solution contains 1.0  10–5 mol dm–3 of hydrogen iodide (a strong acid). Calculate
the concentration of H+ in mol dm–3, and hence the pH of this solution at 25 oC.

HI(aq) → H+(aq) + I–(aq)

[H+] = [HI] = 1.00  10–5 mol dm–3
pH = –lg [H+] = –lg (1.0  10–5) = 5.00

2. An aqueous solution contains 0.010 mol dm–3 of Ba(OH)2 (a strong base) and 0.050 mol dm–3 of
KOH. Calculate the pH of this solution at 25 oC.

Ba(OH)2(aq) → Ba2+(aq) + 2OH–(aq)

KOH(aq) → K+(aq) + OH–(aq) Note: KOH is also a strong base
Total [OH–] = 2  0.010 + 0.050 = 0.070 mol dm–3
pOH = −lg [OH–] = 1.15
pH = 14 – pOH = 12.8

3. An aqueous solution contains 1  10–8 mol dm–3 of HNO3. Calculate the pH of this solution.

HNO3 (aq) → H+ (aq) + NO3– (aq)

H2O (l) ⇌ H+ (aq) + OH– (aq) (auto–ionisation of water)
Hence, [H+] ≈ 10–8 + 10–7 = 1.1  10–7 mol dm–3
pH = – lg (1.1  10–7) = 6.96

Note:
[H+] from water = 10–7 mol dm–3 is an approximation.
As the concentration of the acid is lower than 10–7 mol dm–3, the contribution of H+ from
auto-ionisation of H2O becomes significant.

Exercise 2.3
1. An aqueous solution contains 0.10 mol dm–3 of calcium hydroxide (a strong base). Calculate the
concentration of OH– in mol dm–3, and hence the pH of this solution at 25 oC.
{[OH–] = 0.20 mol dm–3, pH = 13.3}

2. Solution X contains HCl, it has pH 2.2. Solution Y has the same volume as solution X. Solution Y
contains HNO3 and has pH 1.6. The two solutions are mixed. Calculate the pH of the resulting
solution.
[1.80]

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2.5 Acid Dissociation Constant (Ka) and Base Dissociation constant (Kb)
LO 10.1(b)part: explain the terms Ka; pKa; Kb; pKb and apply them in calculations, including the relationship Kw = KaKb

2.5.1 Acid Dissociation Constant (Ka)

A weak acid HA dissociates partially in water to give H3O+.

HA + H2O ⇌ A– + H3O+

In dilute aqueous solution, [H2O] is almost constant (at 55.6 mol dm–3). The equilibrium constant may
be written as:

[H+]eqm[A–]eqm
Ka = mol dm–3
[HA]eqm

and pKa = −lg Ka

• For strong acids, e.g. HCl, Ka is very large and not used.
• The value of Ka indicates the extent to which the weak acid dissociates in water at the specified
temperature.
• To compare the strength of two weak acids, compare their Ka values.
• At the same temperature, larger Ka (smaller pKa)  stronger acid.
• Like other equilibrium constants, the value of Ka depends only on temperature.

Table 3. Some weak acids and their Ka values at 25 oC

Acid dissociation equilibrium reaction Ka /mol dm–3
CH3CO2H + H2O ⇌ CH3CO2– + H3O+ 1.8  10–5
HCO2H + H2O ⇌ HCO2– + H3O+ 1.8  10–4
C6H5CO2H + H2O ⇌ C6H5CO2– + H3O+ 6.5  10–5
HCN + H2O ⇌ CN– + H3O+ 4.9  10–10

2.5.2 Base Dissociation Constant (Kb)

A weak base dissociates partially in water to give OH–.

B + H2O ⇌ BH+ + OH–

In dilute aqueous solution, [H2O] is almost constant (at 55.6 mol dm–3). The equilibrium constant may
be written as:
[BH+]eqm[OH–]eqm
Kb = mol dm–3
[B]eqm

and pKb = −lg Kb

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• For strong bases, e.g. NaOH, Kb is very large and not used.
• The value of Kb indicates the extent to which the weak base dissociates in water at the specified
temperature.
• To compare the strength of two weak bases, compare their Kb values.
• At the same temperature, larger Kb (smaller pKb)  stronger base.
• The value of Kb depends only on temperature.

Table 4. Some weak bases and their Kb values at 25 oC

Base Dissociation equilibrium reaction Kb /mol dm–3
NH3 + H2O ⇌ NH4+ + OH– 1.8  10–5
CH3NH2 + H2O ⇌ CH3NH3+ + OH– 4.4  10–4
CH3CO2– + H2O ⇌ CH3CO2H + OH– 5.6  10–10

• In aqueous solution, the two large classes of weak bases are nitrogen-containing molecules such
as NH3 and amines (e.g. CH3CH2NH2), and the anions or conjugate bases of weak acids (e.g.
ethanoate ion, CH3CO2–).

2.5.3 Relationship between Ka, Kb and Kw for conjugate acid-base pairs

Consider the weak acid, CH3CO2H, and its conjugate base, CH3CO2–.

CH3CO2H ⇌ CH3CO2– + H+

[CH3CO2–][H+]
Ka = –––––––––––––––––––– (1)
[CH3CO2H]

CH3CO2– + H2O ⇌ CH3CO2H + OH–

[CH3CO2H][OH–]
Kb = –––––––––––––––––––– (2)
[CH3CO2–]

(1)  (2), Ka  Kb = [H+] [OH–] = Kw

Therefore, for any conjugate acid–base pair,

Ka  Kb = Kw

Taking –lg on both sides of equation:

(–lg Ka) + (–lg Kb) = –lg Kw

pKa + pKb = pKw * remember the symbol ‘p’ means ‘–log10’

Hence, we can determine the value of Ka of an acid, given the Kb value of its conjugate base and vice
versa.

From Ka  Kb = Kw , we see that for a conjugate acid-base pair,

as the strength of the acid decreases (smaller Ka),
the strength of its conjugate base increases (larger Kb) and vice versa.

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2.6 Degree of dissociation

The fraction of molecules which is ionised into ions in water is called the degree of dissociation, .

For an acid,
amount ionised [acid]dissociated
 = =
initial amount [acid]initial

In general, for a strong acid or strong base,  is close to 1

for a weak acid or weak base,  << 1

2.7 pH of Weak Acid / Weak Base Solutions

LO 10.1(c)part: calculate [H+(aq)] and pH values for weak monobasic (monoprotic) acids, and weak monoacidic bases [Calculations
involving weak acids/bases will not require solving of quadratic equations]

Since weak acids and weak bases dissociate partially in water, [H+] or [OH−] in the solution will be
lower than the initial concentration of the weak acid or weak base.

We use Ka or Kb to calculate the [H+] or [OH−] in the solution at equilibrium.

Exercise 2.4 (Worked Example)

1. Find (a) the pH and (b) the degree of dissociation of a solution of ethanoic acid, CH3CO2H, of
concentration 0.1 mol dm–3. [Given: Ka of CH3CO2H = 1.8  10–5 mol dm–3]

(a)
HA ⇌ H+ + A–
Initial conc 0.1
Change −x +x +x
Eqm conc 0.1 – x x x

Important note:
[H+]eqm = [A–]eqm is true only if the solution contains only weak acid HA (i.e. all H+ ions and A– ions
present in the solution come only from the dissociation of HA and there are no added H+ ions or A–
ions). This equation cannot be used for calculations involving buffer solutions (see Section 4.4).

[H+]eqm[A–] eqm x2 x2
Ka = =  (assume x << 0.1)
[HA] eqm 0.1 – x 0.1

x = [H+] = √1.8 × 10−5 × 0.1 = 1.34  10–3 mol dm–3

pH = – lg (1.34  10–3) = 2.87

Note:
Solving quadratic equations is not required for Chemistry ‘A’ Levels. The assumption (x << 0.1) is
valid since a weak acid only dissociates partially. Without the approximation, [H+] would have been
1.33 × 10–3 mol dm–3. The difference is insignificant because it is within the limits of the accuracy to
which the data is given.

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(b) α = (1.34  10–3)/0.1 = 1.34  10–2 (or 1.34% dissociated)

Exercise 2.5
Calculate (a) the pH and (b) the degree of dissociation of a solution of 0.125 mol dm −3 aqueous
ammonia at 298 K.
[Given Kb for ammonia = 1.78 × 10−5 mol dm−3 at 298 K]
[(a) 11.2 ; (b) 1.19 × 10−2 or 1.19%]

Exercise 2.6 (Worked Example)

Caffeine, C8H10N4O2, a stimulant found in coffee and tea, is a weak base.
C8H10N4O2 + H2O ⇌ (C8H11N4O2)+ + OH–

At 25 oC, a 0.020 mol dm–3 caffeine solution has a pH of 11.5.

(a) Write the Kb expression of caffeine and calculate its value at 25 oC.

[C8 H11 N4 O2 + ][OH− ]

Kb =
[C8 H10 N4 O2 ]

pOH = 14 – pH = 14 – 11.5 = 2.5  [OH–] = 10–2.5 = 3.162  10–3 mol dm–3

2
(3.162 × 10−3 )
Kb = = 5.94  10–4 mol dm–3
0.020 − 3.162 × 10−3

Note: If [H+] at equilibrium is known, the assumption [H+] << [HA] should not be made in the
calculations.

(b) Calculate the degree of dissociation,  for caffeine at 25 oC.

3.162 ×10−3
 = = 0.158
0.020

Exercise 2.7
The pH of a weak acid, HA, of concentration 0.100 mol dm–3 was found to be 3.0.
Calculate the Ka and pKa of the acid.
[Ka = 1.01  10–5 mol dm–3, pKa = 5.00]

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2.8 Strength of Acids and Bases

LO 10.1(a): explain qualitatively the differences in behaviour between strong and weak acids and bases in terms of the extent of
dissociation

The strength of an acid (or base):

• is a measure of how readily the acid (or base) donates its proton (or accepts a proton).
• depends on its structure (refer to Organic Chemistry Topic 16 Hydroxy Compounds, Topic
18 Carboxylic Acids for acid strengths of different phenols and carboxylic acids, as well as
Topic 19 Nitrogen Compounds to compare the basic strength of amines)
• is indicated by its Ka (or Kb) value [see Section 2.5.1 and 2.5.2]
• is different from the concentration of the acid (or base) [see Exercise 2.4]

Are pH or degree of dissociation, α, reliable indicators of the strength of an acid (or base)?

Exercise 2.8
In Exercise 2.4, the pH and the degree of dissociation of a solution of ethanoic acid of
concentration 0.1 mol dm–3 were found to be: pH: …….…… degree of dissociation, α: …………
[Given: Ka of CH3CO2H = 1.8  10 mol dm ]
–5 –3

Now, find (a) the pH and (b) the degree of dissociation of ethanoic acid of concentration
0.001 mol dm–3. How have the pH and α been affected by the dilution?

[(a) 3.87; (b) 0.134 or 13.4%]

The diagrams below show how the values of pH, α and Ka for a weak acid vary with dilution (i.e. volume
of water increases) at a constant temperature:

pH α Ka

7 1 Ka

Volume of water Volume of water Volume of water

(pH → 7 as dilution →  ) (α → 1 as dilution → )

Ka does not vary with concentration. It is a constant at constant temperature. Therefore Ka is the best
indicator of the strength of a weak acid.

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Exercise 2.9

Each of the following reactions contains two BrØnsted acids and two BrØnsted bases. Suggest with
brief reasoning which is the stronger acid and which is the stronger base.

(a) (worked example)

NH3(aq) + H2O(l) ⇌ NH4+(aq) + OH–(aq) Kc = 3.2  10–7
weaker base weaker stronger stronger base
acid acid

Kc is very small, this suggests that the position of equilibrium lies very much to the left.
So NH4+ is a better proton donor than H2O, OH– is a better proton acceptor than NH3.

(b) C6H5O– + CH3CO2H ⇌ C6H5OH + CH3CO2– Kc = 1.3  105

Note:
From part (b), we see that the stronger acid is able to protonate the conjugate base of the weaker
acid.
Strong acids (e.g. HCl) are often used to liberate the weak acids (e.g. CH3CO2H) from their salt (e.g.
CH3CO2–Na+).

HCl (aq) + CH3CO2–(aq) → Cl–(aq) + CH3CO2H(aq)

stronger acid conjugate weaker acid
base

3 pH OF SALT SOLUTIONS
LO 4(b): show understanding of, and apply the Brønsted-Lowry theory of acids and bases, including the concept of conjugate acids and
conjugate bases
LO 10.1(b): explain the terms pH; Ka; pKa; Kb; pKb; Kw and apply them in calculations, including the relationship Kw = KaKb
LO 10.1(c)part: calculate [H+(aq)] and pH values for weak monobasic (monoprotic) acids, and weak monoacidic bases [Calculations
involving weak acids/bases will not require solving of quadratic equations]

An ionic salt may be prepared from a reaction between an aqueous acid and an aqueous base.
E.g. KCl may be prepared from KOH(aq) and HCl (aq).

Salt hydrolysis is a reaction in which ions of a salt react with water to produce OH– or H3O+ ions.

3.1 Salt derived from a strong acid and a strong base

Ions in salts derived from a strong acid and a strong base (e.g. NaCl, KNO3) do not undergo salt
hydrolysis. Hence the resulting solution is neutral  pH = 7 at 25 oC.

However, ions in salts derived from weak acids/bases, as well as metal cations with high charge
density, could undergo hydrolysis to result in acidic or alkaline solutions (pH less/greater than 7 at
25 oC).

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3.2 Salt derived from a weak acid and a strong base

• Consider CH3CO2–Na+ which is derived from the salt of CH3CO2H and NaOH.
• CH3CO2H is a weak acid so its conjugate base CH3CO2– is a stronger base than water. CH3CO2–
undergoes hydrolysis forming OH– ions.

CH3CO2– (aq) + H2O(l) ⇌ CH3CO2H(aq) + OH–(aq)

• Hence [OH–] > [H3O+] and the salt solution of CH3CO2–Na+ is alkaline.
• At 25 oC, pH of a solution of CH3CO2–Na+ is > 7.

Note:
• CH3CO2– (aq) is a stronger base than water so is able to accept a proton from water.
• However, it is still a weak base (Kb of CH3CO2– = 5.6  10–10 mol dm–3). Hence a reversible arrow
‘⇌’ is used in the salt hydrolysis equation.
• The cation Na+ does not undergo hydrolysis due to its low charge density.

3.3 Salt derived from a strong acid and a weak base

• Consider NH4+Cl– which is derived from the salt of HCl and NH3.
• NH3 is a weak base so its conjugate acid NH4+ is a stronger acid than water. NH4+ undergoes
hydrolysis forming H3O+ ions.

NH4+(aq) + H2O(l) ⇌ NH3(aq) + H3O+(aq)

• Hence [H3O+] > [OH–] and the salt solution of NH4Cl is acidic.
• At 25 oC, pH of a solution of NH4Cl is < 7.

Note:
• NH4+ is a stronger acid than water so is able to donate a proton to water. (see Exercise 2.9)
• However, it is still a weak acid (Ka of NH4+ = 5.56  10–10 mol dm–3). Hence a reversible arrow
‘⇌’ is used in the salt hydrolysis equation.
• The anion Cl– (derived from strong acid HCl) is a weaker base than water and so does not
hydrolyse.

3.4 Salt derived from a weak acid and a weak base

E.g. CH3CO2–NH4+
• Both cation and anion hydrolyse.
• pH of the salt solution depends on Ka of the acid (cation) and Kb of the base (anion)

If Ka(cation) > Kb(anion) → salt solution is acidic

Ka(cation) = Kb(anion) → salt solution is neutral

Ka(cation) < Kb(anion) → salt solution is basic

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3.5 Salt containing an aqueous metal cation with high charge density
LO 5(e)(iv)part: describe and explain the reactions of the chlorides with water (for AlCl3)

Consider the ionic compound, aluminium nitrate Al(NO3)3. When it dissolves in water, the Al3+ and
NO3– ions are separated and surrounded by water molecules.

Al(NO3)3(s) + 6H2O(l) → [Al(H2O)6]3+(aq) + 3NO3–(aq)

The Al3+ cations are coordinated to water molecules through dative (co–ordinate) bonds to form the
complex ion, [Al(H2O)6]3+.

The Al3+ ion is small and highly charged, so it has high charge density. It withdraws sufficient electron
density from the O–H bonds of the coordinated H2O molecules, weakening the O–H bonds. When
one O–H bond breaks, a proton is released:

[Al(H2O)6]3+(aq) + H2O(l) ⇌ [Al(H2O)5(OH)]2+(aq) + H3O+(aq)

We call this a hydrolysis reaction. Observe that [Al(H2O)6]3+ is acting as a weak BrØnsted acid. Since
[H3O+] > [OH–], Al3+(aq) is acidic and pH < 7 at 25 oC.

Figure 1. [Al(H2O)6]3+ acting as an acid, donating a proton to another H2O molecule

Other metal cations like Fe3+ and Cr3+ also form complex ions with water which undergo the hydrolysis
reaction to produce an acidic solution.

Table 5. Formula of the complex ions of Fe3+, Cr3+ and Al3+ with water and their Ka values
Metal ion Complex ion formed with water Ka / mol dm–3 (at 25 oC)
Fe3+ [Fe(H2O)6]3+(aq) 6  10–3
Cr3+ [Cr(H2O)6]3+(aq) 1  10–4
Al3+ [Al(H2O)6]3+(aq) 1  10–5

Exercise 3.1
State whether the following solutions are acidic, alkaline or neutral. Write an equation, including state
symbols, for any hydrolysis reaction.

(a) KBr(aq)

(b) Na2CO3(aq)

(c) CH3NH3+Cl– (aq)

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(d) (worked example)

NH4HS(aq), given: Kb of NH3 = 1.8  10–5 mol dm–3
Ka1 of H2S = 9  10–8 mol dm–3 (H2S is a weak diprotic acid)
Ka1 : H2S(aq) ⇌ HS–(aq) + H+(aq)

Both ions undergo hydrolysis:

NH4+(aq) + H2O(l) ⇌ NH3(aq) + H3O+(aq) ––––(1)
HS–(aq) + H2O(l) ⇌ H2S(aq) + OH–(aq) ––––(2)

Ka of NH4+ = Kw / Kb of NH3 = 10−14 / (1.8×10−5) = 5.6  10–10 mol dm–3

Kb of HS– = Kw / Ka of H2S = 10−14 / (9×10−8) = 1.1  10–7 mol dm–3

Since Kb of HS– > Ka of NH4+, (2) occurs to a larger extent than (1).
Thus, resultant [OH–] > [H3O+]. The salt solution is alkaline.

(e) (worked example) FeCl3(aq)

Acidic (Fe3+ is a metal cation with high charge density. The complex ion [Fe(H2O)6]3+(aq)
undergoes hydrolysis.)
[Fe(H2O)6]3+(aq) + H2O(l) ⇌ [Fe(OH)(H2O)5]2+(aq) + H3O+(aq)

3.6 Calculations of pH of salt solutions

The pH of salt solutions can be calculated using the following general strategy:

1. Determine whether the ions in the salt undergoes hydrolysis in water by considering the strength
of acid and base from which the salt is derived
2. Write an equation for any hydrolysis that takes place in water to produce H3O+ or OH– ions.
3. Calculate [H3O+] or [OH–] using the Ka or Kb of the ion that undergoes hydrolysis in water.

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Exercise 3.2 (Worked Example)

Calculate the pH of 0.10 mol dm–3 CH3CO2– Na+(aq) at 25oC.
Ka value for ethanoic acid is 1.8  10–5 mol dm–3.

CH3CO2– + H2O ⇌ CH3CO2H + OH– (salt hydrolysis)

–3
Initial conc / mol dm 0.10
Change / mol dm–3 −x +x +x
Eqm conc / mol dm–3 0.10 − x x x

Kw 10−14
Kb (CH3CO2–) = = = 5.56  10–10
Ka (CH3CO2H) 1.8 × 10−5

x2
Kb = (from ICE table)
0.10 − x

x2
5.56  10–10 ≈ (assuming x <<0.10)
0.10

[OH–] = x = 7.45  10–6 mol dm–3

pOH = ‒ lg [OH–] = 5.13
 pH = 14−pOH = 8.87 (relationship in section 2.3)

Exercise 3.3 (Worked Example)

Calculate the pH of 0.450 mol dm–3 ammonium chloride at 298 K.
(Given Kb for ammonia = 1.78 x 10–5 mol dm–3 )

NH4+ + H2O ⇌ NH3 + H3O+

Initial conc / mol dm–3 0.450
Change / mol dm–3 −x +x +x
Eqm conc / mol dm–3 0.450 − x x x

[NH3 ][H3 O+ ]
Ka =
[NH4 + ]
10−14 x2 x2
−5 = ≈ (assume x << 0.450)
1.78 × 10 0.450 − x 0.450

+ 10-14 -5 −3
[H ] √
x = 3O = -5 × 0.450 = 1.59 × 10 mol dm
1.78 × 10
pH= − lg(1.59 × 10−5 ) = 4.80

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4 BUFFER SOLUTIONS

4.1 Definition of Buffer solutions

LO 10.1(f)(i): explain how buffer solutions control pH

A buffer solution is one that is able to resist pH changes upon addition of a small amount of acid or
base.

A buffer (usually) consists of two species which make up a conjugate acid-base pair of a weak acid or
base – one species acts as weak BrØnsted acid and the other species acts as weak BrØnsted base. An
example is a mixture of ethanoic acid (CH3CO2H) and ethanoate ion (CH3CO2–).

Exercise 4.1
Using your knowledge of strong and weak acids and bases and your understanding of conjugate acid-
base pairs, suggest whether each of the following mixtures can act as a buffer solution.

1. NaHCO3 and Na2CO3

2. CH3CO2H and NaCl
3. HNO3 and NaNO3

4.2 Preparing a Buffer (Background info)

4.2.1 Mixing a weak acid and its conjugate base

Consider a buffer consisting of a weak acid, CH3CO2H, and its conjugate base, CH3CO2– ions

Ethanoic acid is a weak acid and dissociates partially.

CH3CO2H(aq) ⇌ CH3CO2–(aq) + H+(aq) –––––––––––––––––––––(1)

Adding sodium ethanoate (completely soluble in water) to this solution adds a lot of extra ethanoate
ions.
CH3CO2–Na+(aq) → CH3CO2–(aq) + Na+(aq)

According to Le Chatelier's Principle, the position of equilibrium (1) shifts further to the left (i.e. the
dissociation of ethanoic acid is suppressed). Similarly, hydrolysis of the ethanoate ion in water is
suppressed by the presence of the ethanoic acid.

The solution now contains the following:

• large reservoir of un-ionised ethanoic acid;
• large reservoir of ethanoate ions from the sodium ethanoate;
and can act as a buffer solution.

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4.2.2 Mixing a weak base and its conjugate acid

Consider a buffer consisting of a weak base, aqueous NH3 and its conjugate acid, NH4+ ions

Ammonia is a weak base and ionises partially.

NH3(aq) + H2O(l) ⇌ NH4+(aq) + OH– (aq) –––––––––––––––––––(2)

Adding ammonium chloride (completely soluble) to this solution adds a lot of extra ammonium ions.

NH4+Cl–(aq) → NH4+(aq) + Cl–(aq)

In a similar explanation to Section 4.2.1, the solution now contains a large reservoir of un-ionised
ammonia and a large reservoir of ammonium ions from the ammonium chloride, and can act as a
buffer solution.

Note: Buffer solutions with pH < 7 (at 25 oC) may be referred to as ‘acidic’ buffers while buffer solutions
with pH > 7 (at 25 oC) may be referred to as ‘alkaline’ buffers.

4.2.3 Partial neutralisation of a weak acid (or weak base)

Another way to prepare a buffer is to form one of the species by partial neutralisation of the other
species. For example, the ethanoic acid/ethanoate buffer can be prepared by mixing suitable amounts
of ethanoic acid and NaOH. The key is to add less NaOH than is required for complete neutralisation,
such that the OH– ions will react with part of the total ethanoic acid present to produce the ethanoate
ions needed, at the same time leaving some ethanoic acid behind, to give a mixture consisting of both
ethanoic acid and ethanoate ions.

This method is based on the same chemical process that occurs when a weak acid is titrated with a
strong base (see Section 5.1.2) or when a weak base is titrated with a strong acid (see Section 5.1.3).

Exercise 4.2 (Worked Example)

Which combination of substance, when mixed, would not give a buffer solution?

A 25 cm3 of 0.1 mol dm−3 HCl and 50 cm3 of 0.1 mol dm−3 NH3
B 25 cm3 of 0.1 mol dm−3 NaOH and 25 cm3 of 0.2 mol dm−3 NH4+
C 25 cm3 of 0.2 mol dm−3 HCl and 25 cm3 of 0.1 mol dm−3 CH3CO2−
D 25 cm3 of 0.1 mol dm−3 NaOH and 25 cm3 of 0.2 mol dm−3 CH3CO2H

Ans: C
A NH3 is in excess. (NH3 + H+ → NH4+)
After all HCl reacts with NH3, resulting mixture consists of unreacted NH3 (weak base) and
NH4+ (conjugate acid) formed. Hence the resulting mixture is a buffer.

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B NH4+ is in excess. (NH4+ + OH− → NH3 + H2O)

After all NaOH reacts with NH4+, resulting mixture consists of NH3 (weak base) formed and
unreacted NH4+ (conjugate acid). Hence the resulting mixture is a buffer.
C HCl is in excess. (CH3CO2− + H+ → CH3CO2H)
After all CH3CO2− reacts with HCl, the resulting mixture consists of unreacted HCl and
CH3CO2H formed. This mixture does not consist of a conjugate acid-base pair of a weak acid
or base and is not a buffer.
D CH3CO2H is in excess. (CH3CO2H + OH− → CH3CO2− + H2O)
After all NaOH reacts with CH3CO2H, the resulting mixture consists of unreacted CH3CO2H
(weak acid) and CH3CO2− (conjugate base) formed. Hence the resulting mixture is a buffer.

4.3 Explaining Buffer Action

LO 10.1(f)(i): explain how buffer solutions control pH

How does the buffer consisting of large reservoirs of CH3CO2H and its conjugate base CH3CO2– resist
pH changes on addition of small amount of acid or base?

(i) When a small amount of H+ is added to this buffer, the H+ ions react with the large reservoir of
the CH3CO2– (conjugate base):

CH3CO2– + H+ → CH3CO2H

The added H+ ions are removed and [CH3CO2H] increases slightly and [CH3CO2–] decreases
slightly.
As the original amounts of CH3CO2H and CH3CO2– are large compared to the amount of H+ ions
added, the ratio [CH3CO2–] / [CH3CO2H] remains almost constant.
Since Ka = [H+][CH3CO2–] / [CH3CO2H], and Ka is a constant, so [H+] and pH remains almost
constant.

(ii) When a small amount of OH– is added to this buffer, the OH– ions react with the large reservoir
of the un–ionised CH3CO2H molecules:

CH3CO2H + OH– → CH3CO2– + H2O

The added OH– ions are removed and [CH3CO2H] decreases slightly and [CH3CO2–] increases
slightly.
As the original amounts of CH3CO2H and CH3CO2– are large compared to the amount of OH−
ions added, the ratio [CH3CO2–] / [CH3CO2H ] remains almost constant.
Since Ka = [H+][CH3CO2–] / [CH3CO2H], and Ka is a constant, so [H+] and pH remains almost
constant.

Note: Buffer action equations are written with single (non-reversible) arrows.

Exercise 4.3
How does a buffer solution containing NH3(aq) and NH4Cl(aq) resist changes in pH when small amounts
of acid or alkali are added?

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4.4 Calculating pH of Buffer solutions

LO 10.1(g): calculate the pH of buffer solutions, given appropriate data

4.4.1 pH of buffer consisting of weak acid HA and its conjugate base A–

In a buffer consisting of HA and its conjugate base A–, the following equilibrium exists:

HA(aq) + H2O(l) ⇌ H3O+(aq) + A– (aq)

[H+]eqm[A–]eqm
and Ka =
[HA]eqm

As the presence of excess A–(aq) suppresses the dissociation of HA,

[HA]eqm  [HA]initial (since α is very small)
[A ]eqm  [A ]initial
– –
(since [A–] from HA is very small)

[H+]eqm[A–]initial [H+]eqm[conjugate base]

therefore Ka  =
[HA]initial [acid]

[acid]
and [H+] = Ka ×
[conjugate base]

Hence pH of the buffer can be found easily.

Important note:
In this case of the buffer, [H+] ≠ [A– ] since the solution consists of significant amounts of HA and A–
and the A– ions do not just come from the weak acid dissociation of HA alone, unlike in a solution of
pure weak acid HA (see Exercise 2.4).

Alternatively, to find pH of a buffer, take –lg on both sides of boxed equation,

[acid]
− lg[H+ ] = −lgKa − lg
[conjugate base]

[conjugate base]
pH = pKa + lg Henderson–Hasselbalch Equation
[acid]

4.4.2 pH of buffer consisting of weak base and its conjugate acid

In a similar manner as above, the pOH and pH of this buffer can be found using:

[base] [conjugate acid]

[OH−] = Kb × or pOH = pKb + lg
[conjugate acid] [base]

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Exercise 4.4 (Worked Example)

Calculate the pH of a solution consisting of 0.010 mol of ethanoic acid and 0.010 mol of sodium
ethanoate dissolved in 1 dm3 of water. (Ka of ethanoic acid = 1.8  10–5 mol dm–3)

[CH3CO2H] = 0.010 mol dm–3

[CH3CO2–] = 0.010 mol dm–3

[H+][CH3CO2– ]
Ka =
[CH3CO2H]
[H+] (0.010)
1.8  10 –5
=
0.010

[H+] = 1.8  10–5 mol dm–3

 pH = – lg [H+] = 4.74

Note: pKa = − lg Ka = 4.74

In Section 4.5, you will observe that pH = pKa when [weak acid] = [conjugate base].

Application Example
Calculate the change in pH when 1 cm3 of a 1.00 mol dm–3 NaOH is added to 1 dm3 of
(a) water; (b) the buffer solution in Exercise 4.2 above.

(a) No. of moles of NaOH added = 1 ÷ 1000  1.00 = 0.001

[OH–] = (0.001 ÷ 1001 × 1000) Note: Remember to divide by the new total volume as
= 9.99  10–4 mol dm–3 volume of solution has changed upon adding aq. NaOH.

pOH = 3.00  pH = 11.0

Change in pH = 11.0 – 7 = +4 units

(b) CH3CO2H + OH– → CH3CO2– + H2O Strategy: Decide which buffer component removes the
added NaOH, then work out the new concentration of
No. of moles of NaOH added = 0.001
each buffer component.
After the reaction,
[CH3CO2–] = (0.010 + 0.001) / V Tip: The new total volume of the solution can just be
[CH3CO2H] = (0.010 – 0.001) / V denoted as V, as this would cancel in the Ka expression.

[H+] (0.010 + 0.001) / V

Ka = 1.8  10–5 =
(0.010 – 0.001) / V
[H+] = 1.47  10–5 mol dm–3
 pH = – lg [H+] = 4.83
Change in pH = 4.83 – 4.74= +0.09 units
From the above calculation, we can see that a buffer solution resists pH changes much better than
water, when a small amount of strong base is added.

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4.5 Buffer Capacity (Background info)

The capacity of a buffer is the quantity of H3O+ or OH– it can remove before its pH changes drastically.
A buffer should have high [weak acid] and [conjugate base], or high [weak base] and [conjugate acid],
to provide a large reservoir of the relevant components. The more concentrated the components of
a buffer, the greater the buffer capacity.

Buffer capacity also depends on the ratio of [weak acid] and [conjugate base], or ratio of [weak base]
and [conjugate acid]. For example, if a buffer contains a much higher proportion of the weak acid
compared to its conjugate base, then it is more effective in resisting changes in pH on addition of OH−
as compared to the addition of H3O+. It can be shown that the most effective buffer has

[conjugate base] [conjugate acid]

= 1 or = 1
[acid] [base]

LO 10.1(d): describe the changes in pH during acid-base titrations and explain these changes in terms of the strengths of the acids and
bases
Using the boxed equations in Section 4.4.1 and 4.4.2, it follows that, for this most effective buffer,
pH = pKa (for acidic buffer) or pOH = pKb (for alkaline buffer)

This buffer is said to have the maximum buffer capacity and it can most effectively resist a change in
pH in either direction (i.e. when either acid or base is added).

4.6 Effective Buffer Range (Background info)

The further the buffer-component concentration ratio is from 1, the less effective the buffering action
(i.e., lower buffer capacity).

In practice, a buffer is no longer effective when

[acid]/[conjugate base] or [base]/[conjugate acid] > 10/1 or < 1/10.

Since log10 (10/1) = +1 and log10 (1/10) = –1,

[acid]
for an acidic buffer, [H+] = Ka   effective buffer pH range = pKa  1
[conjugate base]

[base]
for an alkaline buffer, [OH–] = Kb   effective buffer pOH range = pKb  1
[conjugate acid]

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Exercise 4.5 (Worked Example)

Which of the following acids would be the best choice to combine with its sodium salt to make a
solution buffered at pH 4.25?
For your choice, calculate the ratio of the conjugate base to the acid concentrations required to
attain the desired pH.

Acid pKa
chlorous acid (HClO2) 1.95
nitrous acid (HNO2) 3.34
methanoic acid (HCO2H) 3.74
hypochlorous acid (HClO) 7.54

The best choice is methanoic acid because the desired pH (4.25) is closest to and is within 1 unit
of its pKa value (3.74 ± 1).

[H+][conjugate base]
Ka =
[acid]

10–4.25 [conjugate base]

–3.74
10 =
[acid]

 [conjugate base] Check: Ratio is between 0.1 and 10

= 3.24
[acid] (effective range)

4.7 Buffer System in Human Blood

LO 10.1(f)(ii): describe and explain uses of buffer solutions, including the role of H2CO3/HCO3– in controlling pH in blood

The pH of our blood must be kept constant at about 7.4 since enzymes operate only within a narrow
pH range. Blood contains large amounts of the weak acid carbonic acid, H2CO3 (an aqueous solution
of CO2), and its conjugate base, HCO3– ions (bicarbonate). Together they help maintain the pH of blood
at 7.4. If blood pH falls below 6.8 or rises above 7.8, one can become sick or die. The bicarbonate
neutralises excess acids in the blood while the carbonic acid neutralises excess bases.

The following equilibria operate in the H2CO3/HCO3– buffer system:

H+(aq) + HCO3– (aq) ⇌ H2CO3(aq) ⇌ H2O(l) + CO2(g)

When H+ is added to the blood as a result of metabolic processes, the following reaction occurs

H+(aq) + HCO3– (aq) → H2CO3(aq)

The amount of HCO3– (relative to the amount of CO2) decreases; however, the amount of the change
is small compared to the large amount of HCO3– present in the blood.

When OH− is added, it is removed by the carbonic acid.

H2CO3(aq) + OH− → HCO3− (aq) + H2O(l)

Or CO2(aq) + OH− (aq) → HCO3− (aq)

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If blood pH rises above about 7.45, you can suffer from a condition called alkalosis.
This can arise from hyperventilation or oxygen deficiency at high altitude. It can lead
to over excitability of the central nervous system, muscle spasms and death. One way
to treat alkalosis is to breathe into a paper bag. The CO2 exhaled is recycled into the
body. Can you explain how that helps?

pH Regulation During Exercise : a tutorial on buffer in the body

http://www.chemistry.wustl.edu/~edudev/LabTutorials/CourseTutorials/bb/Buffer/Buffers.pdf

Exercise 4.6
The main buffering agent in blood plasma is the carbon dioxide/hydrogen carbonate system.

H2O + CO2 ⇌ H+ + HCO3– Ka = 7.90  10–7 mol dm–3

(a) Explain how the system above acts as a buffer when

(i) H+ ions, (ii) OH– ions
are added to the blood plasma.

(b) The pH of normal blood plasma is 7.40. Use the data above to calculate the ratio [HCO 3–]/
[CO2] and hence deduce whether blood has a greater capacity for absorbing H+ or OH– ions.

(c) Using the above buffer system, briefly explain why strenuous exercise leads to an increase
rate of breathing.

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5 ACID-BASE TITRATIONS
LO 10.1(d): describe the changes in pH during acid–base titrations and explain these changes in terms of the strengths of the acids and
bases

5.1 Acid-Base Titration Curves

During an acid-base titration, for example when

a base is added from the burette into an acid
placed in a conical flask, the pH of the solution
in the conical flask changes. Before the point of
complete neutralisation, the acid is in excess
while after the point of complete
neutralisation, the base is in excess. A salt is
also formed in the process. The pH of the
solution depends on the species present in the
conical flask after neutralisation of the acid by
the base. These changes in pH can be
monitored by measuring the pH of the solution
using a pH meter as the base is added to the
acid.

A titration curve is a graph of pH against the

volume of the titrant added and it shows how
the pH changes during a titration.

Figure 2. Monitoring pH changes during a titration with a

pH meter

Four types of acid-base titration curves are shown on the following pages. Note that in all of them,
the acid is in the conical flask while the base is added from the burette. To calculate the pH of the
solution at various points of the curve, you will need to apply the concepts you have learnt earlier on
calculation of pH involving strong acid / base, weak acid / base, salt solutions and buffer solutions.

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5.1.1 Strong Acid – Strong Base Titration

Consider addition of 0.10 mol dm–3 NaOH to 25.0 cm3 of 0.10 mol dm–3 HCl.

Features of the curve:

• At VNaOH = 0 cm3
Initial pH = pH of 0.10 mol dm–3 HCl = –lg 0.10
=1
HCl is a strong acid (fully dissociated in
water), so [H+] = [HCl].
Equivalence
X
point, pH = 7
• At 0 < VNaOH < 25 cm3
pH gradually rises as an increasing amount of
H+ is neutralised by the NaOH added.

• At VNaOH = 25 cm3
Equivalence point is reached. This is the point
where the acid is completely neutralised by
Volume of NaOH added / cm3 the base.
pH = 7 as the salt formed does not undergo
hydrolysis.

Suitable indicator:
methyl orange, screened methyl orange,
phenolphthalein, thymol blue,
thymolphathalein

Note the sharp pH change near equivalence

point (see parts (c) and (e)).

• At VNaOH > 25 cm3

There is excess NaOH present in the solution.
As NaOH is a strong base, [OH–] is high, hence
pH is high (exact value depends on [NaOH]
that is in excess).

[Worked example] Determine the pH of the solution in the conical flask at the point when each of the
following volumes of NaOH is added.

(a) 0.00 cm3

Since HCl is a strong acid, it dissociates completely.

[H+] = 0.10 mol dm–3
 pH = –lg (0.10) = 1.00

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(b) 12.50 cm3 (This is called the half–neutralisation or half–equivalence point.)

No. of moles of NaOH added = 12.50  10–3  0.10 = 1.25  10–3 mol
Initial no. of moles of HCl = 25.0  10–3  0.10 = 2.50  10–3 mol
 HCl is in excess.

No. of moles of HCl remaining = 2.50  10–3 – 1.25  10–3 = 1.25  10–3 mol
1.25 × 10−3
[HCl] remaining = = 0.0333 mol dm–3
(25.0 + 12.50) × 10−3
pH = –lg (0.0333) = 1.48

(c) 24.90 cm3

No. of moles of HCl remaining = 2.50  10–3 – 2.49  10–3 = 1.00  10–5 mol
1.00 × 10−5
[HCl] remaining = = 2.00  10–4 mol dm–3
(25.0 + 24.90) × 10−3
pH = –lg (2.00  10–4) = 3.70

(d) 25.00 cm3 (This is called the equivalence point.)

At this point, HCl is completely neutralised by NaOH. The only species present at this point is
NaCl. Since NaCl does not undergo hydrolysis in water, pH at this point = 7

(e) 25.10 cm3

No. of moles of NaOH added = 25.10  10–3  0.10 = 2.51  10–3 mol
Initial no. of moles of HCl = 25.0  10–3  0.10 = 2.50  10–3 mol
 NaOH is in excess.

No. of moles of NaOH unreacted = 2.51  10–3 – 2.50  10–3 = 1.00  10–5 mol
1.00 × 10−5
[NaOH] remaining = = 2.00  10–4 mol dm–3
(25.0 + 25.10) × 10−3
pOH = –lg (2.00  10–4) = 3.70
pH = 14 – 3.70 = 10.3

(f) 50.00 cm3

No. of moles of NaOH unreacted = 5.00  10–3 – 2.50  10–3 = 2.50  10–3 mol
2.50 × 10−3
[NaOH] remaining = = 0.0333 mol dm–3
(25.0 + 50.00) × 10−3
pOH = –lg (0.0333) = 1.48
pH = 14 – 1.48 = 12.5

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5.1.2 Weak Acid – Strong Base Titration

Consider addition of 0.10 mol dm–3 NaOH to 25.0 cm3 of 0.10 mol dm–3 CH3CO2H

Equivalence
X
point, pH > 7
buffer region

Volume of NaOH added / cm3

Features of the curve:
• At VNaOH = 0 cm3 Calculation of pH of the solution in the conical
–3
Initial pH = pH of 0.10 mol dm CH3CO2H flask when VNaOH = 0 cm3.
pH is not equal to 1.0 as CH3CO2H is a weak Ka of CH3CO2H = 1.8  10–5 mol dm–3
acid (only ionises partially in water).
[H+ ][CH3 CO2 − ] x2
Ka = =
[CH3 CO2 H] 0.10 − x
assume x << 0.10, therefore:
[H+] = x = √1.8 × 10−5 × 0.10
= 1.34  10–3 mol dm–3
pH = −lg (1.34  10–3) = 2.87

• At 0 <VNaOH < 25 cm3 Calculation of pH of the solution in the conical

1. Once the NaOH is added and some acid is flask when VNaOH = 12.50 cm3
neutralised, the solution contains a
mixture of weak acid and its conjugate NaOH added = 1.25  10–3 mol
base  a buffer solution forms. Initial CH3CO2H = 2.50  10–3 mol
2. The pH at the initial part of the titration CH3CO2H is in excess. The salt formed and the
curve and the part immediately before excess weak acid forms a buffer.
complete neutralisation changes more
sharply as these lie outside the effective CH3CO2H left = 1.25  10–3 mol
buffer range of the buffer. CH3CO2– formed = 1.25  10–3 mol
3. The maximum buffer capacity occurs
when half of the number of moles of acid is Ka [CH3 CO2 H]
[H+] =
neutralised at VNaOH = 12.50 cm3 (where [CH3 CO2 − ]
[acid] = [conjugate base]). At this point, pH
1.8 × 10−5 × (1.25 × 10−3 / 37.50 × 10−3 )
= pKa of the weak acid. =
1.25 × 10−3 / 37.50 × 10−3
= 1.8  10–5 mol dm–3
pH = pKa = 4.74

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• At VNaOH = 25 cm3 Equivalence point is reached.

pH > 7 as the anion undergoes hydrolysis to
Suitable indicator: phenolphthalein produce OH–:
or thymol blue or thymolphthalein
CH3CO2–(aq) + H2O(l) ⇌ CH3CO2H(aq) + OH–(aq)
The sharp change in pH in the curve near
equivalence point occurs over a smaller pH Calculation of pH of the solution in the conical
3
range compared to the previous strong acid– flask when VNaOH = 25.00 cm
strong base titration.
CH3CO2– formed = 2.50  10–3 mol
2.50×10−3
[CH3CO2–]=  1000 = 0.0500 mol dm–3
25.0+25.0

[CH3 CO2 H][OH− ]

–14
x2 1.00  10
Kb = = =
[CH3 CO2 − ]
–5
0.05 - x 1.80  10
Assume x << 0.05,
[OH−] = x = 5.27  10–6 mol dm–3

pH = 14 – pOH = 14 + lg (5.27  10–6) = 8.72

• At VNaOH > 25 cm3 Calculation of pH of the solution in the conical

There is excess NaOH present in the solution. As flask when VNaOH = 30.00 cm3
NaOH is a strong base, [OH–] is high and hence
pH is high (exact value depends on [NaOH] in NaOH added = 3.00  10–3 mol
excess). Initial CH3CO2H = 2.50  10–3 mol
NaOH is in excess.

NaOH unreacted = 5.00  10–4 mol

5.00 × 10−4
[NaOH] remaining =
55.00 × 10−3
= 0.00909 mol dm–3

pOH = −lg(0.00909) = 2.04

pH = 14 – pOH = 12.0

Note: OH− from hydrolysis of CH3CO2− is

insignificant compared to OH− from unreacted
strong base NaOH.

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5.1.3 Strong Acid – Weak base Titration

Consider addition of 0.10 mol dm–3 NH3 to 25.0 cm3 of 0.10 mol dm–3 HCl.

Features of the curve:

• At Vweak base = 0 cm3
Initial pH = pH of 0.10 mol dm–3 HCl = –lg 0.10 = 1
HCl is a strong acid (fully dissociated in water).

• At 0 < Vweak base < 25 cm3

pH gradually rises as increasing amount of H+ is neutralised by added weak base. However, no
buffer is formed as there is no weak base present in excess in the conical flask.

• At Vweak base = 25 cm3

Equivalence point is reached. pH < 7 as the cation undergoes hydrolysis to produce H3O+:
NH4+(aq) + H2O(l) ⇌ NH3(aq) + H3O+(aq)

Suitable indicator: methyl orange or screened methyl orange

• At Vweak base > 25 cm3

There is excess weak base present. The solution contains a mixture of weak base and its conjugate
acid  a buffer solution forms.

Exercise 5.1
(a) With reference to the above example, determine the pH of the solution in the conical flask at the
point when 12.50 cm3 of NH3 is added. (Kb of NH3 = 1.8  10–5 mol dm–3)
(b) Calculate the pH at equivalence point.
(c) What is volume of NH3 added when maximum buffer capacity occurs? What is the pH at this point?

[(a) 1.48, (b) 5.28, (c) Volume of NH3 at maximum buffer capacity = 50.00 cm3, pH = 9.26]

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5.1.4 Weak Acid – Weak Base titration

Consider addition of 0.10 mol dm−3 NH3 to 25.0 cm3 of 0.10 mol dm−3 CH3CO2H

Volume of NH3 added / cm3

Features of the curve:

• At Vweak base = 0 cm3
Initial pH = pH of 0.10 mol dm–3 CH3CO2H
pH is not equal to 1.0 as CH3CO2H is a weak acid (only ionises partially in water).

• At 0 < Vweak base < 25 cm3

Once the weak base is added and some acid is neutralised, the solution contains a mixture of weak
acid and its conjugate base  a buffer solution forms.

• At Vweak base = 25 cm3

Equivalence point is reached. There is no sharp change in pH, hence no suitable indicator can be
used, a pH meter may be used to help detect the equivalence point.
Both the cation and anion undergo hydrolysis (see Section 3.4).

• At Vweak base > 25 cm3

There is excess weak base present in the solution together with its conjugate acid  another buffer
region is formed.

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5.1.5 Titration Curves involving polyprotic acids or bases

Polyprotic acids have more than one ionisable proton. The successive Ka values may differ by several
orders of magnitude. This means the first H+ is lost more easily than subsequent ones. (Why?)

E.g. H2SO3(aq) + H2O(l) ⇌ HSO3–(aq) + H3O+(aq) Ka1 = 1.4  10–2 mol dm–3
HSO3–(aq) + H2O(l) ⇌ SO32–(aq) + H3O+(aq) Ka2 = 6.5  10–8 mol dm–3

In a titration of H2SO3, we can assume that all the H2SO3 molecules will lose one H+ ion before any of
the HSO3– ions loses its H+.
OH– OH–
H2SO3 –––––––> HSO3 ––––––> SO32–
–

Volume of NaOH added /cm3

Note that the titration curve usually has two steep portions, which corresponds to two equivalence
points.

A similar curve is also obtained for a titration involving a mixture of two acids with an appreciable
difference in Ka values (or a mixture of 2 bases with an appreciable difference in Kb values). In practice,
we can observe the two separate end–points with the proper choice and use of two different
indicators.

Consider the titration of sodium carbonate with dilute HCl.

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There are 2 stages in the titration:

CO32–(aq) + H+(aq) → HCO3–(aq) –––––––––––––––––––(1)

HCO3–(aq) + H+(aq) → H2O(l) + CO2(g) –––––––––––––––––––(2)

The first rapid change in pH for reaction (1) occurs at pH = 8.5. Therefore a suitable indicator for the
first equivalence point is phenolphthalein.

The second rapid change in pH for reaction (2) occurs at pH = 3.5. Therefore a suitable indicator for
the second equivalence point is methyl orange.

To observe the two end–points separately, phenolphthalein is first added. Methyl orange is added
only after the first equivalence point is reached.

If methyl orange is used at the start of the experiment, only one end–point is observed and the titre
obtained is twice that obtained with phenolphthalein.

Exercise 5.2 (Worked Example)

A 25.0 cm3 portion of a solution containing sodium carbonate and sodium hydrogencarbonate needed
22.50 cm3 of a solution of hydrochloric acid of concentration 0.100 mol dm –3 to decolourise
phenolphthalein. On addition of methyl orange, a further 28.50 cm3 of the acid was needed to turn
this indicator orange. Calculate the concentration of sodium carbonate and sodium
hydrogencarbonate in the solution.

With phenolphthalein indicator:

Na2CO3(aq) + HCl (aq) → NaHCO3(aq) + NaCl (aq) –––––––––––––(1)

No of moles of HCl used = 0.100  0.0225 = 2.25  10–3

No of moles of Na2CO3 = 2.25  10–3

[Na2CO3] = 2.25  10–3 / 0.025 = 0.0900 mol dm–3

With methyl orange indicator:

NaHCO3(aq) + HCl (aq) → NaCl (aq) + H2O(l) + CO2(g)
(from original NaHCO3 and
the NaHCO3 formed in (1))

No of moles of HCl used = 0.100 0.0285 = 2.85 10–3

No of moles of HCl used for NaHCO3 formed from Na2CO3 = 2.25 10–3
No of moles of HCl used for original NaHCO3 = 2.85 x 10–3 – 2.25 10–3 = 0.60 10–3

[NaHCO3] in the original solution = 0.60 10–3 / 0.025 = 0.0240 mol dm–3

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5.2 Acid-Base Indicators (Background Info)

An acid-base indicator is a weak aqueous acid whose acid form, HIn, is a different colour from its
ionised form (or conjugate base form), In–. As such, it shows different colours in solutions of different
pH.

HIn(aq) ⇌ H+(aq) + In–(aq)

General
acid form ionised form
equation
(colour 1) (colour 2)

litmus
⇌ H+(aq) +
red blue

Phenolphthalein
⇌ H+(aq) +

colourless pink

Methyl orange
⇌ H+(aq) +
red yellow

Thymol blue ⇌ H+(aq) +

yellow blue

At different pH values, the proportion of HIn to In– is different, giving rise to different colours.

For litmus:
• In acidic solutions, [H+] is high. The position of equilibrium lies on the left. Predominant form of
litmus is HIn, so the solution will appear red.
• In alkaline solutions, [OH–] is high so [H+] is low. The position of equilibrium lies on the right.
Predominant form of litmus is In–. Hence the solution will appear blue.

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5.3 Working pH Range of Indicators (Background info)

For most indicators, the predominant form must be at least 10 times more concentrated than the
other form for its colour to be distinguished from the other coloured form.

Since for an indicator, HIn (aq) ⇌ H+ (aq) + In– (aq)

The dissociation constant of an indicator, KIn, will be:
[H+][ In–]
KIn =
[HIn]
Taking –lg on both sides and rearranging,
[ In–]
pH = pKIn + lg
[HIn]
For litmus:
If the ratio of [In−]/[HIn] ≥ 10/1, i.e. pH ≥ pKIn + 1, the solution appears blue.

If the ratio of [In−]/[HIn] ≤ 1/10, i.e. pH ≤ pKIn – 1, the solution appears red.

Therefore, the litmus changes from red to blue over a pH range of

pH = pKIn – 1 to pH = pKIn + 1

That is, the working range of an indicator (i.e. pH range where a marked colour change occurs) is
approximately pKIn ± 1 .

Colours of common indicators for acid-base titrations

Table 6 Some common indicators and their working pH range
Indicators pH working range Colour in acidic region Colour in basic region
methyl orange 3.1 – 4.4 red yellow
screened methyl orange 3.0 – 4.6 violet green
bromothymol blue 6.0 – 7.6 yellow blue
phenolphthalein
8.0 – 9.6 colourless pink
(not used in lab)
thymol blue* 8.0 – 9.6 yellow blue
thymolphthalein* 9.3 – 10.5 colorless blue
*can be used as an alternative indicator in place of phenolphthalein to indicate end point of weak
acid-strong base titration

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5.4 Choice of Indicators

LO 10.1(e): explain the choice of suitable indicators for acid–base titrations, given appropriate data

During an acid-base titration, one solution is run into the other in the presence of an indicator.

• End-point: the point in a titration at which the indicator changes colour when 1 drop of excess
titrant is added.

• Equivalence point: the point in a titration at which the exact number of moles of acid and base
react completely.

The end-point tells us the equivalence point only when a suitable indicator is used.
• The indicator must have a distinct colour change.
• The working pH range of the indicator must coincide with the rapid pH change at the
equivalence point for the titration.

The rapid pH change for the titration depends on the strengths of acid and alkali used. Either the acid
or the alkali, or both, may be strong or weak, so that there are four possible combinations.

Table 7. Suitable indicators for different types of titration

Type suitable indicator
strong acid – strong alkali methyl orange or phenolphthalein or thymol blue
strong acid – weak alkali methyl orange
weak acid – strong alkali Phenolphthalein or thymol blue
weak acid – weak alkali no suitable indicator

Exercise 5.3
A 25.0 cm3 solution containing 0.120 mol dm–3 of lactic acid is titrated with aqueous NaOH of
concentration 0.100 mol dm–3. The pH at the equivalence point was found to be 8.29.

The table below lists the working ranges of some acid-base indicators. Suggest which of the
following indicators can be used for this titration and explain your choice.

Indicator Working range Low pH color High pH color

Bromophenol blue 3.0 – 4.6 yellow purple
Thymol blue 8.0 – 9.6 yellow blue
Naphtholphthalein 7.3 – 8.7 colorless green-blue

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Hwa Chong Institution 2024 14 – Acid-Base Equilibria

Planning Questions involving Acid-Base Equilibria

Using the concepts in this chapter, you may be asked to plan experiments involving acid-base equilibria.
Some examples are as follows.
1. Determination of pKa of a weak acid or pKb of a weak base. (See 2013 HCI JC2 BT2 Paper 2 Q1 in
“Examples of Acid-Base Equilibria Planning Qns” on Chemistry Google Site)
2. Preparation of a specific buffer for a particular purpose. (See 2011 HCI JC2 BT2 Paper 2 Q1 in
“Examples of Acid-Base Equilibria Planning Qns” on Chemistry Google Site)

LOOKING AHEAD
Acidity of organic acids and phenols as well as basicity of amines will be covered under organic carboxylic
acids, phenols and amines. The charges in an amino acid is also related to pH of solution.
Salt hydrolysis due to high charge density of cations will be covered in the chapters on Transition
Elements and Periodicity.

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Hwa Chong Institution 2024 14 – Acid-Base Equilibria

Acid-Base Equilibria – Summary

Concept Application

A BrØnsted acid is a proton donor. To identify if a molecule or an ion is behaving as an

A BrØnsted base is a proton acceptor. acid or a base given an equation or vice versa

pX = −log10X  X = 10 – pX To define quantities such as pH, pOH, pKw, pKa and

pKb

Kw = [H+][OH–] = 1  10–14 (at 25C) To calculate [H+] or [OH–] given the value of the
other.
Kw shows the relationship between [H+] and [OH–] in
any aqueous solutions. In pure water, [H+] = [OH–] = 1  10–7 (at 25C)

pKw = pH + pOH = 14 (at 25C) To calculate pH from pOH, or vice versa

For any conjugate acid–base pair, To calculate Ka from Kb, or vice versa.
Ka × Kb = Kw You use this equation when you need one of these K
pKa + pKb = pKw = 14 (at 25 oC) values but have the other.

HA ⇌ H+ + A− To calculate the pH of a
[H+ ]2 eqm
[H+ ]eqm [A− ]eqm • weak acid, Ka 
Ka = [HA]initial
[HA]eqm [H+ ]eqm [salt]initial
• buffer, Ka 
[acid]initial

To compare the strength of weak acids.

The larger the Ka value, the stronger the acid.

B + H2O ⇌ BH+ + OH− To calculate the pH of a

[OH− ]2 eqm
[BH+ ]eqm [OH− ]eqm • weak base, Kb 
[B]initial
Kb =
[B]eqm [OH− ]eqm [salt]initial
• buffer, Kb 
[base]initial

To compare the strength of weak bases.

The larger the Kb value, the stronger the base.

Salt hydrolysis – a reaction in which ions react with To explain why the pH of a salt derived from
water to form acidic or alkaline solutions • strong acid and weak base (e.g. NH4Cl) is < 7
e.g. NH4+ + H2O ⇌ NH3 + H3O+ • weak acid and strong base (e.g. CH3CO2Na) is > 7
CH3CO2– + H2O ⇌ CH3CO2H + OH–

Checklist for pH calculations

Do you know how to calculate the pH of a solution containing each of the following?
✓ a strong acid or strong base
✓ a weak acid or weak base
✓ a salt such as CH3CO2Na or NH4Cl
✓ a buffer
Using the above, can you sketch a titration curve, and mark the various key points on the curve (initial pH,
equivalence point, buffer with maximum capacity)

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Hwa Chong Institution 2024 15 – Halogen Derivatives

15 Halogen Derivatives

GUIDING QUESTIONS
Halogenoalkanes
 How are halogenoalkanes synthesised?
 Which classes of reagents do halogenoalkanes react with and why? What types of reactions do
halogenoalkanes undergo and why?
 How do halogenoalkanes react with nucleophiles? What are the factors which determine the mechanism
of nucleophilic substitution?
 How does the reactivity compare between different halogenoalkanes?

Halogenoarenes
 How are halogenoarenes synthesised?
 How does the reactivity of a halogenoarene compare with that of a halogenoalkane towards nucleophilic
reagents?

LEARNING OUTCOMES
Students should be able to:
11.4(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
11.4(b) describe and explain the mechanisms of nucleophilic substitutions in halogenoalkanes:
(i) SN1, in terms of stability of the carbocation intermediates
(ii) SN2, in terms of steric hindrance in the halogenoalkanes
11.4(c) explain the stereochemical outcome in nucleophilic substitution involving optically active
substrates:
(i) inversion of configuration in SN2 mechanism
(ii) racemisation in SN1 mechanism
11.4(d) interpret the different reactivities of halogenoalkanes, with particular reference to
hydrolysis and to the relative strengths of the C–Hal bonds
11.4(e) explain the unreactivity of chlorobenzene compared to halogenoalkanes towards
nucleophilic substitution, in terms of the delocalisation of the lone pair of electrons on the
halogen and steric hindrance
11.4(f) suggest characteristic reactions to differentiate between
(i) different halogenoalkanes
(ii) halogenoalkanes and halogenoarenes
e.g. hydrolysis, followed by testing of the halide ions
11.4(g) explain the uses of fluoroalkanes and fluorohalogenoalkanes in terms of their relative
chemical inertness
11.4(h) recognise the concern about the effect of chlorofluoroalkanes (CFCs) on the ozone layer
[the mechanistic details of how CFCs deplete the ozone layer are not required]

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Hwa Chong Institution 2024 15 – Halogen Derivatives

REFERENCES

1. Peter Cann and Peter Hughes. Chemistry for Advanced Level. John Murray (Publishers) Ltd.
Chapter 25.
2. John McMurry. Organic Chemistry. Brooks/Cole. Chapters 10-11.

1 INTRODUCTION

There are only a few naturally-occurring organic halogen compounds. One example is thyroxine, a
hormone secreted by the thyroid gland.

thyroxine

Synthetic halogen compounds have a variety of commercial applications such as insecticides,

herbicides, dry-cleaning agents and degreasers, fire-extinguishing chemicals, and polymers. However,
many chlorinated hydrocarbons are suspected to be carcinogenic and are being replaced by other
compounds.

Organic halogen compounds are often used as intermediates in organic synthesis; they are readily
formed from common materials and can easily be transformed into many different functional groups.

Two main types of halogen compounds will be discussed: halogenoalkanes and halogenoarenes.

1.1 Halogenoalkanes (alkyl halides)

They are alkanes with one or more H atoms replaced by the halogen atom, F, Cl, Br or I.

In IUPAC nomenclature, the halogen is considered as a substituent of the hydrocarbon. These

compounds are therefore named using the prefixes, fluoro-, chloro-, bromo- and iodo-. Some
examples are given below.

bromoethane 1,1-dibromoethane 1,2-dibromoethane 3-chloropentane

Halogenoalkanes may show constitutional isomerism and enantiomerism. For example, there are five
isomers with the molecular formula, C4H9Br.

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Hwa Chong Institution 2024 15 – Halogen Derivatives

Exercise 1.1 (Worked Example)

(a) Draw the five isomers (constitutional and enantiomers) with the molecular formula, C4H9Br.
(b) Give the IUPAC names of the four constitutional isomers.

1-bromobutane 2-bromobutane 1-bromo-2-methylpropane 2-bromo-2-methylpropane

2-bromobutane has a pair of enantiomers:

mirror plane

Total five isomers, two of which are a pair of enantiomers.

Halogenoalkanes are classified as primary, secondary or tertiary, depending on how many alkyl
groups are attached to the halogenated carbon (the carbon atom that is joined to the halogen atom,
X).

Primary halogenoalkanes
In a primary halogenoalkane, the halogenated carbon is only attached to one alkyl
group or one other carbon atom.

e.g. CH3CH2Br CH3CH2CH2Cl

Secondary halogenoalkanes
In a secondary halogenoalkane, the halogenated carbon is attached to two alkyl
groups or two other carbon atoms.

e.g.

Tertiary halogenoalkanes
In a tertiary halogenoalkane, the halogenated carbon is attached to three alkyl groups
or three other carbon atoms.

e.g.

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Hwa Chong Institution 2024 15 – Halogen Derivatives

Exercise 1.2 (Worked Example)

Draw the structural formulae of the halogenoalkanes in the table and classify them as primary,
secondary or tertiary.
Classification (primary,
Name Structural formula
secondary or tertiary)

3-chloropropene CH2=CHCH2Cl primary

chlorocyclopentane secondary

1-bromo-1-methylcyclohexane tertiary

1.2 Halogenoarenes (aryl halides)

These compounds have a halogen atom attached directly to a benzene ring.

e.g.

chlorobenzene 1-bromo-3-methylbenzene

1.3 Physical Properties of Halogenoalkanes

Halogenoalkanes are generally colourless liquids with sweetish smells. They are immiscible with and
denser than water. Boiling points of halogenoalkanes are higher than those of their corresponding
alkanes (alkanes with the same number of carbon atoms). For the same alkyl group, the boiling point
increases in the order: chloroalkane < bromoalkane < iodoalkane.

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Hwa Chong Institution 2024 15 – Halogen Derivatives

Exercise 1.3 (Worked Example)

The boiling points of some organic compounds are given below.

Compound Structural formula Name Boiling point /°C

A CH3CH2CH3 propane −42
B CH3CH2CH2Cl 1-chloropropane 47
C CH3CH2CH2Br 1-bromopropane 71
D CH3CH2CH2I 1-iodopropane 102

Note that the main intermolecular forces in halogenoalkanes are dispersion forces (also called
instantaneous dipole-induced dipole attractions). The difference in permanent dipole-permanent
dipole attractions is not as significant as dispersion forces and does not explain the observed boiling
point trend.

Explain each of the following.

(a) The boiling point of compound B is higher than that of A.

Both compounds are simple covalent molecules.

B has more electrons than A or larger electron cloud, so B forms stronger dispersion forces
between its molecules.

In addition, there is some amount of permanent dipole-permanent dipole attractions for B.

Thus, more energy is needed to overcome stronger intermolecular attractions between B

molecules during boiling (than between A molecules). Therefore B has higher boiling point.

(b) The boiling point increases in the order, B < C < D.

All three compounds are simple covalent molecules.

The number of electrons for the molecule increases in the order, B < C < D
or the size of electron cloud for the molecule increases in the order, B < C < D.

So intermolecular dispersion forces increase in strength in the same order.

Energy needed to overcome intermolecular attractions increases in the same order. Thus, boiling
point increases in the same order.

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Hwa Chong Institution 2024 15 – Halogen Derivatives

2 PREPARATION OF HALOGENOALKANES AND HALOGENOARENES

Halogenoalkanes can be prepared from:

 Free radical substitution of alkanes but would give a mixture of halogenated alkanes (unable to
control the position of substitution and how many H atoms become substituted) (Topic 10 Alkanes)
 Electrophilic addition on alkenes (Topic 11 Alkenes)
 Nucleophilic substitution of alcohols (to be covered in Topic 16 Hydroxy Compounds)

Halogenoarenes can be prepared from:

 Electrophilic substitution of arenes (Topic 12 Arenes)

Exercise 2.1

Draw the structure of the organic compound in each of the following boxes.

(i)

HBr

(ii)
Br2 in CCl4

(iii) (iv)
Cl2, FeCl3 catalyst
+

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Hwa Chong Institution 2024 15 – Halogen Derivatives

3 REACTIONS OF HALOGENOALKANES

Halogenoalkanes undergo two types of reactions: nucleophilic substitution and elimination.

3.1 Nucleophilic Substitution Reactions

Halogenoalkanes are fairly reactive compounds, owing largely to the polarity of the C–X bond.
Halogens are more electronegative than carbon, so the carbon-halogen bond is polar. The electron-
deficient carbon atom has a partial positive charge which causes it to be attractive to nucleophiles.

During reaction, the halogen atom in the halogenoalkane can be substituted by a nucleophile e.g. OH−,
CN− and NH3. This reaction typical of halogenoalkanes is called nucleophilic substitution.

The overall reaction for nucleophilic substitution can be represented as:

3.1.1 General mechanisms of nucleophilic substitution mechanisms

Nucleophilic substitution reactions can proceed by either an SN1 or SN2 mechanism. Generally, primary
halogenoalkanes undergo nucleophilic substitution via the one-step mechanism SN2 while tertiary
halogenoalkanes undergo reactions via the two-step mechanism SN1. Secondary halogenoalkanes may
react via either mechanism.

 SN2 mechanism (bimolecular nucleophilic substitution)

– The C–Br bond in bromoethane is polar due to the difference in electronegativity between the
carbon and bromine atoms.
– The nucleophile attacks the partially positively charged carbon atom from the side opposite to
the bromine atom. The nucleophile donates its lone pair to the electron-deficient carbon so that
a bond begins to form between the nucleophile and the carbon atom.
– At the same time, the C–Br bond is simultaneously weakened and begins to break. Both the
bonding electrons in the C–Br bond are donated to the Br atom to form Br−.
– An unstable, activated complex called a transition state is formed where the entering
nucleophile and the leaving Br− ion are partially bonded to the same carbon atom. Bond
breaking and bond forming occur simultaneously. This is a one-step mechanism.

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Hwa Chong Institution 2024 15 – Halogen Derivatives

– Rate = k[RBr][Nu−]
– The mechanism is known as SN2 (bimolecular nucleophilic substitution), because two species
are involved in the rate determining step of the mechanism.
– The energy profile or reaction pathway diagram for the SN2 mechanism is given below.

transition state
Energy/ kJ mol−1

Ea

reactants
−
Nu + CH3CH2Br

∆H products
CH3CH2Nu + Br−

progress of reaction

Stereochemistry
LO 11.4(c)(i) explain the stereochemical outcome in nucleophlic substitution involving optically active substrates: inversion of
configuration in SN2 mechanism

If the original RX molecule is chiral, the stereochemistry at the electron-deficient carbon will be
inverted after the substitution reaction (see below).

If the reaction occurs purely through the SN2 mechanism, only one of the enantiomers will be formed
as the product. There will not be a mixture of two enantiomers. As a result, the product obtained
through the SN2 mechanism will be optically active, if there is a chiral carbon present.

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Hwa Chong Institution 2024 15 – Halogen Derivatives

 SN1 mechanism (unimolecular nucleophilic substitution)

– The C–Br bond in 3-bromo-3-methylhexane is polar due to the difference in electronegativity

between the carbon and bromine atom.
– In the first step, heterolytic fission of the C–Br bond occurs, giving a carbocation intermediate
and a bromide ion. The electron-donating alkyl groups help to stabilise the carbocation
intermediate.
– In the second step, the highly reactive carbocation is readily attacked by the nucleophile to
form the product.
– This is a two-step mechanism.
– Rate = k[RBr]
– The mechanism is known as SN1 (unimolecular nucleophilic substitution) because only one
species is involved in the rate determining step of the mechanism.
– The energy profile or reaction pathway diagram for the SN1 mechanism is given below.
Energy/ kJ mol−1

Ea,1
Ea,2

Intermediates
reactants
R++ Br− + Nu−
Nu− + RBr

∆H products
RNu + Br

progress of reaction

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Stereochemistry
LO 11.4(c)(ii) explain the stereochemical outcome in nucleophilic substitution involving optically active substrates:
racemisation in SN1 mechanism

Since the carbocation is trigonal planar with respect to the electron-deficient carbon, the nucleophile
is able to attack from the top and bottom face of the carbocation with equal probability. If the addition
of the nucleophile results in a chiral product, a racemic mixture is formed in this mechanism as both
mirror image enantiomers are formed in equal quantities.

Exercise 3.1 (Worked Example)

A possible reaction of hydrolysis of 2-chloro-2-methylpropane is as shown.
(CH3)3CCl slow

 (CH3)3C+ + Cl−
(CH3)3C+ + OH− 
fast
(CH3)3COH

Which diagram represents the reaction profile for this mechanism? Hint: Consider the bond energies.

A B C D
energy
energy

energy

energy

reaction path reaction path reaction path reaction path

Ans: D

Remarks: This is a two-step mechanism (SN1 mechanism) and thus there should be two peaks on the
reaction profile. Since the CO bond formed is stronger than the CCl broken (check bond energy data
from Data Booklet), the overall reaction (chloroalkane + OH−  alcohol + Cl−) is exothermic and thus
the energy of the (final) products should be lower than that of the (starting) reactants.

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Exercise 3.2 (Worked Example)

Halogenoalkanes react with aqueous alkali. One mechanism has the energy profile shown below.

Z
energy

Y
X
RHal + OH−

ROH + Hal−

progress of reaction
Which statements are correct?
1 The reaction is an example of nucleophilic substitution.
2 Between X and Z the C–Hal bond will be lengthening.
3 The energy difference between X and Y represents the activation energy.

Ans: Options 1 and 2 are correct.

For Option 2, as the C–Hal bond breaks, the C–Hal lengthens and then breaks.
For Option 3, the energy difference bet. X and Z represents the activation energy and not X and Y.

Effect of structure of the halogenoalkane on the relative rates of SN1 and SN2
LO11.4(b)(i) describe and explain the mechanism of nucleophilic substitution in halogenoalkanes:SN1 in terms of stability of
the carbocation intermediate

 SN1 in terms of stability of the carbocation intermediates

Alkyl groups donate electrons to the carbocations and help to stabilise them. As such, the stability
of carbocations increases in the order primary < secondary < tertiary. As the carbocation becomes
more stable, the activation energy for the reaction leading to it decreases. See the figure below
for the reaction profiles for the SN1 mechanism for a primary vs. a tertiary bromoalkane:
Energy

Ea,1° primary C+

Ea,3°
tertiary C+

RBr + OH−

ROH + Br
progress of reaction

We therefore expect that the rate of SN1 will increase in the order primary < secondary < tertiary.

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Hwa Chong Institution 2024 15 – Halogen Derivatives

LO 11.4(b)(i) describe and explain the mechanism of nucleophilic substitution in halogenoalkanes: S N2 in terms of steric
hindrance of the halogenoalkanes

 SN2 in terms of the steric hindrance of the halogenoalkane

A tertiary halogenoalkane has three alkyl groups attached to the halogenated carbon, while a
primary halogenoalkane has only one alkyl group attached to the halogenated carbon. Alkyl
groups could ‘hinder’ or ‘block’ the attack of a nucleophile on the halogenated carbon in a SN2
mechanism. The rate of SN2 will increase in the order tertiary < secondary < primary.

 Overall, we expect primary halogenoalkanes to undergo nucleophilic substitution

predominantly via the SN2 mechanism, tertiary halogenoalkanes predominantly via the SN1
mechanism, and secondary halogenoalkanes to react via either mechanism.

 There are exceptions to the preference in mechanism due to the same electronic and steric
considerations (and information would be provided in the question for you to make the
conclusion).
E.g. 1-chloro-2,2-dimethylpropane, (CH3)3CCH2Cl, despite being a primary halogenoalkane, is
practically inert to substitution by the SN2 mechanism because of steric hindrance.
On the other hand, (chloromethyl)benzene, despite being a primary halogenoalkane, favours
substitution by the SN1 mechanism due to stabilisation of the carbocation intermediate by
delocalisation of the positive charge into the benzene ring.

Exercise 3.3
Bromoethane, CH3CH2Br, reacts with sodium methoxide, CH3O−Na+, to form CH3CH2OCH3.
Name and describe the mechanism for the reaction.

Relative rates of nucleophilic substitution in terms of the strength of the C–halogen bond
LO 11.4(d) interpret the different reactivities of halogenoalkanes, with particular reference to hydrolysis and to the relative
strengths of the C–Hal bonds

In comparing the reactivity between different halogenoalkanes, there is one main factor at work:

Strength of the C–X bond

The ease of nucleophilic substitution in halogenoalkanes depends on the ease of breaking the C–X
bond. As the size of the halogen atom increases, the C–X bond length increases and the bond strength
decreases, and hence nucleophilic substitution takes place more readily. The C–F bond is very strong,
so fluoroalkanes are extremely unreactive and do not undergo nucleophilic substitution.

Compound C–X bond length /nm Bond energy /kJ mol−1

CH3F 13.9 +485
CH3Cl 17.8 +340
CH3Br 19.3 +280
CH3I 21.4 +240

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Hwa Chong Institution 2024 15 – Halogen Derivatives

LO 11.4(a)(i) recall the chemistry of halogenoalkanes as exemplified by the following nucleophilic substitution reactions of
bromoethane: hydrolysis; formation of nitriles; formation of primary amines by reaction with ammonia

3.1.2 Nucleophilic substitution with OH− to form alcohols

R–X + OH−(aq)  R–OH + X− X = Cl, Br or I

Reagents and conditions: dilute NaOH, heat

This reaction is also known as alkaline hydrolysis.

3.1.3 Nucleophilic substitution with CN− to form nitriles

R–X + CN−  R–CN + X−

Reagents and conditions: ethanolic KCN, heat

The lone pair of electrons is donated by the C atom of CN−.

This reaction serves to increase the length of the carbon chain by one C atom, and is known as
a step-up reaction.

The nitrile formed can be used in the synthesis of carboxylic acids (via hydrolysis) and amines
(via reduction) as shown below.

Acidic hydrolysis of nitriles

R–CN + H+ + 2H2O  RCO2H + NH4+

Reagents and conditions: dilute H2SO4, heat

Alkaline hydrolysis of nitriles

R–CN + OH− + H2O  RCO2− + NH3

Reagents and conditions: dilute NaOH, heat

Reduction of nitriles

R–CN + 4[H]  RCH2NH2

Reagents and conditions: LiAlH4 in dry ether or

H2(g), Ni catalyst, high P

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Hwa Chong Institution 2024 15 – Halogen Derivatives

3.1.4 Nucleophilic substitution with NH3 to form amines

R–X + NH3  R–NH2 + HX

Reagents and conditions: ethanolic concentrated NH3, heat in sealed tube

(the sealed tube is to prevent the ammonia from escaping)
(“ethanolic concentrated NH3” means a concentrated solution of NH3 in ethanol.)

A primary amine is formed in the above reaction. Like ammonia, this primary amine possesses a lone
pair of electrons on the N atom. The electron-donating alkyl group makes the amine more nucleophilic
than ammonia. If an excess of halogenoalkane is present, the amine can readily react with the
halogenoalkane to form a secondary amine. Further reactions can then occur to form more
substituted amines:

RX + RNH2  R2NH + HX (secondary amine formed)

RX + R2NH  R3N + HX (tertiary amine formed)
RX + R3N  R4N+ X− (quaternary ammonium salt formed)

The following mechanisms show how primary and secondary amines may be formed from the
nucleophilic substitution of a halogenoalkane, using ammonia and bromomethane as an example:

Ammonia as the nucleophile can react with bromomethane to form methylamine (primary amine):

If excess bromomethane is present, the 1° amine reacts with the bromomethane:

The formation of the different amines when excess halogenoalkane is used causes the yield of the
primary amine to decrease, and also makes the separation of products difficult. As such, to obtain the
primary amine as the main product and avoid the further reactions described above, excess ammonia
should be used.

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Exercise 3.4

The previous mechanisms showed how a side product, the secondary amine, can be formed from
the reaction between ammonia and excess bromomethane. Suggest mechanisms to show how the
tertiary amine (CH3)3N and quarternary ammonium salt (CH3)4N+Br− may be formed in further
reactions with excess bromomethane.

3.2 Elimination
LO 11.4(a)(ii) recall the chemistry of halogenoalkanes as exemplified by the elimination of hydrogen bromide from
2-bromopropane

Halogenoalkanes take part in elimination reactions resulting in the formation of alkenes.

Reagents and conditions: ethanolic KOH, heat

When KOH is dissolved in ethanol, the OH− behaves more as a base than a nucleophile. It is able to
remove a hydrogen ion from the carbon atom adjacent to the C–X, causing the C–X to break, forming
an alkene.

The same reagent (hydroxide ion) can therefore carry out two different types of reaction (nucleophilic
substitution or elimination) when reacted with the same halogenoalkane. Both reactions do in fact
occur at the same time, but the significance of substitution versus elimination varies, depending on
the solvent, the nucleophile and the halogenoalkane used.

Elimination (E2) mechanism (For your information only)

The ease of elimination reactions depends on the strength of the C–X bond. The weaker the C–X bond,
the more readily the halogenoalkane undergoes elimination.

More than one alkene can be formed when the carbon bonded to the halogen has more than one
adjacent carbon atom with hydrogen atom(s) bonded to it. Both constitutional and cis-trans isomers
may be formed.

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Hwa Chong Institution 2024 15 – Halogen Derivatives

Exercise 3.5
Draw the structural formulae of the three alkenes formed when 2-bromobutane undergoes
elimination with hot ethanolic NaOH.

For your information only:

The major product is the alkene with the largest number of alkyl groups attached to the double-
bonded carbon atoms. This is known as Saytzeff’s rule. (Also spelt Zaitsev in some books.) Based on
Saytzeff's rule, the major product for the above reaction is but-2-ene.

Exercise 3.6
Fill in the boxes with the correct reagents and structures of compounds in the reaction scheme.

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4 REACTIONS OF HALOGENOARENES
LO 11.4(e) explain the unreactivity of chlorobenzene compared to halogenoalkanes towards nucleophilic substitution in terms
of the delocalisation of the lone pair of electrons on the halogen and steric hindrance

4.1 Reactivity of Halogenoarenes

Halogenoarenes are very much less susceptible to nucleophilic substitution than halogenoalkanes.

Reasons:
1. The lone pair of electrons on the halogen atom delocalises into the benzene ring.

As a result, there is partial double bond character in the C–X bond, so its bond length is shorter
and bond strength is stronger than that in the corresponding halogenoalkane. The C–X bond in
halogenoarenes is very difficult to break.

2. Sterically, the rear side of the C–X bond in halogenoarenes is blocked by the benzene ring. Also,
the -electron cloud of the benzene ring will repel the lone pair of electrons of an incoming
nucleophile, rendering attack of the nucleophile difficult.

Hence, nucleophilic substitution of halogenoarenes cannot be achieved by the same reagents and
conditions used for halogenoalkanes, and is only possible under very vigorous conditions.

4.2 Electrophilic Substitution on the Benzene Ring of Halogenoarenes

The halogenoarenes undergo electrophilic substitution on the benzene ring similar to other arenes.
[See Topic 12 Arenes]

However, halogenoarenes are less susceptible to electrophilic substitution as the halogen substituent
is deactivating. The halogen substituent is also 2,4-directing. An example of such a reaction is given
below.

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Exercise 4.1
State whether the following reactions take place in the respective halogen-containing compounds.

Compound CH3CH2Cl

In the benzene ring as

Within benzene ring
Delocalisation of electrons No well as over to the
only
chlorine atom

Nucleophilic substitution Yes No Yes

Elimination Yes No No

Yes (less readily than Yes (less readily than

Electrophilic substitution No
benzene) benzene)

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5 DISTINGUISHING TESTS FOR HALOGENOALKANES

LO 11.4(f)(i) suggest characteristic reactions to differentiate between different halogenoalkanes

5.1 Comparing Colour of AgX Precipitate

The general method for distinguishing between the type of halogen substituents present in
halogenoalkanes is to compare the colour of the silver halide precipitates that are formed after the
compound undergoes nucleophilic substitution by hydroxide ion. The test involves 3 steps.

Step 1: Add NaOH(aq) and heat. [Reaction: RX + OH–  ROH + X– ]

Step 2: Add excess dilute HNO3. [Removes unreacted OH– so that brown Ag2O ppt will not be formed
in the next step]
Step 3: Add AgNO3(aq) and observe the colour of precipitate formed. [ Ag+(aq) + X –(aq)  AgX(s) ]

The expected observations (for the positive tests) are given in the table below. Sometimes, the colours
of AgCl and AgBr are difficult to differentiate. We can follow up by adding NH3(aq); AgCl dissolves in
dilute aqueous NH3 while AgBr does not.

chloroalkane, RCl bromoalkane, RBr iodoalkane, RI

Colour of precipitate formed white cream yellow
Identity of precipitate AgCl AgBr AgI
Solubility of precipitate in dissolves in dilute dissolves in insoluble even in
NH3 solution aqueous NH3 concentrated NH3 concentrated NH3

AgX + 2NH3  [Ag(NH3)2]+ + X−

Colourless complex ion

[Reasons for the solubility are discussed in Topic 13 Solubility Equilibria]

5.2 Comparing Rate of Formation of AgX Precipitate

The three different halogenoalkanes can also be distinguished using ethanolic AgNO3. In this method,
the rates of the formation of the silver halide precipitates will be different. The identity of the
halogenoalkane can also be determined from the colour of the AgX precipitate formed.

chloroalkane, RCl bromoalkane, RBr iodoalkane, RI

Add 1 cm3 of the organic white ppt (AgCl) cream ppt (AgBr) yellow ppt (AgI)
compound in a test tube. formed in a longer formed in a longer formed
Add 1 cm3 of ethanolic time compared to time compared to RI almost immediately
AgNO3 and place the test RBr
tube in a hot water bath.

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Hwa Chong Institution 2024 15 – Halogen Derivatives

Explanation of the difference in the rate of formation of AgX precipitate:

The C–X bond must break in a nucleophilic substitution reaction to give the halide ion. In this reaction,
the nucleophile is ethanol. Bond strength decreases in the order C–Cl > C–Br > C–I, as shown by the
bond energies, +340, +280 and +240 kJ mol−1 obtained from the Data Booklet.

In this mechanism, the C–X is broken in the rate-determining step. Hence the stronger the C–X bond,
the higher the activation energy of the rate-determining step, and hence a slower rate. The weaker
the C–X bond, the easier and more readily it breaks to give the halide ion and the AgX precipitate
forms more quickly.

Exercise 5.1 (Worked Example)

A liquid L gave a pale yellow precipitate when shaken for some time with cold ethanolic silver nitrate.
Which compound could L be?
Ans: Options 1 and 2 are correct.
Remarks: Halogenoalkanes (i.e.
chloroalkane, bromoalkane,
iodoalkane groups) undergo
nucleophilic substitution.
2 CH3CH2CH2I Halogenoarenes (i.e. chlorobenzene,
bromobenzene, iodobenzene) less
susceptible to nucleophilic
substitution as explained in Section
4.1.

Exercise 5.2 (Worked Example)

Which sequence shows the correct order of decreasing ease of hydrolysis?

A CH3CH2Cl > CH3CH2Br > CH3CH2I

B (CH3)2CHCl > (CH3)2CHI > (CH3)2CHBr

Ans: D
Remarks: Ease (and rate) of nucleophilic substitution decreases in the order,
iodoalkane group > bromoalkane group > chloroalkane group
(look at bond energy data from Data Booklet, weaker C–halogen bond  easier to break)
Halogenoarenes – no nucleophilic substitution / very difficult to undergo nucleophilic substitution

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6 HALOGENOALKANES AND THE ENVIRONMENT

6.1 Uses of Halogenoalkanes

LO 11.4(g) explain the uses of fluoroalkanes and fluorohalogenoalkanes in terms of their relative chemical inertness

Halogenoalkanes are used as refrigerants, aerosol propellants and fire extinguishers.

Fluoroalkanes are less reactive than chloroalkanes due to the high bond energy of the C–F bond. They
are more useful in certain applications where their inertness are required, such as non-stick coating
on pots and pans and as taps and stoppers in laboratory glassware like burettes and standard flasks.
The commercial name for polytetrafluoroethene is Teflon®.

Chlorofluorocarbons (CFCs), often known by the trade name ‘Freons’, are used as refrigerants, aerosol
propellants and in fire extinguishers.

These compounds have some useful properties:

(1) they are inert and non-flammable
(2) they are non-toxic
(3) they are compounds that liquefy under pressure and therefore vapourise readily when that
pressure is released
(4) they are odourless

6.2 Effect of CFCs on the Ozone Layer

LO 11.4(h) recognise the concern about the effect of chlorofluoroalkanes (CFCs) on the ozone layer [the mechanistic details
of how CFCs deplete the ozone layer are not required]

Depletion of the ozone layer

Chlorofluorocarbons (CFCs) in aerosol sprays deplete the ozone (O3) layer and expose us to ultraviolet
radiation from the sun. The O3 layer absorbs ultraviolet rays and is vital in screening the earth from
excess ultraviolet radiation. Too much exposure to ultraviolet radiation causes skin cancer and
widespread crop failure.

Due to the strength of C–F and C–Cl bonds, fluoroalkanes and CFCs are stable molecular entities under
ambient conditions, which exhibit low toxicity, low reactivity, and low flammability. However, this lack
of reactivity also provides CFCs a lifespan that can exceed 100 years, giving them time to diffuse into
the stratosphere, where the strong UV radiation will cleave the weaker C–Cl bond (bond energies:
C–Cl = +340 vs. C–F = +485 kJ mol–1) homolytically to generate reactive Cl• radicals, which will catalyse
the decomposition of ozone into oxygen, leading to depletion of the ozone layer.

CF3Cl + uv  Cl + CF3

In the stratosphere, oxygen atoms are produced when O2 absorbs UV light at 250 nm wavelength.
O2  2O

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Once oxygen atoms form, they can react with oxygen molecules to produce ozone, which by
absorption of ultraviolet light, decompose to re-form oxygen atoms and oxygen molecules. An
equilibrium is set up between the two processes.

Natural ozone formation : O + O2  O3

Natural ozone depletion : O3  O + O2
Chlorine atoms (radicals) disrupt the equilibrium by acting as a homogeneous catalyst for the
destruction of ozone:
Cl + O3  ClO + O2 -----------(1)
ClO + O  Cl + O2 -----------(2)

As shown by equations (1) and (2), the chlorine atoms are regenerated, and in the process remove the
oxygen atoms needed to make more ozone by the natural ozone formation reaction. (You are not
required to memorise the above mechanistic details i.e. mechanism equations of how CFCs deplete
the ozone layer.)

Measures to protect the ozone layer

 Reduce use of CFCs in industrial and household applications. Since 1987, at the Montreal Protocol,
the use of CFCs has been increasingly banned in an increasing number of countries.
 Substitutes such as hydrocarbons, hydrofluorocarbons or fluorocarbons have been used in place
of CFCs. For example, some aerosols use propane or butane as propellant instead of CFCs.
However, alkanes are highly flammable and pose a fire hazard.

Exercise 6.1 (Worked Example)

Chlorofluorocarbons (CFCs) have been widely used in aerosol sprays, refrigerators and in making
foamed plastics, but are now known to destroy ozone in the upper atmosphere.

Which of the following compounds will not destroy ozone, and therefore can be used as a replacement
for CFCs?

A CHBr3
B CCl3CBr3
C CHClFCClF2
D CH3CH2CH2CH3

Ans: D
Remarks: A, B and C are incorrect as they contain the weaker C–Cl and C–Br bonds which can be
broken by UV light to form Cl  and Br radicals

ANS: D. [A, B and C are incorrect as they contain weaker C–Cl and C–Br bonds which can be broken by
UV light to form radicals and destroy ozone.]

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State the reagents and conditions needed for the conversions on the arrows below.

Summary of reaction of halogenoalkanes

CH2=CH2 CH3CH2NH2

1 2
3

4
CH3CH2CO2H CH3CH2Cl CH3CH2OH
PCl5
8
9 5

7
CH3CH2CO2− CH3CH2CN

CH3CH2CH2NH2

Summary of reaction of halogenoarenes

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16 Hydroxy Compounds
GUIDING QUESTIONS
● How are alcohols synthesised?
● Which classes of reagents do alcohols react with and why? What types of reactions do alcohols
undergo and why?
● Which classes of reagents do phenols react with and why? What types of reactions do phenols
undergo and why?
● How does the reactivity of phenol compare to benzene towards electrophiles?
● How do we compare the relative acidity of hydroxy compounds?

LEARNING OUTCOMES
Students should be able to:
11.5(a) recall the chemistry of alcohols, exemplified by ethanol:
(i) combustion
(ii) nucleophilic substitution to give halogenoalkanes
(iii) reaction with sodium
(iv) oxidation to carbonyl compounds and carboxylic acids
(v) dehydration to alkenes
11.5(b) suggest characteristic distinguishing reactions for the different classes of alcohols (primary,
secondary and tertiary alcohols), e.g. mild oxidation
11.5(c) deduce the presence of a CH3CH(OH)– group in an alcohol from its reaction with alkaline
aqueous iodine to form tri-iodomethane
11.5(d) recall the chemistry of phenol, as exemplified by the following reactions:
(i) with bases
(ii) with sodium
(iii) nitration of, and bromination of, the aromatic ring
11.5(e) explain the relative acidities of water, phenol and ethanol in aqueous medium (interpret as
Brønsted–Lowry acids)

REFERENCES
1. Cann, P.; Hughes, P. Cambridge International AS and A Level Chemistry; Hodder Education:
London, 2015; pp 281–293, 432–439.
2. McMurry, J. Organic Chemistry, 6th ed.; Brooks/Cole: Belmont, CA, 2004; pp 587–638.
3. Bailey, P. S.; Bailey, C. A. Organic Chemistry – A Brief Survey of Concepts and Applications, 6th
ed.; Prentice Hall: Upper Saddle River, NJ; 2000.

LOOKING BACK
In Topic 4 Reactions and Stoichiometry, we discussed various definitions of acids and bases. In Topic
14 Acid-Base Equilibria, we further learnt that the strength of weak acids and bases can be indicated
by the equilibrium constants Ka and Kb. In our continuation of organic chemistry, we will see the
application of the above acid-base concepts in the context of relatively weak organic acids (e.g.
alcohols, phenols and carboxylic acids) and organic bases (e.g. amines). Fundamental concepts in
Introduction and Isomerism (e.g. types of reactions, polar/non-polar mechanisms, delocalisation,
electronic/steric effects and isomerism) continue to play an important role in explaining the nature
and reactions of these acidic and basic functional groups in organic chemistry. The use of halogen
derivatives as a starting material to prepare these compounds will also be revisited.

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1 INTRODUCTION
LO 11.1(a) part: interpret, and use the nomenclature, general formulae and displayed formulae of the following classes of
compound: (iii) hydroxyl compounds (alcohols and phenols)

LO 11.1(b) part: interpret, and use the following terminology associated with organic reactions: (ii) degree of substitution:
primary, secondary, tertiary, quaternary

Alcohols are compounds of the general formula R–OH, where R is any alkyl or substituted alkyl group.
All alcohols contain the hydroxy (–OH) group, which determines the properties characteristic of this
family of compounds.

Present in alcoholic beverages and Occurs naturally in peppermint oil.

in some modern thermometers. It is well-known for the cooling
sensation that it provokes when
inhaled, eaten or applied to the
skin.

Phenols are compounds in which the hydroxy (–OH) group is directly attached to an aromatic ring.
Phenols differ markedly from alcohols in both physical and chemical properties.

An important chemical produced The primary female sex hormone is an

industrially as a precursor to many important hormone not only in
different compounds, including reproductive and sexual functioning,
polycarbonates, herbicides, and and also affects other organs including
pharmaceutical drugs. the bones.

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1.1 Classification of Alcohols

Alcohols can be subdivided into three different classes (similar to halogenoalkanes). An alcohol is
classified as primary (1°), secondary (2°), or tertiary (3°) according to the number of carbon atoms
bonded to the carbon that bears the –OH group:

Each class of alcohol undergoes chemical reactions differently. When asked to identify the alcohol
functional group in a compound, you should state whether it is a primary, secondary or tertiary alcohol
explicitly and not just a generic “alcohol”.

1.2 Nomenclature

Alcohols are named by replacing the terminal -e of the corresponding alkane name with -ol.

The longest carbon chain containing the hydroxy group is considered the parent structure.

Number the alkane chain beginning at the end nearer the hydroxy group, and use the appropriate
number to indicate the position of the –OH group.

Number any substituents according to their positions on the chain, and list the substituents in
alphabetical order. The priority of the functional groups can be found in Topic 8: Introduction to
Organic Chemistry, subtopic 4.1.

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As a substituent, the –OH group is named “hydroxy”, i.e. when it appears on a structure with a higher
priority functional group, i.e. ketone, aldehyde, nitrile, amide, acid halide, ester and carboxylic acid.

Compounds that have an –OH group directly attached to a benzene ring are called phenols.

Exercise 1.1 (Worked Example)

Name and classify the following alcohols or phenols.

(i) (ii) (iii)

1-bromo-3,3-dimethylbutan-2-ol phenylmethanol 5-bromo-2-methylphenol

(secondary alcohol) (primary alcohol) (phenol)

As OH group is of higher priority The highest priority group The OH group on benzene ring
than the Br group, the parent is the OH group and it is will take the position ‘1’ for a
functional group is an alcohol. located on a 1-carbon phenol.
The longest hydrocarbon chain is chain, hence the parent
4-carbons long, hence the name structure is methanol. The The other substituents will be
of the molecule is butan-2-ol with benzene ring is a numbered to give the smaller
the other substituents numbered substituent and is named set of locants.
accordingly. as ‘phenyl’.

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1.3 Isomerism

Isomerism in alcohols

Alcohols can exhibit chain and positional isomerism, as well as enantiomerism. Of the five isomers
with the formula C4H9OH, two (A and B) are primary alcohols, two (C and D) are secondary alcohols,
and one (E) is a tertiary alcohol.

Isomerism of alcohols and ethers

Ethers are constitutional isomers of alcohols. Ethers do not contain the –OH group and so have none
of the reactions of alcohols, and do not form intermolecular hydrogen bonds. Hence, ethers are fairly
inert compounds with boiling points lower than those of the isomeric compounds. For example:

2 PHYSICAL PROPERTIES OF ALCOHOLS AND PHENOLS

2.1 Boiling Points

Alcohols and phenols have significantly higher boiling points than those of corresponding
(isoelectronic) hydrocarbons.

no. of electrons alkane alcohol

in molecule formula b.p. / °C formula b.p. / °C
18 C2H6 −88 CH3OH 65
26 C3H8 −42 C2H5OH 78
34 C4H10 0 C3H7OH 97
42 C5H12 36 C4H9OH 118
50 C6H14 69 C5H11OH 138
50 C6H5CH3 111 C6H5OH 182
(methylbenzene) (phenol)

● The boiling point of an alcohol is higher than that of the corresponding isoelectronic alkane
(same number of electrons).

o While the strength of the dispersion forces in the alcohol and in the alkane is about the
same due to the similar sizes of the electron clouds, more energy is required to overcome
the intermolecular hydrogen bonding in alcohols which is stronger than the dispersion
forces in alkanes.

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● The boiling point of alcohols increases as the alkyl chain length increases.
o While the strength of intermolecular hydrogen bonding remains largely similar for all the
alcohols, the size of the electron cloud increases as the length of the alkyl chains increases.
More energy is thus required to overcome the stronger dispersion forces between the
alcohol molecules.

● Phenol and its derivatives are colourless solids. The melting point of phenol is 42 °C. The
presence of hydrogen bonds makes the melting point of phenols higher than those of
hydrocarbons with similar numbers of electrons.

2.2 Solubility in Water

Alcohols are more soluble in water compared to their corresponding alkanes due to their ability to
form hydrogen bonds with water molecules.

The solubility of alcohols in water decreases with increasing carbon number due to the increasing
length of the non-polar alkyl chain.

CH3CH2CH2CH2CH2CH2 −O−H

non-polar polar

As the length of the alkyl chain increases, the strength of the dispersion forces between alcohol
molecules increases. Energy released from hydrogen bonding formed between the alcohol molecule
and water is less able to overcome the increasingly stronger dispersion forces between alcohol
molecules, as well as the existing hydrogen bonding in water. In addition, the hydrogen bonding with
water is disrupted by the larger non-polar alkyl chain.

Phenols are only moderately soluble in water due to their large non-polar aryl group; but dissolve
completely when warmed.

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Exercise 2.1
1. (Worked Example) Arrange ethanol, ethane and ethane-1,2-diol in order of increasing boiling
point. Explain your answer.

2. Hexan-1-ol has a boiling point of 158 °C whereas 3,3-dimethylbutan-2-ol has a boiling point of
120 °C. Explain the difference in boiling points.

3. The structure of sucrose is shown below. Predict the physical state and solubility of the
compound under standard conditions.

Answer
1. Boiling point: ethane < ethanol < ethane-1,2-diol
Ethanol has higher boiling point than ethane as the hydrogen bonding between ethanol
molecules is stronger than the dispersion forces between ethane molecules and requires more
energy to overcome. Ethane-1,2-diol has 2 –OH groups while ethanol only has 1 –OH group.
Hence hydrogen bonding is more extensive in ethane-1,2-diol which requires more energy to
overcome.

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3 PREPARATION OF ALCOHOLS

Alcohols can be prepared from:

● Electrophilic addition of water or steam to alkenes (Topic 11 Alkenes)

● Nucleophilic substitution of halogenoalkanes (Topic 15 Halogen Derivatives)

● Reduction of aldehydes and ketones (to be covered in Topic 17 Carbonyl Compounds)

- Reduction of aldehydes yields primary alcohols
- Reduction of ketones yields secondary alcohols

● Reduction of carboxylic acids (to be covered in Topic 18 Carboxylic Acids and Derivatives)
- Reduction of carboxylic acids yields only primary alcohols

4 CHEMICAL PROPERTIES AND REACTIONS OF ALCOHOLS AND PHENOLS

LO 11.5(a): recall the chemistry of alcohols, exemplified by ethanol: (i) combustion, (ii) nucleophilic substitution to give
halogenoalkanes, (iii) reaction with sodium, (iv) oxidation to carbonyl compounds and carboxylic acids, (v) dehydration to
alkenes

The reactivity of the –OH group allows alcohols to be versatile starting materials for the preparation
of a variety of organic compounds. The alcohol functional group can undergo various reactions
involving the cleavage of either the C–O or O–H bonds of the –OH group.

4.1 Combustion

All alcohols burn well in air to form carbon dioxide and water, but only the combustion of ethanol has
significance in everyday life:

CH3CH2OH(l) + 3O2(g) → 2CO2(g) + 3H2O(l) ∆Hc = −1367 kJ mol−1

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4.2 Acid-Base Reactions of Alcohols and Phenols

LO 11.5(e): explain the relative acidities of water, phenol and ethanol in aqueous medium (interpret as Brønsted–Lowry Acids)

Due to the presence of the –OH group, alcohols and phenols can act as either Brønsted acids or
Brønsted bases. The electron-deficient hydrogen can be removed in the presence of a sufficiently
strong base, while the electron-rich oxygen can be protonated in the presence of a sufficiently strong
acid.

While this section mainly focuses on alcohols and phenols acting as Brønsted acids, we do see alcohols
acting as Brønsted bases later in Section 4.3.

In general, the strength of an acid depends on the stability of the conjugate base formed after
dissociation. When a more stable conjugate base is formed, it is less likely to accept a proton to re-
form the acid. Hence, the extent of dissociation is greater, resulting in a stronger acid and a larger Ka
(Topic 14 Acid-Base Equilibria).

4.2.1 Acidity of alcohols

In alcohols, the O−H bond can break to give H+ and R−O− (alkoxide ion). The extent of dissociation is
lower than that of water. Therefore alcohols do not turn blue litmus red.

Why are alcohols weaker acids than water?

Alkyl groups are inductively electron-donating and will intensify the negative charge on the alkoxide
ion. The alkoxide ion has a greater tendency as compared to the hydroxide ion to accept a proton to
re-form the alcohol molecule. Thus the alkoxide ion is said to be destabilised, and deprotonation of
the alcohol does not take place as easily. (Note: the length of the alkyl chain does not have a significant
impact on the acidity.)

Effect of substituents on acidity of alcohols

The presence of electron-withdrawing groups (e.g. −NO2, –F, –Cl, –Br, –I, –COCH3, –CO2H, –CN, −CO2R,
–NH2, –OH, –OCH3) help to stabilise the alkoxide ion formed by dispersing the negative charge on the
alkoxide ion, thus promoting the ionisation of the alcohol.
However, the presence of electron-donating groups (e.g. –CH3) decreases the acidic strength of
alcohols by intensifying the negative charge on the alkoxide ion, destabilising the alkoxide ion.

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The distance of the electron-withdrawing group from the negatively charged oxygen of the alkoxide
ion also affects the degree of dispersion of the negative charge, as the inductive effect decreases with
increasing distance. Thus, the nearer the electron-withdrawing group is to the negatively charged
oxygen in the alkoxide ion, the greater the degree of dispersion of the negative charge and the greater
the acid strength of the alcohol.

Exercise 4.1 (Worked Example)

Arrange the alcohols in order of increasing acid strength, giving your reasoning.

CH3CH2CH2OH CH3CHClCH2OH CH3CH2CH(Cl)OH

Answer: Acid strength: CH3CH2CH2OH < CH3CHClCH2OH < CH3CH2CH(Cl)OH

CH3CHClCH2OH and CH3CH2CH(Cl)OH have an electron-withdrawing chloro group that disperses the
negative charge on the alkoxide ion and stabilises the alkoxide. Hence both alcohols dissociate to a
greater extent than CH3CH2CH2OH, and are stronger acids than CH3CH2CH2OH.

The chloro group in CH3CHClCH2O is further away from the negatively charged oxygen as compared
to that in CH3CH2CH(Cl)O, resulting in a weaker electron-withdrawing effect and dispersing the
negative charge on CH3CHClCH2O to a smaller extent. Thus CH3CHClCH2OH is a weaker acid than
CH3CH2CH(Cl)OH.

4.2.2 Acidity of phenols

Phenols are more acidic than alcohols (and water). The pH of a 0.1 mol dm−3 phenol solution in water
is 5.4, so a solution of phenol will turn blue litmus red.

The negative charge on the phenoxide ion can be delocalised over the benzene ring as shown in the
following diagrams.

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In the phenoxide ion, a p orbital of the negatively charged oxygen is able to overlap with the π-electron
cloud of the benzene ring. The negative charge is able to delocalise into the benzene ring to some
extent, thus the phenoxide ion is stabilised to a larger extent than the alkoxide ion. The phenoxide
anion is less likely to accept a proton to re-form phenol. This makes phenols stronger acids than both
aliphatic alcohols and water.

Effect of ring substituents on acidity of phenols

Similar to alcohols, the presence of electron-withdrawing groups (e.g. –NO2, –F, –Cl, –Br, –I, −COCH3,
–CO2H, –CN, –CO2R) on the benzene ring enables the ring in turn to withdraw more electron density
from the negatively charged oxygen, thus stabilising the phenoxide ion further and promoting the
ionisation of the phenol.

The presence of electron-donating groups (e.g. –CH3, –NH2, –OH, –OCH3) on the benzene ring
decreases the acid strength of phenols by reducing the delocalisation of the negative charge on the
oxygen atom into the ring (or by intensifying the negative charge on the phenoxide ion), thus
destabilising the phenoxide ion.

Exercise 4.2
Arrange the following phenols in order of acid strength (1 for the most acidic, 5 for the least acidic).

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4.2.3 Acid-metal reaction with sodium (redox)

Alcohols and phenols react with Group 1 metals such as sodium and potassium to form alkoxides or
phenoxides respectively and hydrogen gas. This reaction involves the breaking of the O–H bond.

Reagents & Conditions: Na(s), room temperature

Observation: slow effervescence of hydrogen gas

Reagents & Conditions: Na(s), room temperature

Observation: rapid effervescence of hydrogen gas

Alcohols and phenols both act as acids, liberating H+, which is then reduced by sodium to H2. Both
reactions are similar to that of sodium with water. However, alcohols react more slowly as they are
weaker acids than water. Phenols, being stronger acids than water, react more vigourously.

4.2.4 Acid-base reaction with sodium hydroxide

Phenols are acidic enough to react with bases like sodium hydroxide (and potassium hydroxide) to
yield phenoxide salts and water. Phenol will form a cloudy mixture when mixed with water due to its
poor solubility. Upon addition of aqueous NaOH, the phenol will dissolve to form a homogeneous
colourless solution.

Reagents & Conditions: NaOH(aq), room temperature

Observation: cloudy mixture dissolves to form colourless homogeneous
solution

Note that phenols are not acidic enough to react with carbonates to liberate CO2 gas.

Alcohols, being weaker acids than water, are not acidic enough to react with aqueous sodium
hydroxide or carbonates to form the corresponding alkoxides.

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4.3 Nucleophilic Substitution (mechanism not required)

Alcohols can be converted to halogenoalkanes by nucleophilic substitution. In this reaction, the C–O
bond is broken.

We have seen in Topic 15 Halogen Derivatives that the OH– ion can attack a halogenoalkane, e.g. RCl,
to form an alcohol. In this reaction, the halide ion, Cl–, is called the leaving group.

Recall also from Topic 14 Acid-Base Equilibria, that Cl– and OH– ions are conjugate bases of acids HCl
and H2O respectively.

Since HCl is a stronger acid than H2O, its conjugate base Cl– is a weaker base than OH–. Weaker bases
are generally better leaving groups. Hence Cl–, being a better leaving group than OH–, is readily
substituted by OH– ions in halogenoalkanes to form alcohols in nucleophilic substitutions. This also
applies to Br– and I–.

On the other hand, as OH– is a poor leaving group, the conversion of alcohols to halogenoalkanes
involves reagents such as acid or SOCl2. These reagents first convert the –OH group into a better
leaving group before the halide ion attacks, forming the halogenoalkane.

4.3.1 Nucleophilic substitution with hydrogen halides

Reaction with hydrochloric acid

Tertiary alcohols react readily with concentrated hydrochloric acid upon shaking at room temperature
to form the corresponding chloroalkane.

Reagents & Conditions: concentrated HCl, room temperature

Observation: solution turns cloudy

Primary and secondary alcohols also can react with concentrated hydrochloric acid, but at a slower
rate. Anhydrous zinc chloride must be added as a catalyst, and the reaction mixture must be heated.

Reagents & Conditions: concentrated HCl, ZnCl2, heat

Observation: solution turns cloudy

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The reaction takes place via an SN1 mechanism, forming a carbocation intermediate. The rate of
reaction depends on the stability of the carbocation formed (See Topic 15 Halogen Derivatives).
Carbocations formed from tertiary alcohols have three electron-donating alkyl groups and hence are
the most stable. As such, the insoluble chloroalkanes are formed fastest with tertiary alcohols, and
the reaction with primary alcohols is very slow at room temperature.

Figure 1: General mechanism of nucleophilic substitution of alcohols using HCl

These reactions form the basis of the Lucas Test to distinguish between primary, secondary and
tertiary alcohols. The cloudiness of the solution is due to the relative insolubility of the chloroalkane.

type of alcohol observation on adding conc HCl + ZnCl2

R3COH (tertiary) immediate cloudiness appears in solution
R2CHOH (secondary) cloudiness appears within 5 min (at room temperature)
RCH2OH (primary) no cloudiness appears unless warmed

Reaction with hydrogen bromide

An alcohol can be converted to a bromoalkane by reacting it with either concentrated hydrobromic

acid (HBr) or a mixture of sodium bromide with concentrated acid to generate HBr in situ.

Reagents & Conditions: concentrated HBr, heat

-or- NaBr, conc. H2SO4 (to generate HBr in situ), heat

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4.3.2 Nucleophilic substitution with phosphorus halides

Reaction with phosphorus trihalides:

Alcohols react with the various phosphorus trihalides to form the corresponding halogenoalkanes and
phosphoric(III) acid.

Reagents & Conditions: PCl3, room temperature

-or- P, Br2, heat
-or- P, I2, heat
Comment: PBr3 and PI3 are prepared in situ by heating red phosphorus
with bromine and iodine respectively.
2P + 3X2 → 2PX3 X = Br, I

Reaction with phosphorus(V) chloride:

Phosphorus(V) chloride converts an alcohol into the corresponding chloroalkane with the evolution
of hydrogen chloride. As it is highly reactive with water, the reagents must be free of water or moisture.
PCl5 is a good distinguishing test for an alcohol functional group if a carboxylic acid is absent (as PC l5
will also react with carboxylic acids to produce HCl gas; see Topic 18 Carboxylic Acids and derivatives).

Reagents & Conditions: PCl5, room temperature

Observation: dense white fumes of HCl produced
Comment: Good distinguishing test for alcohol group (if carboxylic acid
is absent)

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4.3.3 Nucleophilic substitution with thionyl chloride

Another good reagent to convert alcohols to chloroalkanes is thionyl chloride, SOCl2. Thionyl chloride
and PCl5 will react with both alcohols and carboxylic acids, liberating HCl in the process. The use of
thionyl chloride confers an additional advantage over the use of PCl5 in that both by-products are
acidic gases and are hence more easily separated from the chloroalkane product. Also, since both by-
products are gases, the reaction is entropically driven (entropy change more positive, reaction more
thermodynamically feasible).

Reagents & Conditions: SOCl2, warm

Observation: SO2 gas and white fumes of HCl produced
Comments: Good distinguishing test for alcohol group (if carboxylic acid
is absent)
Gaseous by-products easy to separate from the liquid
product.
Thionyl bromide, SOBr2, may also be used to produce
bromoalkanes with HBr and SO2 as by-products.

4.3.4 Non-reactivity of phenols towards nucleophilic substitution

Phenols are very much less susceptible towards nucleophilic substitution, in which the –OH group is
replaced by a halide, than alcohols. Extremely harsh conditions are required for conversion of phenols
to halogenoarenes (which will not be discussed in this syllabus).

Reasons for the inertness of phenols towards nucleophilic substitution

There are several reasons for the reduced susceptibility of phenols to form halogenoarenes. These
reasons are similar to those given for the reduced susceptibility of halogenoarenes to nucleophilic
substitution reactions (see Topic 15 Halogen Derivatives).

1. The lone pair of electrons on the O atom in phenol delocalises into the benzene ring, resulting
in partial double bond character in the C−O bond. The C−O bond strength in phenols is higher
than in an alcohol, making it more difficult to break.

2. Sterically, the approach of a nucleophile to the rear side of the C−O bond in phenols is
hindered by the benzene ring. The π-electron cloud of the benzene ring will also repel the lone
pair of electrons on the approaching nucleophile.

These two factors make the attack by the nucleophile difficult.

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4.4 Dehydration (Elimination)

Dehydration of alcohols is carried out by heating the alcohol in the presence of a suitable catalyst. The
loss of the hydroxy group together with a H atom bonded to an adjacent carbon will result in the
formation of an alkene and a water molecule.

Reagents & Conditions: excess concentrated H2SO4, heat

-or- concentrated H3PO4, heat
-or- Al2O3, heat
Comments: Only alcohols with at least one H atom on the carbon atom
adjacent to the carbon atom bearing the hydroxy group
can undergo dehydration (shown in diagram above).
Concentrated phosphoric(V) acid is sometimes preferred
over sulfuric acid as sulfuric acid may act as an oxidising
agent, producing unwanted side products. Phosphoric(V)
acid is not an oxidising agent so side product formation is
minimised.

Dehydration may form a mixture of alkenes, depending on the position of the hydroxy group. Consider
the reaction of butan-2-ol with excess concentrated sulfuric acid:

Note: There are some similarities and differences between the dehydration reaction of alcohols and
elimination of halogenoalkanes. In both cases, an alkene is formed, but the differences are in the
reagents used, as well as formation of H2O and HX in the cases of alcohols and halogenoalkanes
respectively. (See Topic 15 Halogen Derivatives)

If there are no hydrogen atoms bonded to the carbon atom that is adjacent to the carbon atom bearing
the hydroxy group, dehydration cannot take place:

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Phenols cannot undergo dehydration. This is because the C−O bond is very strong as explained in the
previous section on nucleophilic substitution.

Exercise 4.3

Give structures of all organic products formed when 1-methylcyclohexanol reacts with each of the
following reagents.
(a) phosphorus pentachloride
(b) NaBr, conc H2SO4, heat
(c) hot concentrated sulfuric acid (excess)

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4.5 Condensation

Alcohols and phenols possess an –OH group with two lone pairs of electrons on the oxygen atom. This
allows them to act as nucleophiles (Lewis base) in their reaction with carboxylic acids and/or
acyl chlorides to form esters in a condensation process.

4.5.1 Condensation with carboxylic acids

Alcohols will react with carboxylic acids in a slow and reversible reaction, with a few drops of
concentrated sulfuric acid as catalyst, to form the ester with the condensation of a water molecule.
Note that concentrated sulfuric acid can act as a catalyst for both dehydration (to alkenes) and
condensation. In this case, only a few drops of concentrated sulfuric acid are used, making the sulfuric
acid less likely to act as a dehydrating agent.

Reagents & Conditions: alcohol, carboxylic acid, few drops of concentrated H 2SO4,
heat
Reagents & Conditions: alcohol, carboxylic acid, few drops of concentrated H2SO4, heat
Comment: reactionslow
slowand
andreversible
reversible
Comment: reaction

Unlike alcohols, phenols do not react with carboxylic acids in a similar condensation reaction. This is
due to the delocalisation of the lone pair of electrons on the oxygen atom into the benzene ring. The
lone pair of electrons is thus less available to attack the carboxyl carbon of the carboxylic acid to form
the ester.

4.5.2 Condensation with acyl chlorides

Acyl chlorides react much more readily with alcohols in condensation reactions than their
corresponding carboxylic acids. No heating and no catalysts are required, and the reaction goes to
completion instead of establishing an equilibrium.

Reagents & Conditions: acyl chloride, alcohol, room temperature

Observation: white fumes of HCl produced
Comment: reaction goes to completion

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The only method to form a phenyl ester is from the condensation reaction between a phenol and an
acyl chloride. As the lone pair of electrons on the oxygen atom in phenol is delocalised into the
π-electron cloud of the benzene ring, phenols are less nucleophilic than alcohols. As a result, only the
acyl chloride and not the carboxylic acid is used for this condensation reaction.

Reagents & Conditions: acyl chloride, phenol, room temperature

Observation: white fumes of HCl produced

For a better yield, the reaction is carried out under basic conditions (by using Na or NaOH) to first
generate the phenoxide ion. The negative charge of the phenoxide ion increases the electron density
around the oxygen atom, making it a stronger nucleophile than phenol. Hence the phenoxide ion
attacks the acyl chloride more readily.

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4.6 Oxidation

Two common sets of reagents and conditions are used for the oxidation of alcohols:

● K2Cr2O7 / dilute H2SO4, heat

● KMnO4 / dilute H2SO4, heat

The product of oxidation is determined largely by the type of alcohol.

Note:

For the oxidation of an alcohol to occur (using the above reagents), the alcohol must have at least one
hydrogen atom bonded to the carbon atom bearing the –OH group:

For this reason, tertiary alcohols and phenols cannot be oxidised using the above reagents:

4.6.1 Oxidation of primary alcohols

Primary alcohols are readily oxidised to aldehydes on heating. With excess oxidising agent, the
reaction proceeds further, yielding carboxylic acids. The oxidation pathway for ethanol is shown
below.

Oxidation to aldehydes

● Controlled oxidation of primary alcohols yields aldehydes.

● Once the aldehyde is formed in the reaction vessel, it will come into contact with more oxidant
and this will lead to further oxidation, forming a carboxylic acid. This can be avoided by
distilling the aldehyde away from the reaction mixture as soon as it forms. This is possible as
the aldehyde lacks intermolecular hydrogen bonding and thus has a lower boiling point than
the corresponding alcohol.

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● The distillation setup is shown in the diagram below.

Figure 2. Experimental setup

for the distillation of aldehydes
by oxidising primary alcohols.
(Diagram taken from
Chemistry for Advanced Level
by P. Cann and P. Hughes;
Hodder Murray)

Reagents & Conditions: K2Cr2O7, H2SO4(aq), heat with immediate distillation

Observation: orange solution (Cr2O72−) turns green (Cr3+)
Comments: Only K2Cr2O7 is selective enough to oxidise primary
alcohols to the aldehydes. KMnO4, being a stronger
oxidising agent, will oxidise them directly to carboxylic
acids.

Oxidation to carboxylic acids

To obtain carboxylic acids from primary alcohols, the reacting solution needs to be heated under
reflux. This prevents the aldehyde formed from evaporating and allows further oxidation to the
carboxylic acid. The reflux setup is shown in the diagram below.

water out

condenser

water in

reaction mixture
water/oil bath

heat Figure 3. Example of a typical reflux setup

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Reagents & Conditions: K2Cr2O7, H2SO4(aq), heat under reflux

-or- KMnO4, H2SO4(aq), heat under reflux
Observation: orange solution (Cr2O72−) turns green (Cr3+)
-or- purple solution (MnO4−) turns colourless (Mn2+)

4.6.2 Oxidation of secondary alcohols

Secondary alcohols are oxidised to ketones which are resistant to further oxidation.

Reagents & Conditions: K2Cr2O7, H2SO4(aq), heat under reflux

-or- KMnO4, H2SO4(aq), heat under reflux
Observation: orange solution (Cr2O72−) turns green (Cr3+)
-or- purple solution (MnO4−) turns colourless (Mn2+)

Oxidation as a distinguishing test to identify primary, secondary and tertiary alcohols

LO 11.5(b): suggest characteristic distinguishing reactions for the different classes of alcohols (primary, secondary and tertiary
alcohols), e.g. mild oxidation

Oxidation may be used as a method to distinguish between the various classes of alcohols (primary,
secondary or tertiary), based on the products of oxidation (if any). The alcohol is first heated under
reflux with excess potassium dichromate(VI) and dilute sulfuric acid. Tertiary alcohols will not be
oxidised by K2Cr2O7, so the colour of the reaction mixture remains orange.

Primary and secondary alcohols will be oxidised by K2Cr2O7 to carboxylic acids and ketones respectively,
causing the orange solution to turn green. To distinguish between these two classes of alcohols, the
organic product must be isolated (e.g. by distillation), and distinguishing tests for the carboxylic acid
or the ketone should be carried out on the product to identify the class of alcohol. (These
distinguishing tests will be covered in Topic 17 Carbonyl Compounds and Topic 18 Carboxylic Acids
and Derivatives.)

Note that in simple chemical tests, reflux and distillation setups are not used.

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Exercise 4.4
Draw the structures of the compounds formed by oxidation of each of the following compounds.

(a) (Worked Example)

Comments: There are two functional groups that can be oxidised, an alkene and a secondary
alcohol. Hence when a milder oxidising agent like K2Cr2O7 is used, only the secondary alcohol
will be oxidised to a ketone. The alkene will remain unchanged. When KMnO4 is used, the
alkene will also undergo oxidative cleavage to form oxidation products as shown in the
answer.

(b)

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4.7 The Tri-iodomethane (iodoform) Test

LO 11.5(c): deduce the presence of a CH3CH(OH)– group in an alcohol from its reaction with alkaline aqueous iodine to form
tri-iodomethane

Alcohols with a CH3CH(OH)− group will react with warm alkaline aqueous iodine. In this reaction, the
carbon bearing the hydroxy group is oxidised to a carboxyl carbon.

Reagents & Conditions: I2(aq), NaOH(aq), warm

Observation: yellow ppt (CHI3) formed
(Note that CHI3 is an organic compound.)
Comment: Another name for tri-iodomethane is iodoform.

Note that this reaction involves the breaking of a C−C bond with the removal of the methyl (−CH3)
group. It is therefore a useful method to shorten a carbon chain by a single carbon (known as a step-
down reaction).

Examples:

For your information:

Why do both the CH3CH(OH)− and the CH3CO− groups give a positive iodoform test?
(Mechanism not required)

In this reaction, the CH3CH(OH)− group is first oxidised in-situ to the corresponding CH3CO− group
(a methyl ketone) by the iodate(I) ion. This is then followed by a series of substitutions, leading to
cleavage of the −CI3 group to give CHI3.

Hence, methyl ketones also give a positive iodoform test, forming CHI3 (to be covered in Topic 17
Carbonyl Compounds).

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Exercise 4.5

1 (Worked Example) Which alcohols would give a positive tri-iodomethane reaction?

Answer
Both 1 and 4 will give positive results. Both have the CH3CH(OH)− group present.

2 Chemical tests were carried out on four organic compounds are labelled A, B, C and D.

The compounds are ethanol, propan-1-ol, 2-methylpropan-2-ol and cyclohexene but not
necessarily in that order.

The observations of each test are detailed in the table below.

observations
chemical test
A B C D
no
add Na(s) effervescence effervescence effervescence
effervescence
add K2Cr2O7
orange solution orange solution orange solution orange solution
and dilute
remains orange remains orange turns green turns green
H2SO4, heat
add aqueous I2,
no yellow ppt no yellow ppt yellow ppt no yellow ppt
aqueous NaOH,
formed formed formed formed
heat

Deduce the identity of the four compounds.

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4.8 Other Reactions of Phenols

In addition to the reactions discussed in earlier sections, phenol also undergoes some other reactions
of interest.

4.8.1 Electrophilic substitution of the benzene ring

LO 11.5(d): recall the chemistry of phenol, as exemplified by the following reactions: (i) with bases, (ii) with sodium, (iii)
nitration of, and bromination of, the aromatic ring

Due to the delocalisation of the lone pair of electrons of oxygen into the benzene ring, the electron
density in the ring is greatly increased, making phenol much more susceptible to electrophilic attack
than benzene (contrast this to the reagents and conditions required for electrophilic substitution of
benzene in Topic 12 Arenes). Hence, the presence of the –OH group highly activates the benzene ring
towards electrophilic substitution. Two general observations are noted:

1. Electrophilic substitution of the benzene ring in phenols takes place under milder conditions
compared to benzene: no catalyst and no heating required.

2. The –OH group is strongly activating and 2,4- directing, which may result in multi-substituted
products at the 2-, 4-, and 6- positions easily.

Note: as the –NH2 group in phenylamine is even more strongly activating than the –OH group in
phenol, similar observations will be made regarding electrophilic substitution of the benzene ring in
phenylamine (to be covered in Topic 19 Nitrogen Compounds).

Electrophilic substitution with nitric acid (nitration)

When phenol is treated with dilute aqueous nitric acid at room temperature, mono-substitution
occurs to form a mixture of 2- and 4- nitrophenol.

If concentrated nitric acid at room temperature is used, 2,4,6-trinitrophenol is produced.

Reagents & Conditions: dilute HNO3, room temperature

-or- concentrated HNO3, room temperature
Observation: pale yellow liquid formed

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Electrophilic substitution with bromine (bromination)

Phenol will react with aqueous bromine at room temperature to form a white precipitate of
2,4,6-tribromophenol. No Lewis acid catalyst is required.

Reagents & Conditions: aqueous bromine (bromine water), room temperature

Observation: yellow-orange solution decolourised, white ppt formed

To achieve mono-bromination of phenol, low temperatures must be used as the –OH group is strongly
activating. Also, the reaction must be carried out using either liquid bromine or bromine dissolved in
a non-polar organic solvent (such as CCl4) with a 1:1 ratio of phenol to bromine.

Reagents & Conditions: Br2(l) –or- Br2 dissolved in CCl4

Observation: reddish-brown liquid decolourised, white fumes of HBr
evolved

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4.8.2 Complex formation with iron(III) chloride

When a neutral solution of iron(III) chloride is added to a dilute solution of a phenol, a coloured
complex is formed. (The reason for the complex having colour will be discussed in Topic 22 Chemistry
of the Transition Elements.) The colour of the complex depends on the other substituents (if any) on
the benzene ring. With phenol, a violet colour is observed.

Reagents & Conditions: neutral FeCl3(aq), room temperature

Observation: violet colouration

This reaction is used as a distinguishing test for the presence of a phenolic group in an organic
compound.

Summary of reactions for alcohols and phenols

Complete the mind map below with (i) reagents and conditions; (ii) type of reaction for steps 1 –
13.

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17 Carbonyl Compounds
GUIDING QUESTIONS
 How are carbonyl compounds synthesised?
 Which class of reagents do carbonyl compounds react with and why? What types of reactions do
carbonyl compounds undergo and why?
 How do carbonyl compounds react with HCN in nucleophilic addition?

LEARNING OUTCOMES
Students should be able to:
11.6(a) describe the formation of aldehydes and ketones from, and their reduction to, primary and
secondary alcohols respectively
11.6(b) describe the mechanism of the nucleophilic addition reactions of hydrogen cyanide with
aldehydes and ketones
11.6(c) explain the differences in reactivity between carbonyl compounds and alkenes towards
nucleophilic reagents, such as lithium aluminium hydride and hydrogen cyanide.
11.6(d) describe the use of 2,4-dinitrophenylhydrazine (2,4-DNPH) to detect the presence of carbonyl
compounds
11.6(e) deduce the nature (aldehyde or ketone) of an unknown carbonyl compound from the results
of simple tests (i.e. Fehling’s and Tollens’ reagents; ease of oxidation)
11.6(f) deduce the presence of a CH3CO– group in a carbonyl compound from its reaction with
alkaline aqueous iodine to form tri-iodomethane

REFERENCES
1. Peter Cann & Peter Hughes (2014). Chemistry, Hodder Education, Chapter 17
2. John McMurry (2012). Organic Chemistry. 9th Edition, Cengage Learning, Chapter 19

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1 INTRODUCTION

Carbonyl compounds are commonly found in biologically important molecules such as carbohydrates
and hormones, as well as other natural and synthetic dyes, fragrances and pharmaceuticals.

Hedione (methyl hydrojasmonate) was discovered in the early 1960s and is one ingredient found in
almost all fine fragrances. During a quest to identify the characteristic smell of Bulgarian rose oil, the
rose ketones, damascenones, were discovered and synthesised. In general, aldehydes contribute to
the floral concept in feminine perfumery and aliphatic aldehydes with 8–13 carbon atoms have a very
pleasant odour, and can be detected in very low concentrations.

Benzaldehyde, the simplest aromatic aldehyde, has a pleasant almond-like odour, while
cinnamaldehyde gives cinnamon note. Vanillin (4–hydroxyl–3–methoxybenzaldehyde) is used as
vanilla note, an ubiquitous note in almost all fragrances.

A carbonyl group is composed of a carbon atom which is double bonded to an oxygen atom.

Carbonyl Group

The two simplest types of carbonyl compounds are aldehydes and ketones.

Aldehydes (RCHO) Ketones (RCOR’)

R = H, alkyl or aryl R/ R’ = alkyl or aryl

For the 1st member of the aldehydes, R = H The 1st member of the ketones can only be
propanone
Examples of molecules containing the aldehyde Examples of molecules containing the
group: ketone group:

Propanone (acetone)
Benzaldehyde

Ethanal Butanone (MEK)

Cinnamaldehyde(cinnamon) Cyclohexanone

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1.1 Nomenclature

Alkanes Aldehydes Ketones

Name ends in –e Name ends in –al Name ends in –one
e.g. propane e.g. propanal e.g. propanone

No. of
C Aldehyde Ketone
atoms

1 methanal - -

2 ethanal - -

3 propanal propanone

4 butanal butanone

pentan-2-one
5 pentanal
pentan-3-one

• For aldehydes, the longest chain carrying the –CHO group is considered the parent structure and
the –CHO carbon is numbered as carbon 1.

2-ethylpentanal

• Aldehydes in which the –CHO group is attached directly to a ring system are named by adding the
suffix -carbaldehyde.

cyclohexanecarbaldehyde (benzenecarbaldehyde)
benzaldehyde

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• For ketones, the parent chain is the longest one that contains the ketone group, and the
numbering begins at the end nearer the carbonyl carbon.

If the position of the carbonyl group is obvious, the number can be omitted.

hexa-3-one butanone cyclohexanone

Exercise 1.1 (Worked Example)

Draw the structural formula of each of the following compounds.
(i) 2-chloro-3-methylbutanal (ii) 4-phenylpentan-2-one

‘butanal’ is the parent structure, ‘pentan-2-one’ is the parent structure,

aldehyde-carbon is numbered 1: with carbon-2 bearing the ketone group:

then put a Cl at carbon-2 and a CH3 at carbon-3

‘phenyl’ refers to a benzene ring, put it at
carbon-4

Answer:

Answer:

1.2 Isomerism

• Saturated aliphatic aldehydes and ketones have the general formula CnH2nO where n equals to the
number of the carbon atoms in the compound. The aliphatic aldehydes and ketones are
constitutional isomers if they have the same number of carbon atoms, n, in the compound.

propanal propanone

• For ketones, the ketone group may occur at different positions.

pentan-2-one pentan-3-one

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2 PHYSICAL PROPERTIES OF ALDEHYDES AND KETONES

2.1 Boiling Points

Aldehydes and ketones have higher boiling points than corresponding hydrocarbons of similar number
of electrons in the molecule, but have lower boiling points than their corresponding alcohols and
carboxylic acids.

Structural No. of electrons

Compound b.p. / oC Predominant intermolecular forces
formula in the molecule
butane CH3CH2CH2CH3 34 –0.5 dispersion forces
propanal CH3CH2CHO 32 49 permanent dipole - permanent dipole
propanone CH3COCH3 32 56 permanent dipole - permanent dipole
propan-1-ol CH3CH2CH2OH 34 97 hydrogen bonding
ethanoic acid CH3CO2H 32 118 hydrogen bonding

• The carbonyl group is polar, thus permanent dipole-permanent dipole interactions exist between
molecules in aldehydes and ketones (in addition to dispersion forces) which require more energy
to overcome compared to only dispersion forces present in non-polar alkanes. Hence, carbonyl
compounds have higher boiling point than the corresponding alkanes.

• Alcohols and carboxylic acids can form hydrogen bonds between molecules, which are stronger
and require more energy to overcome than permanent dipole-permanent dipole interactions in
the corresponding aldehydes and ketones. Hence, carbonyl compounds have lower boiling point
than the corresponding alcohols and carboxylic acids.

2.2 Solubility in Water

Aldehydes and ketones have both polar and non-polar regions. They can act as solvents to both polar
and non-polar solutes, which gives them a wide range of uses as solvents.

The smaller aliphatic aldehydes and ketones are soluble in water due largely to their ability to form
hydrogen bonds with water molecules.

Carbonyl compounds containing more than 5 carbons or aromatic rings, are virtually insoluble in
water. As the number of carbon atoms in the alkyl chain increases, the strength of the dispersion
forces between molecules of the carbonyl compound increases. Energy released from hydrogen
bonding formed between the carbonyl group and water is less able to overcome the increasingly
stronger dispersion forces, as well as the existing hydrogen bonding in water. In addition, the hydrogen
bonding with water is disrupted by the larger non–polar alkyl chain.

Non–polar alkyl chain reduces solubility

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Exercise 2.1
The boiling points and solubility in water of some organic compounds are given below:

Compound Structural formula No. of electrons in b.p. / oC Solubility in 100g

the molecule of water/g
A CH3CH2CHCH2 32 6 
B (CH3)2CO 32 56 
C CH3CH2CH2OH 34 78 
D CH3CH2CHO 32 49 16
E CH3CH2CH2CHO 40 76 7

Explain each of the following.

(a) The boiling point increases in the order, A < B < C.

(b) The solubility of D is higher than that of E.

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3 PREPARATION OF ALDEHYDES AND KETONES

LO 11.6(a): describe the formation of aldehydes and ketones from, and their reduction to, primary and secondary alcohols
respectively

Aldehydes can be prepared from:

• Oxidation of primary alcohols (Topic 16 Hydroxy Compounds)

Ketones can be prepared from:

• Oxidation of secondary alcohols (Topic 16 Hydroxy Compounds)
• Oxidative cleavage of substituted alkenes (Topic 11 Alkenes)

Exercise 3.1
Draw the products formed from the following reactions:

K2Cr2O7 / H+
(i) heat with immediate
distillation

KMnO4 / H+
(ii)
heat

KMnO4 / H+
(iii)
Heat

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4 REACTIONS OF ALDEHYDES AND KETONES

Reactivity of aldehydes and ketones towards nucleophilic reagents and addition

LO 11.6(c): explain the differences in reactivity between carbonyl compounds and alkenes towards nucleophilic reagents, such
as lithium aluminium hydride and hydrogen cyanide

carbonyl group alkene group

• LiAlH4, NaBH4 and HCN are nucleophilic reagents.

(LiAlH4 and NaBH4 can be considered as sources of the hydride anion, H–)

• The +C=O– bond is polar, so the aldehyde-carbon or the ketone-carbon has + charge.
+ carbon attracts nucleophiles. Hence, aldehydes and ketones react with the above nucleophilic
reagents.

• The C=C bond (in alkenes) is non-polar and has no + carbon to attract nucleophiles. In fact
the electron rich C=C bond would repel nucleophiles (e.g. H– anion, or the AlH4– or BH4– anions
themselves).

4.1 Nucleophilic Addition Reaction

The overall reaction for nucleophilic addition of carbonyl compounds can be represented as:

Examples of nucleophiles that can react with aldehydes and ketones in a nucleophilic addition include
CN–, H2O and ROH.

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4.1.1 General mechanism of nucleophilic addition

Step 1: A nucleophile attacks the electron-deficient carbonyl carbon, breaking the  bond of the C=O
group, to form an alkoxide ion.

Step 2: The tetrahedral intermediate is protonated by water or acid to give an alcohol as the final
product.

4.1.2 Relative reactivity of aldehydes and ketones in nucleophilic addition reactions

Aldehydes are generally more reactive than ketones in nucleophilic addition reactions.

(i) Steric reason:

The presence of two relatively large substituents in ketones versus only one large substituent in
aldehydes means that attacking nucleophiles are able to approach the carbonyl carbon in aldehydes
with less steric hindrance than in ketones.

(ii) Electronic reason:

Aldehydes have one electron donating alkyl group while ketones have two. Hence, an aldehyde-
carbon has a higher partial positive charge compared to a ketone-carbon, making the former more
susceptible towards nucleophilic attack.

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4.1.3 Nucleophilic addition with hydrogen cyanide, HCN

LO 11.6(b): describe the mechanism of the nucleophilic addition reactions of hydrogen cyanide with aldehydes and ketones

Aldehydes and ketones undergo nucleophilic addition with hydrogen cyanide, HCN, under appropriate
conditions to form cyanohydrins.

trace KCN
+ H–CN
cold
aldehyde or ketone cyanohydrin

Reagents and HCN with trace KCN, cold

conditions:

Comments: KCN is used as a catalyst; CN– ion is regenerated at the

end of the reaction.

Note:
HCN is a toxic gas and has a boiling point of 25.6oC . It is usually generated in situ by the reaction
between KCN(s) and cold dilute H2SO4.
2 KCN + H2SO4  K2SO4 + 2 HCN

The reaction mixture is kept cold (at 10-20C) to ensure that HCN remains as a liquid.

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Mechanism

The mechanism of the nucleophilic addition with HCN involves two steps:

Step 1: The carbonyl carbon is attacked by the CN– nucleophile

 The CN– ion acts as nucleophile and attacks the electron-deficient carbonyl carbon breaking the
π-bond of the C=O.
 This leads to the formation of a stable tetrahedral intermediate anion (an alkoxide ion).
 This is the rate-determining step.

Step 2: Protonation of the intermediate to give a cyanohydrin

 The tetrahedral alkoxide ion intermediate is protonated by attacking an undissociated HCN

molecule to yield the cyanohydrin.
 The CN– nucleophile is regenerated.
potential energy

+HCN
–
+CN
+ HCN tetrahedral
intermediate
reactants

+CN–

cyanohydrin

Progress of reaction

Kinetics

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This nucleophilic addition mechanism is bimolecular, as it involves both the carbonyl compound and
the nucleophile :CN– in the rate-determining step. Hence, the rate equation is:

rate = k [carbonyl compound] [CN–]

To increase the rate of reaction, the following methods are used:

1. add a trace amount of KCN as catalyst

• HCN is a weak acid, which only partially ionises in water to give CN−.
HCN + H2O ⇌ H3O+ + CN– Ka = 6.2  10–10 mol dm–3
• The reaction takes place very slowly if only HCN is used because the solution contains a very low
concentration of CN– ions.
• The reaction can be speeded up by adding a trace amount of KCN, a salt which completely
dissociates to provide free CN– ions.
KCN (aq)  K+ (aq) + CN– (aq)
• CN– ions used in the addition reaction are regenerated at the end of the reaction as shown in the
mechanism.

2. add a small amount of base (e.g. NaOH)

HCN + H2O ⇌ H3O+ + CN−

When a small amount of base is added, the H3O+ ions are neutralised, which by Le Chatelier’s Principle,
shifts the position of the above equilibrium to the right such that the concentration of the CN–
increases. Hence the rate of reaction increases.

Stereochemistry

The geometry about the carbonyl carbon atom in aldehydes and ketones is planar. Hence the
nucleophile can attack the + carbonyl carbon atom in equal probability from the top or bottom of
the plane, producing equal amounts of both enantiomers to give a racemic mixture, if the resulting
sp3 carbon is chiral.

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Refer to the similar circumstances leading to the formation of racemic mixtures in Topic 11 Alkenes
and Topic 15 Halogen Derivatives. In electrophilic addition and SN1 mechanisms, the geometry about
the positively-charged carbon in the carbocation intermediate is also planar, allowing a nucleophile to
attack from either side of the plane with equal probability.

Importance of cyanohydrins in synthesis

• Nucleophilic addition with CN– ion is an important method of lengthening the carbon chain by 1
carbon (step-up reaction).

• The cyanohydrin product can be easily converted to other usable forms since the nitrile group
(–CN) can be converted to other functional groups such as:
 carboxylic acids by acid hydrolysis using mineral acids such as dilute H2SO4
 carboxylate salts by alkaline hydrolysis using alkalis such as dilute NaOH
 amines by reduction using lithium aluminium hydride (LiAlH4) in dry ether or hydrogen with
nickel catalyst

Exercise 4.1
Draw the products formed from the following reactions:

(i) HCN, trace KCN LiAlH4 in dry ether

cold

HCN, trace KCN

(ii) cold dil. H2SO4, heat

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4.2 Condensation Reaction (Application Example)

Nucleophiles having two H atoms on a nitrogen atom readily add onto carbonyl compounds. But
usually, the initially formed addition product is not isolated because it easily loses water via
elimination to give stable compounds containing a C=N bond.

The overall reaction can be represented as:

4.2.1 General mechanism (application example)

The reaction can be viewed as an addition, followed by an elimination, hence it may be referred to
as an addition-elimination reaction.

Step 1: Addition of nucleophile to carbonyl compound

Step 2: Elimination of a water molecule

Elimination of H2O

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4.2.2 Condensation reaction with 2,4-dinitrophenylhydrazine (2,4-DNPH)

LO 11.6(d): describe the use of 2,4-dinitrophenylhydrazine (2,4-DNPH) to detect the presence of carbonyl compounds

2,4-dinitrophenylhydrazine, also known as Brady’s reagent, is a yellow solution. It reacts with

aldehydes and ketones to form a 2,4-dinitrophenylhydrazone derivative, which is an orange
precipitate. A water molecule is eliminated in the reaction. This is a characteristic test for the presence
of aldehydes and ketones.

+ + H2O

aldehyde
2,4-dinitrophenylhydrazine a 2,4-dinitrophenylhydrazone derivative
or ketone

Reagents and 2,4-dinitrophenylhydrazine (2,4-DNPH), room temperature

conditions:

Observations: Orange precipitate formed

Exercise 4.2
Which of the following compounds will give an orange precipitate with 2,4-dinitrophenylhydrazine?

A B C D E

4.3 Reduction

Aldehydes and ketones undergo reduction to form primary and secondary alcohols respectively.

LiAlH4 in dry ether

+ 2[H]
room temperature
aldehyde primary alcohol

LiAlH4 in dry ether

+ 2[H]
room temperature
ketone secondary alcohol

Reagents and LiAlH4 in dry ether, room temperature

conditions:
Note: When the aldehyde or ketone react with LiAlH4, the
alkoxide ion is form. H2O needs to be added to protonate the
alkoxide to form the alcohol.
Comments: Other reducing agents like NaBH4 in methanol or, H2(g)/ Ni at
high pressure may be used.

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4.3.1 Comparing reducing agents LiAlH4 and NaBH4

Lithium aluminium hydride (LiAlH4) and sodium borohydride (NaBH4) are

useful hydride reagents that can reduce aldehydes and ketones in excellent
yields.

 LiAlH4 is a grayish powder that is soluble in ether. It reacts violently with water to form H2
gas and decomposes explosively when heated above 120 oC. NaBH4 is a white, crystalline
solid that can be handled in the open atmosphere and used in either water or alcohol
solution.

 Due to the hazardous nature of LiAlH4 and ether (which forms highly explosive mixtures in
air), the use of NaBH4 is usually preferred.

 Both LiAlH4 and NaBH4 can be considered as sources of the nucleophilic hydride anion, H–.
They both have hydrogen atoms covalently bonded to aluminium and boron respectively
and because hydrogen is more electronegative than aluminium and boron, the hydrogen
atoms will bear the negative charge, making it a good nucleophile. As such, LiAlH4 and
NaBH4 are able to react with aldehydes and ketones bearing the polar C=O group with an
electron-deficient carbon.

 Aluminium is less electronegative than boron, thus more of the negative charge in the AlH4–
ion is borne by the hydrogen atoms. Therefore, LiAlH4 is a much stronger reducing agent,
and is much less selective than NaBH4.

 Both LiAlH4 and NaBH4 do not reduce the non-polar electron-rich alkene group. The alkene
functional group is reduced using H2(g) over a nickel catalyst. Refer to Topic 6 Reaction
Kinetics for the mechanism of this heterogeneous catalysis reaction.

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4.4 Oxidation
LO 11.6(e): deduce the nature (aldehyde or ketone) of an unknown carbonyl compound from the results of simple tests (i.e.
Fehling’s and Tollens’ reagents; ease of oxidation)

The aldehyde group undergoes oxidation reactions with acidified potassium dichromate(VI), Tollens’
reagent and Fehling’s solution, while the ketone group does not. As such, these three tests are good
distinguishing tests between aldehydes and ketones.

4.4.1 Oxidation with acidified potassium dichromate(VI) or acidified potassium manganate(VII)

Aldehyde has a hydrogen atom attached directly to the carbonyl carbon. This enables it to be oxidised
to carboxylic acids.

K2Cr2O7 / dilute H2SO4 or

KMnO4 / dilute H2SO4
+ [O] heat under reflux
aldehyde carboxylic acid

Reagents and K2Cr2O7 / dilute H2SO4 or KMnO4 / dilute H2SO4, heat under reflux
conditions:

Comments: Orange solution (Cr2O72–) turns green (Cr3+) or

Purple solution (MnO4–) turns colourless (Mn2+)

Ketones do not have a hydrogen atom attached directly to the carbonyl carbon, thus are not easily
oxidised.

K2Cr2O7 / dilute H2SO4

no reaction
heat
ketone

Exercise 4.3
How would you oxidise only the aldehyde group in cinamaldehyde to carboxylic acid?

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4.4.2 With Tollens’ reagent (silver mirror test)

Tollens’ reagent (ammoniacal silver nitrate) contains diamminesilver(I) ions, [Ag(NH3)2]+.

Aldehydes reduce silver(I) in Tollens’ reagent to silver metal. Under carefully controlled conditions,
silver metal will deposit on the walls of the reaction vessel as a mirror.

heat
+ 2[Ag(NH3)2]+ + 3OH– + 2Ag + 4NH3 + 2H2O

aldehyde silver mirror

Reagents and Tollens’ reagent, heat

conditions:

Observations: Silver mirror formed

Comments: [Ag(NH3)2]+ is unstable and should always be freshly prepared. It can

be prepared as follows:
1. One drop of dilute NaOH(aq) is added to about 3 cm3 of
AgNO3(aq) to produce a dark brown precipitate of Ag2O.

2. Dilute NH3(aq) is then added dropwise until the brown

precipitate first formed just redissolves.

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4.4.3 With Fehling’s reagent

Fehling’s reagent is an alkaline solution of copper(II) tartrate.

Aldehydes (except benzaldehyde and its derivatives) reduce the copper(II) in Fehling’s reagent to the
reddish-brown copper(I) oxide, which is precipitated.

+ 2Cu2+ + 5OH– + Cu2O + 3H2O

heat
aliphatic
blue solution reddish-brown ppt
aldehyde only

Reagents and Fehling’s reagent, heat

conditions:

Observations: Reddish-brown (brick-red) precipitate formed

Comments: Ketones, benzaldehyde and its derivatives do not reduce Fehling’s reagent.

In fact, benzaldehyde undergoes disproportionation instead due to the

presence of NaOH in Fehling’s reagent.

Fehling’s reagent deteriorates on keeping. and is usually prepared in two

parts which are added together just before the test is carried out.

It consists of:
1. Fehling’s solution A (CuSO4 solution) and
2. Fehling’s solution B (sodium potassium tartrate + excess NaOH)

A deep blue solution is obtained on mixing the two solutions owing to the
formation of copper(II) tartrate, the tartrate ions present prevent the
tartrate ion precipitation of Cu(OH)2 by complexing with the copper(II) ions.

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Exercise 4.4
Which of the following compounds will give a positive Tollens’ reagent test?

X Y Z

(i) Which of the following compounds will reduce Fehling’s reagent?

A B C D

4.5 Tri-iodomethane (iodoform) Test

LO 11.6(f): deduce the presence of a CH3CO– group in a carbonyl compound from its reaction with alkaline aqueous iodine to
form tri-iodomethane

This test specifically identifies aldehydes and ketones with the structure:

“R” can be a hydrogen atom or a hydrocarbon group (alkyl or aryl).

If “R” is hydrogen, the compound is ethanal, CH3CHO. Ethanal is the only aldehyde that gives positive
tri-iodomethane test.

warm
+ 3I2(aq) + 4OH- + CHI 3 + 3I– + 3H2O

ethanal or methyl ketones carboxylate ion iodoform

Reagents and
conditions: Aqueous I2 with NaOH(aq), warm

Observations: Yellow crystals of CHI3 (iodoform) formed.

Note:
This reaction breaks a C–C bond and removes a methyl (–CH3) group. It is therefore a useful method
of shortening a carbon chain by a single carbon atom (step-down reaction).

Recall: Alcohols with the structure below also give a positive tri-iodomethane test. Refer to the
tri-iodomethane test in Topic 16 Hydroxy Compounds.

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Exercise 4.5
Suggest a structure for each of the isomers, X, Y and Z of the compound C3H6O2, based on the
following reactions:
X: gives tri-iodomethane with aqueous alkaline iodine and reduces Fehling’s solution;
Y: gives tri-iodomethane with aqueous alkaline iodine but does not reduce Fehling’s
solution;
Z: does not give tri-iodomethane with aqueous alkaline iodine but does reduce
Fehling’s solution.

Exercise 4.6
Which compound will not give tri-iodomethane on warming with alkaline aqueous iodine?

A CH3COCHClCOCH3 B

C I2CHCH(OH)CO2H D CI3CO2CH3

[N2010/1]

Summary of Distinguishing Tests

Reagents &
Aldehyde Benzaldehyde Ketone Comments
Conditions

 A characteristic test for aldehydes and

ketones
 All other functional groups will give
+ + + negative results.
2,4-DNPH
 This test differentiates aldehydes and
ketones from ALL other functional
groups.

K2Cr2O7 /
 Good test to differentiate aldehydes and
dilute H2SO4 + + –
benzaldehydes from ketones.
Heat

 Another method to differentiate

Tollens’
aldehydes from ketones.
reagent, + + –
 ALL aldehydes give positive Tollens’
Heat
Test.
Fehling's  Good test to further differentiate
reagent, + – – aldehydes from benzaldehydes.
Heat

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Exercise 4.7

Describe a simple chemical test to differentiate the following sets of compounds:

(i) butanal and butanone

(ii) propanone and propan-1-ol
(iii) propanal, propanone and benzaldehyde

Summary of reactions of aldehydes and ketones

State the reagents and conditions needed for the conversions on the arrows below:

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18 Carboxylic Acids & Derivatives

GUIDING QUESTIONS
Carboxylic Acids
● How are carboxylic acids synthesised?
● What types of reactions do carboxylic acids undergo and why?

Acid Derivatives
● How are acyl chlorides and esters synthesised?
● What types of reactions do acyl chlorides and esters undergo and why?
● How do the ease of hydrolysis of acyl chlorides compare with that of alkyl and aryl chlorides?

How do we compare the acidity of organic compounds in aqueous medium?

LEARNING OUTCOMES
Students should be able to:
11.7 (a) describe the formation of carboxylic acids from alcohols, aldehydes and nitriles
11.7 (b) describe the reactions of carboxylic acids in the formation of:
(i) salts
(ii) esters on condensation with alcohols, using ethyl ethanoate as an example
(iii) acyl chlorides, using ethanoyl chloride as an example
(iv) primary alcohols, via reduction with lithium aluminium hydride, using ethanol as an
example.
11.7 (c) explain the acidity of carboxylic acids and of chlorine-substituted ethanoic acids in terms
of their structures
11.7 (d) describe the hydrolysis of acyl chlorides
11.7 (e) describe the condensation reactions of acyl chlorides with alcohols, phenols and primary
amines
11.7 (f) explain the relative ease of hydrolysis of acyl chlorides, alkyl chlorides and aryl chlorides
11.7 (g) describe the formation of esters from the condensation reaction of acyl chlorides, using
phenyl benzoate as an example
11.7 (h) describe the acid and base hydrolysis of esters

REFERENCES
1. Peter Cann & Peter Hughes, Chemistry, 2015, Hodder Education, Chapter 18
2. Graham C. Hill & John S. Holman, Chemistry in Context, Nelson, Chapter 29

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1 INTRODUCTION TO CARBOXYLIC ACIDS

All carboxylic acids contain the carboxyl group (–CO2H), as shown below:

The molecule is trigonal planar about the carboxyl carbon, which is sp2 hybridised, with bond angles
approximately 120o.

Examples of carboxylic acids:

CO2H
O O

HO C CH2CO2H
C C
HO H HO CH3
CH2CO2H
formic acid (methanoic acid) acetic acid (ethanoic acid)
citric acid
Simplest carboxylic acid. First isolated Important chemical A tribasic acid. Found in citrus
in the 17th century by distillation of reagent and industrial fruits. Often used as a
dead ants. chemical. flavouring in soft drinks.

HO

eicosapentaenoic acid
aspirin
A commonly used pain-killer, which is An omega-3 fatty acid.
also an anti-inflammatory medicine. Found in fish such as salmon and cod.

Did you know?

Ant hills had long been known to emit acidic vapour when the English naturalist John Ray attempted
his somewhat brutal distillation of ants, but it is thanks to him that the source was discovered.
Methanoic acid, also known by its trivial name, formic acid, is the weapon of choice for the members
of the family formicidae, along with hundreds more species of wasp, bee and termite in the
invertebrate order Hymenoptera. Sprayed or stung (along with a variety of other substances) the acid
is a powerful and painful deterrent for would-be aggressors, and an effective biocide. A paste of baking
soda (sodium hydrogencarbonate) and very cold water can be applied to neutralise the acid and sooth
the pain.

John Ray (1628-1705)

Picture source: http://www.ucmp.berkeley.edu/history/ray.html Picture source: www.CartoonStock.com

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1.1 Nomenclature

Straight chain carboxylic acids are named by replacing the terminal ‘-e’ of the corresponding alkane
with “-oic acid”. For branched carboxylic acids, find the longest chain containing the
–CO2H group, and change the terminal ‘-e’ of the parent alkane to the suffix ‘-oic acid’. The carboxyl
carbon is numbered C1.

methanoic acid cis-but-2-enoic acid 2-propylpentanoic acid 2-chloropropanoic acid

Compounds that contain the –CO2H group bonded to a ring are named using the suffix ‘carboxylic
acid’. If the carboxyl group is directly attached to an aromatic ring, the suffix used is ‘benzoic acid’.
The carbon in the ring that is attached to the –CO2H group is numbered C1.

For aromatic acids which have 2 –CO2H groups attached directly to the benzene ring, it is named as
dicarboxylic acids.

cyclopent-1-ene 2-hydroxy-5-methylcyclohexane 4-nitrobenzoic acid benzene-1,2-

carboxylic acid carboxylic acid dicarboxylic acid

Exercise 1.1 (Worked Example)

Draw the structural formula for each of the following compounds:
1. 2-hydroxy-3-methylbutanoic acid 2. cyclohept-4-ene-1,3-dicarboxylic acid

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2 PHYSICAL PROPERTIES OF CARBOXYLIC ACIDS

2.1 Boiling Points

b.p. b.p.
Alcohol Mr Carboxylic acid Mr
/oC /oC
Ethanol CH3CH2OH 46 78 Methanoic acid HCO2H 46 101
Propan-1-ol CH3CH2CH2OH 60 97 Ethanoic acid CH3CO2H 60 118
Butan-1-ol CH3CH2CH2CH2OH 74 118 Propanoic acid CH3CH2CO2H 74 141

Carboxylic acids have higher boiling points than corresponding alcohols with similar size of electron
cloud (size of electron cloud may be compared based on Mr) because:

1. Hydrogen bonding between carboxylic acid molecules is stronger than that between alcohol
molecules. This is due to the presence of the electron-withdrawing C=O group causing the δ+ on
the H atom to be intensified and the O−H bond to be more polarised in the carboxylic acid.

2. Carboxylic acids can dimerise (in the pure liquid) through hydrogen bonding (diagram below),
effectively doubling the number of electrons (or size of electron cloud) in the dimer. This results
in stronger dispersion forces between dimers.

hydrogen bond

2.2 Solubility

In non-hydrogen-bonding solvents such as benzene, carboxylic acids can form the hydrogen-bonded
dimers. Carboxylic acids, especially those with longer hydrocarbon chains, are generally soluble in such
non-polar solvents as dispersion forces can be formed between the solvent molecules and the
hydrocarbon chain of the dimers.

In water, the carboxylic acid does not dimerise. The carboxylic acid molecules (the –CO2H group) can
form hydrogen bonding with the water molecules.

For carboxylic acids with longer hydrocarbon chains, solubility in water decreases as the hydrocarbon
chain gets longer. The longer the non-polar hydrocarbon chain, the stronger the dispersion forces

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between carboxylic acid molecules. Energy released from hydrogen bonding between –CO2H group
and water molecules is less than the energy needed to overcome these dispersion forces, as well as
the existing hydrogen bonding between water molecules.

Similarly, benzoic acid (a white crystalline solid at room temperature) is only slightly soluble in cold
water but dissolves readily in hot water.

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3 PREPARATION OF CARBOXYLIC ACIDS

LO 11.7 (a): describe the formation of carboxylic acids from alcohols, aldehydes and nitriles

Carboxylic acids can be prepared from:

● Oxidative cleavage of alkenes (Topic 11 Alkenes)
● Side chain oxidation of alkylbenzenes (Topic 12 Arenes)
● Acid and alkaline hydrolysis of nitriles (Topic 15 Halogen Derivatives)
● Oxidation of primary alcohols (Topic 16 Hydroxy Compounds)
● Oxidation of aldehydes (Topic 17 Carbonyl Compounds)
● Hydrolysis of acyl chlorides (covered later in Section 6.2.1)
● Acid and alkaline hydrolysis of esters/amides (esters covered later in Section 7.4, amides in Topic
19 Nitrogen Compounds)

Exercise 3.1 (Worked Example)

1. Suggest the product formed from the oxidation of 2-methyl-1-butanol, using hot acidified
potassium manganate(VII).

The primary alcohol is oxidised to a carboxylic acid.

2. Give the synthetic routes to show the conversion of the halogenoalkane to propanoic acid:

(i) CH3CH2Br
CH3CH2Br  CH3CH2CN  CH3CH2CO2H
Step 1: ethanolic KCN, heat (bimolecular nucleophilic substitution SN2)
Step 2: dilute H2SO4 (aq), heat (acid hydrolysis)

(ii) CH3CH2CH2Br
CH3CH2CH2Br  CH3CH2CH2OH  CH3CH2CO2H
Step 1: NaOH(aq), heat (bimolecular nucleophilic substitution SN2)
Step 2: KMnO4, dilute H2SO4, heat (oxidation)

(iii) CH3CH2CHBrCH2CH2CH3
CH3CH2CHBrCH2CH2CH3  CH3CH2CH=CHCH2CH3  CH3CH2CO2H
Step 1: ethanolic NaOH, heat (elimination)
Step 2: KMnO4, dilute H2SO4, heat (oxidative cleavage)

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4 REACTIONS OF CARBOXYLIC ACIDS

LO 11.7 (b): describe the reactions of carboxylic acids in the formation of:
(i) salts
(ii) esters on condensation with alcohols, using ethyl ethanoate as an example
(iii) acyl chlorides, using ethanoyl chloride as an example
(iv) primary alcohols, via reduction with lithium aluminium hydride, using ethanol as an example.

The characteristic chemical behaviour of carboxylic acids is determined by the carboxyl group.

There are 3 main kinds of reactions that carboxylic acids undergo:

(i) Acid-metal/Acid-base reactions (O–H bond is broken to form salts)
(ii) Nucleophilic (acyl) substitution (replacement of the –OH group)
(iii) Reduction of the CO2H group

The C=O and O–H bonds are so close in proximity that carboxylic acids do not behave exactly like
alcohols, aldehydes or ketones. For example,
(i) carboxylic acids are stronger acids than alcohols (discussed further in Section 4.1.1)
(ii) carboxylic acids do not undergo nucleophilic addition like aldehydes and ketones and do not
give a positive test with 2,4-dinitrophenylhydrazine and aqueous alkaline iodine. This is
because the delocalisation of electrons from the O–H group into the C=O group makes the
carboxyl carbon less electron deficient and less readily attacked by nucleophiles.

4.1 Acidity of Carboxylic Acids

LO 11.7 (c): explain the acidity of carboxylic acids and of chlorine-substituted ethanoic acids in terms of their structures

Carboxylic acids are weak Bronsted acids. The O–H bond breaks to give H+ and the conjugate base,
RCO2– (carboxylate ion).

As seen in Topic 16 Hydroxy Compounds, the strength of acids depends on the stability of the
conjugate base formed.

The conjugate base is negatively charged. The more dispersed the negative charge, the less likely the
conjugate base will accept a proton (to re-form the acid), the more stable it is.

The more stable the conjugate base, the greater the extent of acid dissociation, the larger the Ka (the
smaller the pKa) and the stronger the acid.

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4.1.1 Relative acidities of carboxylic acids, phenols and aliphatic alcohols

Ethanol Water Phenol Ethanoic acid

CH3CH2OH H2O C6H5OH CH3CO2H
pKa 15.9 15.7 9.95 4.75
Table 1. pKa values to compare the acidities of ethanol, water, phenol and ethanoic acid.

From the pKa values above, carboxylic acids are stronger acids than phenols or aliphatic alcohols.

The negative charge on the carboxylate ion is delocalised equally over two highly electronegative
oxygen atoms. The negative charge is dispersed and the carboxylate anion is greatly stabilised.

Recall that the negative charge on the phenoxide ion is also delocalised i.e. over the benzene ring
which explains why phenol is more acidic than alcohols and water. However, the delocalisation in the
phenoxide ion is less than that in the carboxylate ion, as the carbon atoms in the benzene ring do not
bear the negative charge as well as the two electronegative O atoms in the carboxylate ion. Hence the
carboxylate ions are more stabilised than the phenoxide ion and phenols are weaker acids than
carboxylic acids.

OH O
+ H2O + H3O

phenol phenoxide ion

The electron-donating alkyl group (–R) intensifies the negative charge on the alkoxide anion and the
alkoxide anion is destabilised.

The difference in acidity of carboxylic acids, phenols and alcohols affects their behaviour with sodium
metal, sodium hydroxide and sodium carbonate (or sodium hydrogencarbonate):
NaOH(aq) Na2CO3(aq) / NaHCO3(aq)
Na
a strong base weak bases
Aliphatic alcohols (ROH) √ x x
Phenols √ √ x
Carboxylic acids (RCO2H) √ √ √
(√: react x: does not react)

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Recall from Topic 14 Acid-Base Equilibria that the stronger acid is able to protonate the conjugate
base of the weaker acid. Carboxylic acids (e.g. ethanoic acid, pKa = 4.75) are stronger acids than
carbonic acid, H2CO3, (pKa = 6.4) so they can donate a proton to the carbonate or hydrogencarbonate
ion.

CH3CO2H + HCO3− CH3CO2− + H2CO3

stronger acid stronger base weaker base weaker acid

Hence whenever we add carbonate or hydrogencarbonate to carboxylic acid, an acid-base reaction

occurs. Effervescence of CO2 is observed as the H2CO3 produced decomposes readily into CO2 and H2O.

H2CO3 CO2 + H2O

Phenol (pKa = 9.95) is a weaker acid than carbonic acid, hence phenol is unable to donate a proton to
the carbonate or hydrogencarbonate ion.

weaker acid weaker base stronger base stronger acid

Similarly, alcohols (e.g. ethanol, pKa = 15.9) do not react with sodium hydroxide, as being weaker acids
than water (pKa = 15.7), they are unable to donate a proton to the hydroxide ion.

CH3CH2OH + OH− CH3CH2O− + H2O

weaker acid weaker base stronger base stronger acid

Exercise 4.1 (Worked Example)

(a) Arrange the following molecules in order of decreasing acid strength (as Bronsted acid).
C6H5OH, H2CO3, CH3CO2H, HCl, CH3CH2OH

● Recall: HCl is a strong acid that dissociates completely in water

● Refer to the pKa values given in Section 4.1.1

HCl, CH3CO2H, H2CO3, C6H5OH, CH3CH2OH

(b) State if each of the following reactions will occur. If yes, complete the equation.

(i) C6H5O– + H2CO3

Yes, carbonic acid has lower pKa and hence is a stronger acid than phenol. It will be able to

protonate a phenoxide ion. C6H5O– + H2CO3  C6H5OH + HCO3−

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(ii) CH3CO2− + H2CO3

No reaction. Because H2CO3 has higher pKa and hence is a weaker acid than CH3CO2H. It will

not be able to protonate an ethanoate ion.

(iii) CH3CO2− + HCl

Yes HCl is a strong acid while ethanoic acid is a weak acid. HCl will be able to protonate
ethanoate ion. CH3CO2− + HCl  CH3CO2H + Cl−

(iv) CH3CH2O− + CH3CO2H

Yes ethanoic acid is a stronger acid than ethanol. Ethanoic acid will be able to protonate
the ethoxide ion. CH3CH2O− + CH3CO2H  CH3CH2OH + CH3CO2−

4.1.2 Effect of substituents on acidity of carboxylic acids

Electron-donating groups
Electron-donating groups (e.g. alkyl groups) intensify the negative charge on the carboxylate anion,
destabilise the anion and decrease the acidity of the carboxylic acid.

(The similar pKa values of ethanoic acid, propanoic acid and butanoic acid suggest that the length of
the alkyl chain does not have a significant impact on acidity.)

Electron-withdrawing groups
Electron-withdrawing groups (e.g. halogens, NO2, OH, NH2) disperse the negative charge on the
carboxylate anion, stabilise the anion and increase the acidity of the carboxylic acid.

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The halogen (e.g. Cl), –OH or –NH2 group exert an electron-withdrawing inductive effect (O and N are
electronegative atoms). The more electronegative the halogen atom, the greater the electron-
withdrawing effect, the stronger the acid.

Number of electron-withdrawing groups

Increasing the number of electron-withdrawing groups increases acidity.

Proximity of electron-withdrawing groups to the –CO2H group

The nearer the electron-withdrawing group is to the carboxyl group, the greater the inductive effect,
and the stronger the acid. As inductive effect decreases with increasing distance, it becomes
insignificant when the electron-withdrawing effect is acting through more than 4 atoms.

The effects of electron-donating and electron-withdrawing groups are also observed for substituted
benzoic acids.

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Exercise 4.2 (Worked Example)

Arrange these compounds in order of increasing pKa values.

ethanoic acid, chloroethanoic acid, ethanol, phenol, water

pKa: chloroethanoic acid < ethanoic acid < phenol < water < ethanol

The higher the pKa value, the weaker the acid. The strength of the acid depends on the stability of
its anion. The more stabilised the anion, the stronger the acid.

Ethanol is less acidic than water. The electron donating alkyl group (R) intensifies the negative
charge on the alkoxide anion, destabilising it.

Phenol is more acidic than ethanol and water. The negative charge on the phenoxide anion is
delocalised over the benzene ring. The negative charge is dispersed and phenoxide anion is
stabilised.

Ethanoic acid is more acidic than phenol. The negative charge on the ethanoate anion is delocalised
equally over two highly electronegative oxygen atoms. The delocalisation in the ethanoate anion is
greater than that in the phenoxide ion so the ethanoate anion is more stabilised than the phenoxide
ion.

Chloroethanoic acid is more acidic than ethanoic acid. The electron-withdrawing chlorine atom in
chloroethanoic acid disperses the negative charge on the carboxylate anion causing it to be more
stabilised.

4.1.3 Acid-metal (redox)/acid-base reactions

Like inorganic acids, carboxylic acids react with metals, bases, carbonates and hydrogencarbonate to
form salts.

With metals CH3CO2H + Na CH3CO2ˉNa+ + ½ H2

With bases CH3CO2H + NaOH CH3CO2ˉNa+ + H2O

With carbonates 2 CH3CO2H + Na2CO3 2 CH3CO2ˉNa+ + CO2 + H2O

With hydrogencarbonate CH3CO2H + NaHCO3 CH3CO2ˉNa+ + CO2 + H2O

The effervescence of CO2 with carbonates or hydrogencarbonates can be used as a distinguishing test
for the presence of carboxylic acids. CO2 forms a white ppt when bubbled through limewater.

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4.2 Nucleophilic (acyl) Substitution

Carboxylic acid and its derivatives can undergo nucleophilic (acyl) substitution reactions at the C=O
carbon. This type of reaction occurs because:
● the C=O carbon has a partial positive charge due to the electronegative O
● the C=O carbon has a planar geometry and is relatively unhindered, which makes it susceptible
towards nucleophilic attack.

For your information only (not in H2 syllabus)

Nucleophilic (acyl) substitution reactions of carboxylic acids, esters, amides and acyl chlorides involves
first the nucleophilic addition of nucleophile across the C=O, to form a tetrahedral intermediate,
followed by elimination of a small molecule of H2O, ROH, NH3 or HCl respectively:

R= alkyl, aryl, H
X = OH, OR, NH2, Cl, etc

4.2.1 Condensation to form esters

Carboxylic acids can react with alcohols, but not phenols, in a condensation reaction to form esters,
when heated in the presence of concentrated sulfuric acid (refer to Topic 16 Hydroxy Compounds).

In this reaction, the C–O bond of the –CO2H group is broken, as evidenced by isotopic labelling (recall
this technique under Reaction Mechanisms in Topic 6 Reaction Kinetics).

4.2.2 Formation of acyl chlorides

Like alcohols, the –OH group in carboxylic acids can be replaced with a –Cl group to form acyl chlorides,
using the same chlorinating reagents: PCl5, PCl3 and SOCl2.

Reagents and conditions: PCl5 , room temperature

Observations: White fumes of HCl produced.

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Reagents and conditions: PCl3 , room temperature

Comments: PBr3 or P/I2 heat may be used to obtain respective acyl halides.

Reagents and conditions: SOCl2 , warm

Comments: Most convenient industrial method as by-products are gases and
easily removed. Unreacted SOCl2 is also easily distilled off (b.p. 79oC).

Carboxylic acids are often converted into acyl chlorides, which are highly reactive and could in turn be
easily converted to other compounds.

4.3 Reduction to Primary Alcohols

Carboxylic acids are reduced to primary alcohols using lithium aluminium hydride.

Reagents and conditions: LiAlH4, dry ether, room temperature

The LiAlH4 must be used in anhydrous conditions! Note that carboxylic acids can only be reduced back
to primary alcohols and not aldehydes.

Weaker reducing agents, such as NaBH4 or H2 with catalyst, will not work. Refer to Topic 17 Carbonyl
Compounds for the comparison between the different reducing agents. With careful consideration of
the reducing agents to be used, selective reduction can be done. For example,

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4.4 Special Case: Oxidation of Methanoic Acid and Ethanedioic Acid

Only TWO carboxylic acids undergo further oxidation – methanoic acid and ethanedioic acid.
All other acids cannot be oxidised by KMnO4.

Reagents and conditions: KMnO4, dilute H2SO4, heat under reflux

Observations: Purple solution (MnO4–) decolourises (Mn2+).
Effervescence of CO2 observed.

Exercise 4.3 (Worked Example)

Substance P is now commonly used in antiseptic creams. P could be synthesised in the lab from
compound Q by a method which involves an intermediate R.

(i) Draw the structure of the intermediate R.

The –CH3 group undergoes side-chain oxidation to become –CO2H

(ii) Suggest reagents and conditions for Steps 1 and 2.

Step 1: KMnO4, dilute H2SO4, heat under reflux (side-chain oxidation)

Step 2: CH3OH, conc. H2SO4, heat under reflux (nucleophilic substitution/condensation)

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Exercise 4.4 (Worked Example)

The reaction scheme below shows how compound C can be made from malonic acid. C is made from
B via intra-molecular esterification.

Suggest the structures for compound B and C.

In step 1, only one of the –CO2H groups is reduced to a primary alcohol.

In step 2, B undergoes intramolecular esterification (condensation reaction) to form C.

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5 CARBOXYLIC ACID DERIVATIVES

5.1 Introduction

Carboxylic acid derivatives are compounds in which the –OH group in the acid is replaced by –Y.

where Y = –X (F, Cl, Br, I), –OR’, –NH2

Some examples of acid derivatives are as follows:

In the following sections, we will focus on acyl chlorides and esters.

Amides will be covered in Topic 19 Nitrogen Compounds.

5.2 Nomenclature

Functional Acyl chloride (RCOCl) Ester (RCO2R’)

Group
Nomenclature Replace the ‘-oic acid’ of the parent First, name the R group attached to the
carboxylic acid with ‘-oyl chloride’. oxygen, followed by the parent carboxylic
acid, replacing the ‘-oic acid’ with ‘oate’.
Examples O O

Cl OCH3
pentanoyl chloride methyl 3-methylbutanoate
O

O
CH3 O

Cl phenyl ethanoate

3-ethylhexanoyl chloride
CO2CH3

COCl
methyl benzoate

benzoyl chloride Note that condensed structural formula

of esters can also be written as
R–OCO–R’ which just refers to:

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5.3 Physical Properties of Carboxylic Acid Derivatives

5.3.1 Boiling points

Name Formula Mr Boiling point/ °C

ethanoic acid CH3CO2H 60 118
ethanoyl chloride CH3COCl 78.5 51
methyl ethanoate CH3CO2CH3 74 58

Esters and acyl chlorides have lower boiling points than their corresponding carboxylic acids. Their
intermolecular permanent dipole-permanent dipole attractions are weaker than the hydrogen
bonding for carboxylic acids, and require less energy to break. (Esters and acyl chlorides are unable to
form intermolecular hydrogen bonding as they lack a hydrogen atom directly attached to a highly
electronegative oxygen atom.)

5.3.2 Solubility

Esters are much less soluble in water compared to carboxylic acids and alcohols. Many esters are
immiscible with water. Acyl chlorides, on the other hand, hydrolyse in water:

5.3.3 Odour

Acyl chlorides are colourless liquids with a sharp, irritating odour (partly due to the rapid hydrolysis to
HCl and carboxylic acids).
Esters are colourless liquids with a pleasant and sweet or fruity smell. Esters are often used in the
preparation of perfumes and artificial flavourings.

Exercise 5.1 (Worked Example)

Suggest a reason why the boiling point of ethanoyl chloride is higher than that of 2-chloropropane.
In the ethanoyl chloride, the C=O group provides a stronger electron-withdrawing effect which results
in a larger permanent dipole compared to 2-chloropropane. Hence more energy is required to
overcome the stronger permanent-dipole-permanent dipole interactions between ethanoyl chloride
compared to 2-chloropropane.

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5.4 Chemical Reactivity of Carboxylic Acid Derivatives

Relative reactivity of carboxylic acids and their derivatives

Carboxylic acids and their derivatives differ greatly in reactivity towards nucleophilic substitution.

Reasons for the above trend:

1. Electronic Effects
● A halogen substituent withdraws electrons through inductive effect from the C=O group, thus
increases the partial positive charge on the carbon atom. This makes acyl halides more readily
attacked by nucleophiles.
● An amino group (—NH2 ) or alkoxy group (—OR’ ) donates electrons to the carbonyl carbon
through resonance effect. This decreases the partial positive charge on C=O carbon atom.
Hence, amides and esters are less readily attacked by nucleophiles.

2. Leaving Group
● In general, the weaker the base, the better the leaving group. Halide anions are better leaving
groups compared to the hydroxide ion as halides are weaker bases while the hydroxide ion is
a stronger base (refer to discussion of leaving groups under nucleophilic substitution of
alcohols in Topic 16 Hydroxy Compounds).

Because of these reactivity differences, it is usually possible to convert a more reactive acid derivative
into a less reactive one.

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6 ACYL CHLORIDES

6.1 Preparation of Acyl Chlorides

Acyl chlorides can be prepared from the following:

● Nucleophilic substitution of carboxylic acids (Section 4.2.2)

6.2 Reactions of Acyl Chlorides

6.2.1 Hydrolysis to form carboxylic acids (nucleophilic (acyl) substitution with water)
LO 11.7 (d): describe the hydrolysis of acyl chlorides

Acyl chlorides react with water violently at room temperature to give a carboxylic acid and white
fumes of HCl. In fact, aliphatic acyl chlorides usually fume in moist air due to the formation of hydrogen
chloride.

Reagents and conditions: water, room temperature

Comments: Rapid reaction forming white fumes of HCl

Exercise 6.1 (Worked Example)

Suggest a simple chemical test to distinguish CH3CO2H from CH3COCl.

Add a few drops of water – dense white fumes of HCl will be observed for acyl chloride, no white
fumes for carboxylic acid.
OR
Add a few drops of aqueous silver nitrate – white ppt of AgCl observed for acyl chloride, no white ppt
for carboxylic acid.

6.2.2 Condensation to form esters (nucleophilic (acyl) substitution with alcohols/phenols)

LO 11.7 (e)part: describe the condensation reactions of acyl chlorides with alcohols, phenols
LO 11.7 (g)part: describe the formation of esters from the condensation reaction of acyl chlorides

Acyl chlorides react with both alcohols and phenols to form esters via a condensation reaction. Refer
to Topic 16 Hydroxy Compounds for the details of the reaction.

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6.2.3 Condensation to form amides (nucleophilic (acyl) substitution with ammonia/amines)

LO 11.7 (e)part: describe the condensation reactions of acyl chlorides with primary amines

Acyl chlorides react readily with ammonia to form amides, and with primary and secondary amines to
form N-substituted amides. Tertiary amines do not form amides as they do not contain a replaceable
H atom on the N.

Reagents and conditions: ammonia or primary amines or secondary amines

(in excess), room temperature

Ammonia or amines are added in excess to ensure complete reaction as some ammonia or amines
reacts with the acidic HCl to form an ammonium salt via acid-base reaction, i.e., NH3 + HCl → NH4Cl

Carboxylic acids cannot be used in place of the acyl chlorides. This is because they react with
amines/ammonia in an acid-base reaction instead. E.g. CH3CO2H + NH3 → CH3CO2−NH4+

Exercise 6.2 (Worked Example)

Which of these compounds cannot be made in one step from ethanoyl chloride?
A CH3COC2H5 C CH3CONH2
B CH3CONHC6H5 D CH3CO2H
[N1997/III/28]
Answer: A
CH3COC2H5 is a ketone and it cannot be synthesised in one step from an acyl chloride.

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6.3 Relative Rate of Hydrolysis of Acyl Chlorides, Alkyl Chlorides and Aryl Chlorides
LO 11.7 (f): explain the relative ease of hydrolysis of acyl chlorides, alkyl chlorides and aryl chlorides

Type of chlorides Acyl chlorides Alkyl chlorides Aryl chlorides

Rate of hydrolysis

Note: The relative reactivity of alkyl chlorides and aryl chlorides was covered in
Halogen Derivatives.
ethanoyl chloride chloroethane Chlorobenzene
 
O Cl
Example 
CH3 C  C Cl
H
Cl CH 3
 H

Not possible under ordinary

H2O aqueous NaOH/ KOH lab conditions (only
Hydrolysis
possible under very high
conditions room temperature heat under reflux temperature and pressure
with aq. alkali)
C–Cl cleaves easily C–Cl cleaves only with C–Cl does not cleave easily
without heating heating

Highly electron Less electron deficient Least electron deficient

deficient carbon on carbon on C–Cl due to carbon on C–Cl due to the
C–Cl due to 2 polarisation by one delocalisation of the lone
electronegative atoms electronegative Cl atom pair of electrons on Cl into
Electronic
Cl and O only the benzene ring imparting
factor
partial double bond
Reasons character to the C– Cl bond
in aryl chlorides,
strengthening the bond.
Attracts nucleophile Attracts nucleophile less
more strongly strongly Attracts nucleophile
minimally
Planar acyl carbon Tetrahedral geometry Bulky aromatic ring hinders
Steric makes it less hindered around chloro-substituted nucleophilic attack.
factor for the nucleophile to carbon is relatively more Electron-rich benzene ring
attack. hindered. repels nucleophile.
White ppt of AgCl No ppt formed in the cold. No ppt observed even after
Reaction with observed immediately. To obtain AgCl ppt, aqueous prolonged boiling with
NaOH and heating are aqueous NaOH.
aq AgNO3
required (refer to Topic 15
Halogen Derivatives)

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Exercise 6.3 (Worked Example)

Liquid L gives a white precipitate immediately when shaken with aqueous silver nitrate. Which
of the following structure(s) could be L?

Answer:

Only could be L because it is the only acyl chloride in the

list (which gives white ppt immediately with AgNO3.

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7 ESTERS

7.1 Introduction

Esters are generally sweet-smelling compounds and are widely used as flavourings and perfumes.
Ester linkages also occur naturally in fats and lipids. Small esters, together with other volatile organic
compounds, often give off fragrances that are characteristic of fruits.

O O

methyl butanoate methyl trans-cinnamate isoamyl acetate

(apples) (strawberry) (banana)

Some esters are pheromones (chemicals that will influence the behavior of animals of the same species).
For instance, isoamyl acetate is a pheromone that attracts other bees and is released by a honey bee’s
sting. This serves as a trigger for other bees to congregate and attack!

Fats are made up of triglycerides which are esters of fatty acids, as shown below (the R groups represent
long hydrocarbon chains). Saponification is used in making soap from fats.

Saponification involves base (such as NaOH) hydrolysis of triglycerides to form the sodium salt of a
carboxylate, which has a long chain hydrocarbon non-polar “tail” and a polar negatively charged “head”.
These carboxylate salts are effectively soap. Your hands feel slippery when they come into contact with
alkalis because of the saponification of fats and oils on your hands. The esters in the oil (triglycerides)
undergo saponification in the presence of hydroxide ions and soap is effectively produced!

Esters are prepared industrially mainly for use as essence, perfumes and artificial flavourings, e.g.:
(i) ethyl methanoate – rum flavouring
(ii) methyl butanoate – apple flavour
(iii) propyl pentanoate – pineapple flavour

Esters are also widely used as organic solvents, e.g.:

(i) ethyl ethanoate – paints and varnishes
(ii) butyl ethanoate – extraction of penicillin
(iii) pentyl ethanoate – nitrocellulose

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7.2 Isomerism

Saturated esters and carboxylic acids have the general formula CnH2nO2 where n equals to the number
of carbon atoms in the compound. Esters and carboxylic acids are constitutional isomers if they have
the same number of carbon atoms in the compound.

For esters only, the carboxyl group may occur at different positions along the alkyl chain.

Exercise 7.1 (Worked Example)

Draw the structures of four isomeric esters with the formula C4H8O2, and name them.

7.3 Preparation of Esters

LO 11.7 (g)part: describe the formation of esters from the condensation reaction of acyl chlorides

Esters can be prepared from:

● condensation reaction between carboxylic acid and an alcohol (Topic 16 Hydroxy Compounds)
● condensation reaction between acyl chloride and an alcohol (Section 6.2.2)

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7.4 Reactions of Esters

LO 11.7 (h): describe the acid and base hydrolysis of esters

Esters can undergo acid or base hydrolysis to yield the alcohols and carboxylic acids. These reactions
occur via the general nucleophilic (acyl) substitution mechanism shown in Section 4.2.

7.4.1 Acid hydrolysis

Reagents and conditions: dilute H2SO4, heat under reflux

The acid hydrolysis reaction is reversible. A large excess of water (dilute acid) is used to ensure
equilibrium lies to the right. Notice that this is the reverse of the condensation reaction of alcohols
and carboxylic acids to form esters.

7.4.2 Base hydrolysis (saponification)

Reagents and conditions: dilute NaOH, heat under reflux

followed by acidification with dilute H2SO4 at room temperature and
pressure

The base hydrolysis reaction is rapid and irreversible. The RCO2 ion formed has little tendency to
undergo nucleophilic attack again by the alcohol, thus the reaction goes to completion.

To obtain the carboxylic acid from its salt, aqueous acid is added to the mixture at the end of the
reaction to protonate the carboxylate anion.

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Exercise 7.2 (Worked Example)

Draw the structures of the products formed when the following ester is subjected to

(i) acid hydrolysis,

(ii) base hydrolysis.

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Summary of reactions of carboxylic acids and derivatives

Summary Exercise
State the reagents and conditions needed for the conversions on the arrows below:

Carboxylic acids

3 9

10

11

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Acyl chlorides

1 4

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19 Nitrogen Compounds
GUIDING QUESTIONS
Amines
 How are amines synthesised?
 What types of reactions do amines undergo and why?
Phenylamines
 How are phenylamines synthesised?
 What types of reactions do phenylamines undergo and why?
 What are the effects of the delocalisation of the lone pair of electrons on nitrogen of phenylamine into
the benzene ring?
Amides
 How are amides synthesised?
 Why are amides neutral?
 What types of reactions do amides undergo and why?
Amino Acids
 What are the properties of amino acids?
 What types of reactions do amino acids undergo and why?

How do we compare the basicity of organic nitrogen compounds?

LEARNING OUTCOMES
Students should be able to:
19(a) describe the formation of amines as exemplified by ethylamine (through amide and nitrile
reduction; refer to Topic 15 Halogen Derivatives) and by phenylamine (through the
reduction of nitrobenzene)
19(b) describe the reaction of amines in the formation of salts
19(c) describe and explain the basicity of primary, secondary and tertiary amines in the gaseous
phase (interpret as Lewis bases)
19(d) explain the relative basicities of ammonia, ethylamine and phenylamine, in aqueous
medium, in terms of their structures
19(e) describe the reaction of phenylamine with aqueous bromine
19(f) describe the formation of amides from the condensation reaction between RNH2 and R'COCl
19(g) explain why amide is neutral in terms of delocalisation of the lone pair of electrons on
nitrogen
19(h) describe the chemistry of amides, exemplified by the following reactions:
(i) hydrolysis on treatment with aqueous alkali or acid
(ii) reduction to amines with lithium aluminium hydride
19(i) describe the acid/base properties of amino acids and the formation of zwitterions
(knowledge of isoelectric points is not required)
19(j) describe the formation of peptide (amide) bonds between α-amino acids and, hence explain
protein formation
19(k) describe the hydrolysis of proteins

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REFERENCES
1. Peter Cann & Peter Hughes (2014). Chemistry, Hodder Education, Chapter 27
2. John McMurry (2012). Organic Chemistry. 9th Edition, Cengage Learning, Chapter 24

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1 INTRODUCTION

Amines are derivatives of ammonia, NH3, in which one or more hydrogen atoms are
replaced by alkyl or aryl groups.

Amines are classified as primary, secondary and tertiary according to the number of
carbon atoms directly attached to the N atom.
Primary (1°) Secondary (2°) Tertiary (3°) Quaternary
amines amines amines ammonium ions
Amines
Aliphatic

e.g. CH3CH2NHCH3 e.g. (CH3)4N+

e.g. CH3CH2NH2 e.g. (CH3)3N
N-methyl Tetramethyl-
ethylamine trimethylamine
ethylamine ammonium ion
Nitrogen Compounds

Aromatic

e.g. e.g. e.g.

e.g. N,N,N-trimethyl
phenylamine N-methylphenyl N,N-dimethyl
amine phenylamine phenyl-ammonium
ion
For aromatic amine, the nitrogen atom is directly attached to the benzene ring
Amides are derivatives of carboxylic acids.
Primary amides Substituted amides e.g.
Amides
Amino Acids

Amino acids contain both an acidic carboxyl group (-CO2H) and

a basic amino group (-NH2) on the same molecule.

Table 1. Various functional groups of nitrogen compounds

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1.1 Nomenclature
1.1.1 Amines
Simple amines are named by adding the suffix –amine to the name of the longest alkyl group that is
attached to the nitrogen atom.

The longest carbon chain containing the amine group is considered the parent structure. Number the
alkane chain beginning at the end nearer the amine group.
Note: An alternative way of naming amines is to replace the final –e in the name of the parent
compound with the suffix –amine.

In secondary and tertiary amines, the capital N denotes the location of the substituents directly
attached to the nitrogen atom.

If there is a functional group of higher priority, the –NH2 group can be considered as an amino
substituent in the prefix.

1.1.2 Amides
Primary amides with an unsubstituted –NH2 group are named by replacing the –oic acid of the parent
carboxylic acid with –amide.

If the nitrogen atom is further substituted, the location of the substituent group is denoted by a capital
N.

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Exercise 1.1
Name the following compounds and indicate whether it is a primary, secondary or tertiary amine:
(Worked Example) (Worked Example)

1. 2.

2-chlorocyclohexylamine N-ethylpropylamine
(primary amine) (secondary amine)

3. 4.

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2 PHYSICAL PROPERTIES OF AMINES AND AMIDES

2.1 Odour
The aliphatic amines of lower molecular weight have a characteristic pungent smell whereas the
higher members have strong “fishy” odours. Sometimes even “foul smelling” is an understatement,
and two of the amines produced in decaying flesh are named cadaverine and putresine.

2.2 Boiling points

Number of
Structural
Name electrons in b.p. / oC Predominant Intermolecular forces
formula
the molecules
Methylamine CH3NH2 18 6 hydrogen bonding
Ethylamine CH3CH2NH2 26 17 hydrogen bonding
Propylamine CH3CH2CH2NH2 34 50 hydrogen bonding
N-methylethanamine CH3CH2NHCH3 34 34 hydrogen bonding
N,N- permanent dipole-permanent dipole
(CH3)3N 34 3
dimethylmethanamine interactions
Table 2. Boiling points of some amines

 Comparing methylamine, ethylamine and propylamine, as the number of carbon atoms and
electrons increases, more energy is required to overcome the increasing strength of dispersion
forces between the molecules. Thus, boiling point increases with increasing number of carbon
atoms.
 Primary and secondary amines have higher boiling points than tertiary amines. Since tertiary
amines have no N—H bond, they are unable to form hydrogen bonds. Their molecules are held
together by weaker permanent dipole – permanent dipole interaction which requires less energy
to overcome as compared to stronger hydrogen bonds between molecules of primary and
secondary amines.

Number of
Structural
Name electrons in the b.p. / oC Predominant Intermolecular forces
formula
molecules
Methylamine CH3NH2 18 6 hydrogen bonding
Ethane CH3CH3 18 89 dispersion forces
Methanol CH3OH 18 65 hydrogen bonding
Table 3. Boiling points of corresponding alkane, alcohol and amine (similar no. of electrons in the molecules)

 Methylamine, CH3NH2, has a considerably higher boiling point compared to its corresponding
alkane (ethane) due to the presence of stronger intermolecular hydrogen-bonding compared to
only weaker dispersion forces in the alkane.
 However, boiling point of CH3NH2 is lower than that of the corresponding alcohol (methanol), since
the N-H bond is less polar than the O-H bond. Hence, the intermolecular hydrogen-bonds in
alcohols are stronger than those between amine molecules and require more energy to overcome.

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Amides are white crystalline solids at room temperature, apart from

methanamide, which is a liquid. Amides can form extensive
intermolecular hydrogen bonds as a result of the polar nature of the
N–H bond, and these hydrogen bonds result in relatively high melting
and boiling points.

2.3 Solubility in water

Aliphatic amines with four carbon atoms or fewer are readily soluble in water due to their ability to
form strong hydrogen bonds with water molecules.

Phenylamines and amines with increasing length of hydrocarbon chain are virtually insoluble in water
because the energy released from hydrogen bonding formed between these amines with water is less
able to overcome the energy required to overcome the increasing strength of dispersion forces
between larger hydrocarbon chains, as well as the existing hydrogen bonding in water. In addition,
the non-polar large hydrocarbon skeletons also disrupt the hydrogen bonding with water molecules.
These compounds do dissolve, though, in organic solvents, e.g. benzene.

For amides, their ability to form extensive hydrogen bonds with water also means that simple amides
are very soluble in water.

Exercise 2.1
(a) (Worked Example)
Propylamine is highly soluble in water. Draw a diagram to illustrate how a molecule of
propylamine interacts with a molecule of water.

(b) Explain why H2NCH2CH2NH2 has a boiling point of 116C while propylamine has a boiling point of
50C.

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3 BASICITY OF NITROGEN COMPOUNDS

LO 19(c): describe and explain the basicity of primary, secondary and tertiary amines in the gaseous phase (interpret as Lewis bases)
LO 19(d): explain the relative basicities of ammonia, ethylamine and phenylamine, in aqueous medium, in terms of their structures

3.1 Amines
Like ammonia, amines contain a lone pair of electrons on the nitrogen atom that can form a co-
ordinate (dative covalent) bond with a proton. Hence, amines can act as proton-acceptors or
Bronsted-Lowry bases. Amines can also act as Lewis bases by donating this electron pair to an acid.
(Refer to Topic 4 Reactions and Stoichiometry for the theories of acids and bases.) The basicity of
amines depends on the availability of the lone pair of electrons on nitrogen for protonation (or
donation to an acid).

3.1.1 Basicity of amines in the gaseous phase (Lewis bases)

In the gaseous phase, aliphatic amines are more basic than ammonia because alkyl groups are
electron-donating; they increase the electron density on nitrogen atom, making the lone pair of
electrons more available to form a dative bond with an acid.

Therefore,

3.1.2 Basicity of amines in the aqueous medium

When amines are dissolved in water, an equilibrium is established in which the water donates a
hydrogen ion to the amine. The extent of this reaction is a measure of the amine’s basicity.

RNH2 + H2O RNH3+ + OH— [RNH 3 ][OH  ]

Base Conjugate acid Kb  and pK b   lg K b
[RNH2 ]
The larger the Kb values, the greater its basicity; the smaller the pKb, the stronger the base.

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3.2 Phenylamines
The pKa values below show phenylamines are considerably less basic than ammonia.

This is because in phenylamine, the lone pair of electron on nitrogen is delocalised into the benzene
ring. This decreases the electron density on the nitrogen atom, making the lone pair of electrons less
available to form a dative bond with a proton.

Figure 1. Extended delocalised π- electron cloud is present in phenylamines

Figure 1. Resonance structure of phenylamines

3.2.1 Substituted Phenylamines

Their relative basicity depends on the nature of the substituent attached to the benzene ring.

Electron-donating groups increase electron density

on the benzene ring, making the lone pair of
electrons on nitrogen atom more available for
donation to an acid. Hence these substituted
phenylamines are more basic than phenylamine.

Electron-withdrawing groups decrease electron

density on the benzene ring, making the lone pair of
electrons on nitrogen atom less available for
donation to an acid. Hence, these substituted
phenylamines are less basic than phenylamine.

Therefore,
stronger base weaker base

4-methylphenylamine phenylamine 4-nitrophenylamine

pKb 8.92 9.40 13.0

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3.3 Amides
LO 19(g): explain why amide is neutral in terms of delocalisation of the lone pair of electrons on nitrogen

Amides give neutral solutions in water (not basic). The delocalisation of the lone pair of electrons on
the nitrogen atom over the C=O bond reduces the electron density on the nitrogen atom such that
the lone pair of electrons on the nitrogen atom is not available for protonation.

Therefore, the relative basicity of ammonia, ethylamine, phenylamine and amide are as follows:

stronger base weaker base

CH3CH2NH2 NH3

ethylamine ammonia phenylamine ethanamide

pKb 3.35 4.74 9.40 14.50

Exercise 3.1
Arrange the following compounds in order of increasing basicity, giving your reasoning.

Basicity of amines in the aqueous phase (Background info)

In the aqueous medium, tertiary amines are less basic than expected because the resulting conjugate
acids are not as effectively solvated through hydrogen bonding by the surrounding water molecules
(absent in gaseous phase) as compared to conjugate acids of primary and secondary amines. Thus, the
conjugate acids are less stable, resulting in tertiary amines to ionise in water to a smaller extent.

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4 PREPARATION OF AMINES AND AMIDES

LO 19(a): describe the formation of amines as exemplified by ethylamine and by phenylamine
LO 19(f): describe the formation of amides from the condensation reaction between RNH2 and R'COCl

Amines can be prepared from:

 Nucleophilic substitution of halogenoalkanes (Topic 15: Halogen Derivatives)
 Reduction of nitriles (Topic 15: Halogen Derivatives) and amides (to be covered later in this
topic)
 Reduction of nitrobenzene
Phenylamine can be prepared by reduction of aromatic nitro-compounds using tin and excess
concentrated hydrochloric acid. The product first forms as a salt, C6H5NH3+Cl– and excess
NaOH(aq) is then added to liberate the free phenylamine. Aliphatic nitro-compounds are not
reduced using the same reagent.

Reagents & Conditions: 1. Sn, excess concentrated HCl, heat

2. NaOH(aq)

LiAlH4 and NaBH4 are not used in this above reaction because NaBH4 does not reduce nitro groups
at all, while LiAlH4 will reduce nitrobenzene to azo compounds instead, giving C6H5–N=N–C6H5.

Amides can be prepared from:

 Condensation of acyl chlorides (Topic 18: Carboxylic Acids & Derivatives)

Note: Carboxylic acids cannot be used in the preparation of amides. This is because they react
with amines/ammonia in an acid-base reaction instead. E.g. CH3CO2H + NH3  CH3CO2−NH4+.

Exercise 4.1
Give the reagents and conditions that you would use in the following conversions:
(a) (Worked Example)

(b)

(c)

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5 REACTIONS OF AMINES AND AMIDES

5.1 Amines
The chemistry of amines is dominated by the lone pair of electrons on nitrogen atom. They can
behave:
 as bases (donating the lone pair to a H+ ion or an acid)
 as good nucleophiles (being able to attack at the partial positive end of a polarized bond)
 as excellent ligands (with transition metals) – refer to Topic 22: Chemistry of the Transition
Elements

5.1.1 Reaction with acids

LO 19(b): describe the reaction of amines in the formation of salts
Amines (both aliphatic and phenylamines) can act as a base to react with acids (mineral or carboxylic
acids) to form salts.

Amines with bulky R-groups are insoluble in water (forming two immiscible layer when mixed) due to
the presence of non-polar hydrocarbon skeleton which hinder the formation of hydrogen bonds with
water molecules.
However, soluble ionic salts are formed through acid-base reaction when acids are added. The ionic
salts are soluble in water (forming a homogeneous solution as they can form favourable ion-dipole
interaction with water molecules) but insoluble in organic solvents. Thus an amine can be separated
from other organic compounds by converting it to a water-soluble ammonium salt. You may refer to
Topic 8: Introduction to Organic Chemistry on the details of the extraction procedure.

The amines can be regenerated from their corresponding salts by using strong bases, such as
NaOH(aq).

Stronger acid Stronger base Weaker base Weaker acid

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5.1.2 Nucleophilic substitution

Primary, secondary and tertiary amines can act as a nucleophile to react with halogenoalkanes and
form secondary amines, tertiary amines and quaternary ammonium salts respectively (refer to Topic
15: Halogen Derivatives).

5.1.3 Condensation
Primary and secondary amines (both aliphatic and phenylamines) can act as a nucleophile to react
with acid chlorides to form amides (refer to Topic 18: Carboxylic Acids & Derivatives).

5.1.4 Electrophilic substitution of phenylamine

LO 19(e): describe the reaction of phenylamine with aqueous bromine

Phenylamine reacts very quickly with aqueous bromine via an electrophilic substitution mechanism to
form a white precipitate. This is similar to the reaction of phenol with bromine (refer to Topic 16:
Hydroxy Compounds). Aliphatic amines do not react with bromine.

Reagents & Conditions: Aqueous bromine, room temperature

Observations: Yellow-orange solution decolourise; white ppt formed
(White fumes of HBr may not be observed as HBr dissolved in aqueous solution.)

Comments: 2,4,6-tribromophenylamine is formed because the –NH2 group is 2,4-directing. No

Lewis acid catalyst (halogen carrier) is required for this reaction, unlike bromination
of benzene (which requires AlCl3 or FeCl3).
Explanation: Like phenol, the lone pair of electrons on the nitrogen atom is delocalised into the
benzene ring, the electron density in the ring is greatly increased, making it much
more susceptible to electrophilic attack than benzene. Hence, the presence of the –
NH2 group highly activates the benzene ring towards electrophilic substitution and
no catalyst is required.

5.2 Amides
LO 19(h): describe the chemistry of amides, exemplified by the following reactions:
(i) hydrolysis on treatment with aqueous alkali or acid
(ii) reduction to amines with lithium aluminium hydride

In amides, the lone pair of electrons on the nitrogen atom is delocalised into the adjacent C=O bond.
Thus, the electron density on the nitrogen atom is reduced, making it unable to act as a nucleophile,
unlike amines.

The delocalisation also gives good stability to amides and makes them the least reactive of the
carboxylic acid derivatives.

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5.2.1 Reduction of amides

Amides can be reduced to amines by lithium aluminium hydride.

Reagents & Conditions: LiAlH4 in dry ether

5.2.2 Hydrolysis of amides

Amides can be hydrolysed by aqueous acids (e.g. dil H2SO4) or alkalis (e.g. dil NaOH) when heated
under reflux to yield the carboxylic acid or salt respectively. Although the exact same bond is cleaved
in both acidic and alkaline hydrolysis, the products of hydrolysis depend on the pH of the environment.

Reagents and conditions: dilute H2SO4, heat under reflux

Reagents and conditions: dilute NaOH, heat under reflux, followed by acidification with dilute
H2SO4 to yield the carboxylic acid
Comments: Ammonia will be produced if the primary amides undergo alkaline hydrolysis (a
distinguishing test). For substituted amides, amines are formed instead.

Exercise 5.1
Predict the products of the following reactions:
a) (Worked Example) b) c)
N,N-dimethylamine,
(CH3)2NH, and ethanoic
acid at room temperature and NaOH(aq) heat
and Br2 (aq)
(CH3)2NH2+ CH3CO2–
Acid-base reaction to
produce a salt.

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6 AMINO ACIDS

-Amino acids are the building blocks for all the proteins in the human
body. Naturally occurring amino acids are -amino acids where the
amino and carboxyl groups are bonded directly to the same α-carbon.
The general formula of an -amino acid is as follows:

There are 20 naturally occurring -amino acids (as shown in the next two pages), differing only in the
identity of the R group bonded to the α-carbon. The R group is called the side chain of the amino acid.
The simplest amino acid, called glycine, has R = H. Except for glycine, all other α-amino acids are chiral
and exist in optically active forms (enantiomers).

For your information

There are some non--amino acids in nature apart from the 20 common -amino acids. One notable
example is γ-aminobutanoic acid (GABA), which is the chief inhibitory neurotransmitter in the
mammalian central nervous system. Note that the amino and carboxyl groups are attached to
different carbons.

γ-aminobutanoic acid

6.1 Formation of zwitterion

LO 19(i): describe the acid/base properties of amino acids and the formation of zwitterions (knowledge of isoelectric points
is not required)

Amino acids can undergo an intramolecular acid-base reaction, and exist as dipolar ions with no overall
electrical charge called zwitterions.

Amino acids exist as zwitterions in aqueous solutions and in the solid state. Therefore, many physical
properties of amino acids resemble that of ionic compounds.

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6.2 Physical properties of amino acids

The formation of zwitterions gives amino acids some unusual properties:
 Amino acids are crystalline solids with high melting points, e.g. glycine has a melting point of
262°C. This is due to strong electrostatic forces of attraction between the dipolar zwitterions in
the solid lattice structure. Large amount of energy is required to
overcome the strong ionic bonds between oppositely charged
ions.

 Amino acids are more soluble in water than in organic solvents.

This is due to the strong ion-dipole interaction between the
zwitterions and water molecules.

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For your information

Here are 20 naturally occurring -amino acids and their names can be represented by either a one-
letter or a three-letter abbreviation as shown in the table.

Structure at pH = 7.3

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Table 4. 20 naturally occurring amino acids (at pH = 7.3). Extracted from McMurry J., Organic Chemistry. 8th ed. USA:
Brooks/Cole

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6.3 Acid-Base behaviour (Application Example)

Having both the acidic and basic groups, amino acids are amphoteric, reacting with both acids and
bases to form ionic salts.

Isoelectric point (pI) of an amino acid (or protein) is the pH at which the overall net charge on the
amino acid is zero and it exists primarily as the neutral zwitterion. This isoelectric pH depends on the
nature of the side chain, R.

Amino acid Alanine Lysine Aspartic acid

Structure

Nature of side-chain neutral basic acidic

Isoelectric point 6.01 9.74 2.77

At a pH below isoelectric point (pH << pI), the amino acid exists predominantly as cations. However,
when pH >> pI, the amino acid exists predominantly as anions.

Exercise 6.1 (Worked Example)

Draw the structures of the major species of lysine that can exist in aqueous solution of various pH.
Start with the species in a solution of very low pH and consider the change in structure as pH
increases. Hence identify the major species that exists at isoelectric point.

Structure

pH Very low pH Very high pH

Increasing pH

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6.4 Titration curves of amino acids (Application Example)

Titration of amino acids are very similar to the titration of polyprotic acids. Refer to Topic 14 Acid-Base
Equilibria for titration curves and polyprotic acids.
Using glycine as an example,

pKa2 = 9.60 pKa1 = 2.34

pH < 2.34 2.34 < pH < 9.60 9.60 < pH

At pH < 2.34, all possible sites of glycine are protonated. Since –CO2H group is a stronger acid than –
NH3+ group, the stronger acidic –CO2H group will be neutralised first by the addition of base, OH—,
followed by the –NH3+ group. The reaction is as follows:

In the titration curve, the protonated

(cationic) form of glycine was titrated against
NaOH of same concentration. The cationic
form predominates at low pH before OH— is
added. When some OH— is added, a portion
of the cationic form undergoes
neutralisation to form zwitterion, resulting
in buffer region X (mixture of cationic form
and zwitterion).

Note that when 0.5 equivalent of OH— is

added, amount of cationic form unreacted =
amount of zwitterion formed. This is the
maximum buffering capacity where pH=pKa1.

The solution only contains zwitterion when at the first equivalence point and pH = pI of glycine.

As more OH— is added, the –NH3+ group is neutralised to form the anionic form, leading to a new
buffer mixture containing zwitterion and the anionic form in region Y. Note that when 1.5 equivalent
of OH— is added, amount of zwitterion unreacted = amount of anionic form produced. This is the
maximum buffering capacity where pH=pKa2.

At the second equivalence point and beyond, all sites are de-protonated and the solution only contains
the anionic form of glycine.

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6.5 Peptide bond formation to form polypeptides and proteins

LO 19(j): describe the formation of peptide (amide) bonds between α-amino acids and, hence, explain protein formation

Amino acids are the basic units of polypeptides and proteins. An amide bond between amino acids is
also called a peptide bond. Peptide bonds are formed from the condensation reaction between the
–CO2H and the –NH2 groups on two amino acids through the elimination of a water molecule. In this
manner, any number of amino acids can be bonded in a continuous chain.
peptide bond

A dipeptide is the result of 2 amino acid molecules condensing together to form a peptide bond with
the elimination of a water molecule while a tripeptide results from 3 amino acids molecules doing so
with the formation of two peptide bonds and the elimination of two water molecules, and so on.

Exercise 6.2 (N2009/I/30) (Worked Example)

A small peptide X is hydrolysed according to the following reaction.
hydrolysis

Mr = 75 Mr = 89 Mr = 105

What is the Mr of X?

Mr = 75 x 2 + 89 + 105 x 2 – 4(18) = 377

Since there are five amino acids obtained as products, peptide X must be a pentapeptide with four
peptide bonds broken during hydrolysis.

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Peptides made from the condensation of up to about 50 amino acid molecules are called polypeptides
(or polyamides). Anything larger is classified as a protein molecule.

Note: In the lab, the reaction

between a carboxylic acid and an
amine would result in salt
formation, but living organisms
employ enzymes to form peptide
bonds.

Exercise 6.3
Draw the structural formula of a dipeptide with the sequence asn-lys, showing the ionic form which
it would exist at pH 3.

Asparagine (asn) Lysine (lys)

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7 PROTEINS

Proteins are naturally occurring polypeptides of molecular weight > 5000 and are formed when over
105 amino acids condense together, all linked by peptide bonds. They are essential for life in all living
organisms and have many biological functions in the body, for example:
Type of Protein Function Examples
Structural Provide the framework which Keratin is the protein of hair, nails, horns and
proteins defines the size and shape of feathers. Collagen and elastin provide a
cells fibrous framework in animal connective
tissues
Catalytic Accelerate metabolic processes Pepsin, trypsin and chymotrypsin which
proteins to produce energy, build new cell hydrolyses proteins in our diets so that
(enzymes) structures and destroy old ones subunits can be absorbed for use by our cells.

7.1 Hydrolysis of Proteins

LO 19(k): describe the hydrolysis of proteins

Proteins can by hydrolysed into their constituent amino acids either by an appropriate enzyme or
heating under reflux in the presence of aqueous acid or alkali for several hours in the laboratory.

Exercise 7.1
Aspartame is the name for an artificial sweetener used as a sugar substitute in many foods and
beverages. Draw the structural formulae of all the organic products obtained when aspartame is
heated with dilute H2SO4.

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Summary of reactions of amines and amides

State the reagents and conditions needed for the conversions on the arrows below. Draw the
structure of the organic products formed in the boxes.

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Summary of oxidising and reducing agents

Ability to be oxidised by Ability to be reduced by

Functional KMnO4, KMnO4, K2Cr2O7,
groups H2 / Ni LiAlH4 in NaBH4 in
dilute dilute dilute
high P dry ether methanol
NaOH, cold H2SO4, heat H2SO4, heat
alkenes   X  X X
alkylbenzenes  X
nitriles (-CN)   X
1° & 2°
 
alcohol
aldehydes     
ketones X X   
carboxylic X X
X  X
acids
esters X X
amides X X  X

Note that nitrobenzene may be reduced to phenylamine using Sn, conc HCl, heat followed by dilute
NaOH.

LOOKING AHEAD
In our study of the extension topic on organic chemistry, we have learnt the general concepts in organic
chemistry (Topic 8 Introduction and Topic 9 Isomerism) and the nature & reactions of specific functional
groups, which exemplify these general concepts as well as earlier concepts of structure and bonding,
thermodynamics and kinetics. As we move on to the next topic of Electrochemistry and Transition Elements,
bear in mind that organic compounds can undergo redox reactions and act as fuels in electrochemical cells
(e.g. methane and ethanol). Organic molecules are also common ligands in transition metal complexes as
many contain electron-rich centers e.g. alcohols, phenols, carboxylic acids, amines, alkenes and arenes.

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20 Electrochemistry
GUIDING QUESTIONS
Electrochemical Cell
● What happens in a redox reaction?
● How can the tendency of a substance to be reduced or oxidised be measured?
● What are the factors affecting electrode potential?
● How can the direction and feasibility of a redox reaction be predicted, and what are the
limitations?

Electrolytic Cell
● What are the factors affecting the discharge of a substance during electrolysis?
● How to calculate the amount of substance liberated during electrolysis?
● What are some industrial applications of electrolysis?

What are the differences between an electrochemical cell and an electrolytic cell?

LEARNING OUTCOMES
Students should be able to:
12(a) describe and explain redox processes in terms of electron transfer and/or of changes in
oxidation number (oxidation state)
12(b) define the terms:
(i) standard electrode (redox) potential
(ii) standard cell potential
12(c) describe the standard hydrogen electrode
12(d) 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
12(e) calculate a standard cell potential by combining two standard electrode potentials
12(f) use standard cell potentials to:
(i) explain/deduce the direction of electron flow from a simple cell
(ii) predict the spontaneity of a reaction
12(g) understand the limitations in the use of standard cell potentials to predict the spontaneity
of a reaction
12(h) construct redox equations using the relevant half-equations (Refer to Topic 4 Reactions &
Stoichiometry)
12(i) state and apply the relationship ΔG = –nFEo to electrochemical cells, including the
calculation of Eo for combined half reactions
12(j) predict qualitatively how the value of an electrode potential varies with the concentration
of the aqueous ion
12(k) 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
12(l) state the relationship, F = Le, between the Faraday constant, the Avogadro constant and
the charge on the electron
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12(m) 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
12(n) calculate:
(i) the quantity of charge passed during electrolysis
(ii) the mass and/or volume of substance liberated during electrolysis
12(o) explain, in terms of the electrode reactions, the industrial processes of:
(i) the anodising of aluminium
(ii) the electrolytic purification of copper
[technical details are not required]

REFERENCES
1. Peter Cann & Peter Hughes (2015). Chemistry. Hodder Education.
2. Martin S. Silberberg (2006). Chemistry – The Molecular Nature of Matter & Change, 4th Edition.
McGraw Hill. Section 21.7.

LOOKING BACK
This topic is closely linked to redox chemistry covered in Topic 4, where we learnt how to construct an
equation for a redox reaction by combining two half-equations. In this topic, we will study how
electricity can be harnessed from redox reactions, and how we can predict whether a redox reaction is
spontaneous by using standard electrode potentials, Eo. Since we are dealing with spontaneity here, we
will see how Eo is related to Gibbs’ free energy change, G, from Topic 5. We will also look at electrolysis,
in which electricity (produced by spontaneous redox reactions) is used to drive many reactions that are
otherwise not spontaneous to produce useful chemicals.

1 INTRODUCTION

Electrochemistry is the study of the inter-conversion of chemical and electrical energy. The study is
typically done using cells in which redox reactions either produce or consume electrical energy.

There are two types of cells.

● Electrochemical cell (also known as galvanic cell or voltaic cell)

The redox reaction is spontaneous. Chemical energy from the reaction is converted to
electrical energy.
Examples: batteries, fuel cells

● Electrolytic cell
The redox reaction is non-spontaneous. Electrical energy is used to cause the reaction to
occur.
Examples: electrolysis of water, purification of copper, extraction of aluminium metal from
molten aluminium oxide, electroplating

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1.1 REDOX REACTIONS

LO12(a): describe and explain redox processes in terms of electron transfer and/or of changes in oxidation number (oxidation
state)
LO12(h): construct redox equations using the relevant half-equations

Whether the redox reaction occurs in an electrochemical cell or electrolytic cell, it always involves the
transfer of electrons. The number of electrons lost by the reducing agent must be equal to the number
of electrons gained by the oxidising agent.

Consider the reaction between Zn metal and Cu2+ ions. If a strip of Zn metal is placed in a solution of
Cu2+ ions, the blue solution turns pale blue (eventually colourless) and red Cu solid forms on the Zn
strip (Figure 1).

(a) start of experiment (b) after some time

Figure 1. Reaction between Zn and Cu2+

In the reaction, Zn is the reducing agent and reduces Cu2+ to Cu metal. Cu2+ is the oxidising agent as it
oxidises Zn metal to Zn2+ ions. The overall reaction consists of two half-reactions:

Reduction half-reaction: Cu2+(aq) + 2e– → Cu(s)

Oxidation half-reaction: Zn(s) → Zn2+(aq) + 2e–
Overall redox reaction: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

Electrons are transferred from Zn metal (reducing agent) to Cu2+ ion (oxidising agent). Each Zn atom
loses 2 electrons while each Cu2+ ion gains 2 electrons. Hence, one Zn atom reacts with one Cu2+ ion
in the overall reaction. This is because the number of electrons lost must equal to the number of
electrons gained when combining two half-equations to give the overall equation.

Table 1 summarises the terminology used to describe redox reactions.

reducing agent oxidising agent

undergoes oxidation undergoes reduction
loses electrons gains electrons
oxidation number increases oxidation number decreases
Table 1. Summary of redox terminology

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In the above set-up (Figure 1), Zn and Cu2+ ions are in the same beaker so the electrons are transferred
directly from Zn to Cu2+ hence no electrical energy can be generated. If, however, the half-reactions
are physically separated in an electrochemical cell (Figure 2), we can harness the electrical energy
from the spontaneous reaction. Each half-reaction occurs in a half-cell. The electrons are now ‘forced’
to move through an external circuit, resulting in an electric current. The electrical energy produced
can be used to operate electrical devices such as a light bulb. Hence, an electrochemical cell is
essentially a battery.

1.10

Reduction half-reaction
Oxidation half-reaction occurs in this half-cell:
occurs in this half-cell: Cu2+(aq) + 2e– ⇌ Cu(s)
Zn(s) ⇌ Zn2+(aq) + 2e–
1 mol dm–3 ZnSO4(aq) NO3 1 mol dm–3 CuSO4(aq)
K+

Figure 2. An electrochemical cell consisting of a Zn2+/Zn half-cell and a Cu2+/Cu half-cell

We will discuss more about half-cells and electrochemical cells in Section 2 and Section 3 respectively.

2 HALF-CELL AND ELECTRODE POTENTIAL

2.1 HALF-CELL

In every half-reaction, there is an oxidised form and a reduced form. An oxidised form in equilibrium
with the reduced form makes a half-cell.

oxidised form + ne– ⇌ reduced form

For a half-cell containing a metal placed in a solution containing its ions, Mn+ is the oxidised form while
M is the reduced form.
Mn+(aq) + ne– ⇌ M(s)

At equilibrium, the rate of M dissolving into the solution as Mn+ is equal to the rate of Mn+ reforming
M. The position of equilibrium depends on the reactivity of the metal. The more reactive the metal,
the more the position of equilibrium lies on the left.

Consider a reactive metal such as Zn. As Zn tends to dissolve into the solution to form Zn2+ ions, there
is a build-up of electrons on the Zn rod. This results in a negative charge on the Zn rod which is
surrounded by a layer of positive ions (Figure 3). A potential difference develops between the metal
and its solution. This is the electrode potential of the metal (symbol: E(Mn+/M)).

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Figure 3. Zn2+/Zn half-cell

Nickel is a less reactive metal than zinc. The position of equilibrium for Ni lies less on the left. The
build-up of electrons on the Ni rod is smaller so the potential difference between Ni metal and its
solution is smaller.

We cannot measure the absolute electrode potential of a half-cell. In practice, the electrode potential
of a half-cell has to be measured by connecting it to a reference half-cell (Section 2.1.1).

Besides the metal-metal ion half-cell, a half-cell can also consist of a non-metal in contact with its
aqueous ions (Figure 4) or ions of the same element in different oxidation states (Figure 5).

Cl2(g) bubbled into

solution

platinum electrode
l−
C (aq)

Figure 4. Cl2/ Cl– half-cell

platinum electrode

a solution containing
Fe3+(aq) and Fe2+(aq)

Figure 5. Fe3+/ Fe2+ half-cell

In half-cells that consist of a metal and its ions (e.g. Zn2+/Zn), the metal acts as the electrode which is
used to transfer electrons in the electrochemical cell. In half-cells that do not include a metal, platinum
(Pt) is usually used as the inert electrode. It transfers electrons without taking part in the reaction.

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2.1.1 STANDARD HYDROGEN ELECTRODE

LO12(c): describe the standard hydrogen electrode

The standard hydrogen electrode (Figure 6) is a commonly used reference half-cell or reference
electrode against which the electrode potential of all other half-cells are measured. Its electrode
potential is assigned a value of 0.00 V.

H2(g) at 298 K
and 1 bar

Figure 6. The standard hydrogen electrode

The standard hydrogen electrode comprises:

● a platinum wire and a piece of platinum foil covered with finely divided platinum (platinised
platinum) that serves as an inert surface for redox reaction to take place,
● a solution of 1 mol dm–3 H+(aq) ions, in which the platinum electrode, encased in a glass tube, is
immersed,
● hydrogen gas at a pressure of 1 bar and 298 K bubbling over the electrode.

On the surface of the platinum, equilibrium is established between hydrogen gas and hydrogen ions.

H+(aq) + e– ⇌ ½ H2(g) Eo (H+/H2) = 0.00 V

2.2 MEASURING STANDARD ELECTRODE (REDOX) POTENTIAL, Eo

LO12(b)(i): define the term standard electrode (redox) potential

Electrode potential, E, depends on the position of equilibrium so its value depends on conditions such
as temperature, pressure and concentration (to be discussed in Section 3.4.1). As such, electrode
potentials are measured under a set of standard conditions.

Standard conditions for measuring electrode potential are:

● temperature of 298 K
● pressure of 1 bar for any gas
● concentration of 1 mol dm–3 for any aqueous ions / species

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The standard electrode potential of a half-cell is the potential difference between the half-cell and a
standard hydrogen electrode at standard conditions (298 K, 1 bar for gases, 1 mol dm–3 for solutions).

LO12(d): 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

To measure the standard electrode potential of a half-cell, we connect the half-cell to a standard
hydrogen electrode and measure the potential difference with a high resistance voltmeter. A high
resistance voltmeter takes very little current to operate so the potential difference measured is the
highest possible value. This is known as the electromotive force (e.m.f.).

Since the standard hydrogen electrode is assigned an electrode potential of 0.00 V, the potential
difference measured by the voltmeter gives the standard electrode potential of the respective half-
cell.

(1) To measure Eo of a metal in contact with its ions in aqueous solution

Example: Zn2+(aq) / Zn(s) half-cell

Zn2+(aq) + 2e– ⇌ Zn(s) Eo= ?

high resistance voltmeter

H2(g) at 298 K
and 1 bar salt bridge

platinised
platinum
electrode Zn metal electrode

1 mol dm–3 H+(aq) 1 mol dm–3 Zn2+(aq)

Figure 7. Measuring the standard electrode potential of Zn2+(aq) / Zn(s) half-cell

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(2) To measure Eo of a non-metal in contact with its ions in aqueous solution

Example: Cl2(g) / Cl− (aq) half-cell

Cl2(g) + 2e– ⇌ 2Cl−(aq) Eo = ?

high resistance voltmeter

H2(g) at 298 K
and 1 bar Cl2(g) at 298 K
salt bridge and 1 bar

platinised
platinum
electrode platinum electrode

1 mol dm–3 H+(aq) 1 mol dm–3 Cl– (aq)

Figure 8. Measuring the standard electrode potential of Cl2(g) / Cl− (aq) half-cell

(3) To measure Eo involving ions of the same element in different oxidation states
Example: Fe3+(aq) / Fe2+(aq) half-cell

Fe3+(aq) + e– ⇌ Fe2+(aq) Eo = ?

high resistance voltmeter

H2(g) at 298 K
and 1 bar
salt bridge

platinised
platinum platinum electrode
electrode
1 mol dm–3 Fe2+(aq)
1 mol dm–3 H+(aq) and
1 mol dm–3 Fe3+(aq)

Figure 9. Measuring the standard electrode potential of Fe3+(aq) / Fe2+(aq) half-cell

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2.3 Understanding Standard Electrode Potential, Eo

● Standard electrode potentials, Eo values, can be obtained from the Data Booklet. By
convention, the half-reactions are written as reductions (i.e. electrons are written on the left).
Hence Eo value is also called standard reduction potential or standard redox potential.

For example, in the Data Booklet, we see:

Cr2O72– + 14H+ + 6e– ⇌ 2Cr3+ + 7H2O +1.33 V

This means that the “standard reduction potential of Cr2O72– (to be reduced to Cr3+)” is
+1.33 V. We can also write “EoCr2O72–/Cr3+” = +1.33 V.

● When the half-reaction is reversed, the Eo of the reversed half-reaction will have the same
magnitude but opposite sign.

Using the same example as above:

2Cr3+ + 7H2O ⇌ Cr2O72– + 14H+ + 6e– –1.33 V

The value –1.33 V is the standard oxidation potential of Cr3+ (to be oxidised to Cr2O72–) and is
less commonly used.

● The standard electrode potential (or standard reduction potential) is a measure of how
favourable the forward reduction process is.

The more positive the Eo value, the more favourable the forward reduction half-reaction.
The more negative the Eo value, the more favourable the backward oxidation half-reaction.

● Multiplying a half-equation by a factor will not change the Eo value (as it is an intensive
property.

Example: Ag+(aq) + e– ⇌ Ag(s) Eo = +0.80 V

2Ag+(aq) + 2e– ⇌ 2Ag(s) Eo = +0.80 V

Intensive Property and Extensive Property (Background Info)

Intensive property is a physical property that does not depend on the amount of substance present.
Examples: density, concentration

Extensive property is a physical property that depends on the amount of substance present.
Examples: volume, mass

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2.4 Using Eo to compare relative strengths of oxidising and reducing agents

As mentioned in Section 2.3, by convention, the half-reactions are written as reductions. Hence, the
chemical species on the left is the oxidising agent (accepts electrons and undergoes reduction) while
the chemical species on the right is the reducing agent (donates electrons and undergoes oxidation).

oxidised form + ne– ⇌ reduced form

oxidising agent reducing agent

Table 2 shows the electrochemical series arranged in order of increasing standard electrode potential.

half-reaction Eo / V
Li+ + e− ⇌ Li −3.04
K+ + e− ⇌ K −2.92
Ba2+ + 2e− ⇌ Ba −2.90
Ca2+ + 2e− ⇌ Ca −2.87
Na+ + e− ⇌ Na −2.71
Oxidising agent Mg2+ + 2e− ⇌ Mg −2.38 Reducing agent
accepts electron Al3+ + 3e− ⇌ Al −1.66 donates electron
Cr2+ + 2e− ⇌ Cr −0.91
2H2O + 2e− ⇌ H2 + 2OH− −0.83
increasing Zn2+ + 2e− ⇌ Zn −0.76 increasing
ease of Fe2+ + 2e− ⇌ Fe −0.44 ease of
reduction & Cr3+ + e− ⇌ Cr2+ −0.41 oxidation &
increasing increasing
Co2+ + 2e− ⇌ Co −0.28
oxidising reducing
Ni2+ + 2e− ⇌ Ni −0.25
strength strength
Sn2+ + 2e− ⇌ Sn −0.14
Pb2+ + 2e− ⇌ Pb −0.13
2H+ + 2e− ⇌ H2 0.00
Cu2+ + 2e− ⇌ Cu +0.34
O2 + 2H2O + 4e− ⇌ 4OH− +0.40
I2 + 2e− ⇌ 2I− +0.54
O2 + 2H+ + 2e− ⇌ H2O2 +0.68
Ag+ + e− ⇌ Ag +0.80
Br2 + 2e− ⇌ 2Br− +1.07
O2 + 4H+ + 4e− ⇌ 2H2O +1.23
Cr2O72− + 14H+ + 6e ⇌ 2Cr3+ + 7H2O +1.33
Cl2 + 2e− ⇌ 2Cl− +1.36
MnO4− + 8H+ + 5e− ⇌ Mn2+ + 4H2O +1.52
H2O2 + 2H+ + 2e− ⇌ 2H2O +1.77
F2 + 2e− ⇌ 2F− +2.87
Table 2. The Electrochemical Series

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● The more positive the Eo value, the more easily the oxidised form is reduced
⇒ the oxidised form is a stronger oxidising agent

Example: Cl2(g) + 2e– ⇌ 2Cl– (aq) Eo = +1.36 V

Br2(l) + 2e– ⇌ 2Br– (aq) Eo = +1.07 V
Cl2 is more easily reduced than Br2. Hence, Cl2 is a stronger oxidising agent than Br2 (which
also means Cl– is a weaker reducing agent than Br–).

● The more negative the Eo value, the more easily the reduced form is oxidised
⇒ the reduced species is a stronger reducing agent

Example : Ca2+(aq) + 2e ⇌ Ca(s) Eo = –2.87 V

Mg2+(aq) + 2e ⇌ Mg(s) Eo = –2.38 V

Ca is more easily oxidised than Mg. Hence, Ca is a stronger reducing agent than Mg (which
also means Ca2+ is a weaker oxidising agent than Mg2+).

Exercise 2.1
(a) Decide if each of the following statements is true or false.
● Br2 is more easily reduced than I2. True
● Ba is more readily oxidised than Cu. True
● Br2 is a stronger oxidising agent than Fe2+. True
● Al is a weaker reducing agent than Cr. False
● It is easier to reduce Cr2+ than to oxidise it. False
● Reducing power is in the order Cl– > Pb > Al False

(b) Among the species given in Table 2 on the previous page,

● Which is the strongest oxidising agent?
● Which has the strongest reducing power?
● Which species can act as both oxidising and reducing agents? H2O2, Cr2+

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3 THE ELECTROCHEMICAL CELL AND CELL POTENTIAL

3.1 THE ELECTROCHEMICAL CELL

An electrochemical cell consists of two half-cells. In one half-cell, oxidation takes place. In the other,
reduction takes place. The redox reaction is spontaneous and chemical energy is converted to
electrical energy. Figure 2 in Section 1 and Figures 7 to 9 in Section 2.2 are examples of
electrochemical cells. We can connect any two half-cells together to make an electrochemical cell.

1.10

1 mol dm–3 ZnSO4(aq) 1 mol dm–3 CuSO4(aq)

+
NO3 K

Figure 2 (from Section 1). An electrochemical cell consisting of a Zn2+/Zn half-cell and a Cu2+/Cu half-cell

We use the following to connect the two half-cells and to complete the circuit:
● wires to connect the two metal electrodes
● salt bridge which also serves to maintain charge neutrality

The salt bridge is an inverted U-tube containing a solution of non-reacting ions, in this case, K+ and
NO3–, in a gel. Each end of the tube is dipped into a half-cell. It has porous plugs on the ends that allow
ions to flow through while minimising the mixing of the electrolytes by diffusion. Other non-reacting
ions such as Na+ and SO42– can also be used in a salt bridge.

To measure the potential difference between the two half-cells, a high resistance voltmeter is added
in the path of the wires connecting the electrodes.

When the above electrochemical cell is set-up, we observe a voltmeter reading of +1.10 V. This reading
is the cell potential. It is the potential difference between the two half-cells, which (in this case) arises
due to the difference in reactivity of the two metals, Cu and Zn.

Zn is a more reactive metal than Cu. This means that Zn has a higher tendency to lose electrons and
be oxidised to Zn2+ compared to Cu. Hence, oxidation occurs in the Zn2+/Zn half-cell while reduction
occurs in the Cu2+/Cu half-cell.

Oxidation half-reaction: Zn(s) → Zn2+(aq) + 2e–

Reduction half-reaction: Cu2+(aq) + 2e– → Cu(s)
Overall redox reaction: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

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An electrode is identified as either anode or cathode depending on the half-reaction that takes place
there. The oxidation half-reaction occurs at the anode while the reduction half-reaction occurs at the
cathode.

Electrons are produced by the oxidation half-reaction hence the anode has an excess of electrons and
a negative polarity relative to the cathode. Electrons are consumed at the cathode by the reduction
half-reaction. Hence electrons flow from the oxidation half-cell to the reduction half-cell, i.e. from
the anode to the cathode. In the above electrochemical cell, the electrons produced at the Zn anode
(negative electrode) will flow to the Cu cathode (positive electrode) via the electrical wire (in the
external circuit).

Table 3 summarises the differences between the electrodes in an electrochemical cell.

Electrode Anode Cathode

Polarity Negative Positive
Half-reaction Oxidation Reduction
Table 3. Differences between the electrodes in an electrochemical cell

How does the salt bridge work? (Background Info)

We mentioned that the salt bridge completes the circuit and also allows ions to flow through. The
flow of ions occurs to maintain neutrality in the solutions in the half-cells. At the start, both half-
cells contain a neutral solution (ZnSO4 and CuSO4) where the number of positive charges equals to
the number of negative charges. As the reaction occurs, Zn2+ enters the solution in the anode so
the solution develops a net positive charge. In the cathode, Cu2+ leaves the solution to form Cu so
the solution develops a net negative charge.
This charge imbalance would stop the reaction as excess charges in the solutions will prevent more
ions from being formed.
To maintain neutral charge in the solutions, NO3– ions move from the salt bridge into the solution
at the anode (and some Zn2+ ions can also enter the salt bridge). At the cathode, K+ ions move from
the salt bridge into the solution (and some SO42– ions can also enter the salt bridge).

Cell notation (Background Info)

A cell notation can be written to represent an electrochemical cell. For example, the cell notation
for the electrochemical cell in Figure 2 (Section 3.1) is:

Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)

● The half-cell where oxidation takes place is placed on the left while the half-cell where
reduction takes place is placed on the right.
● The electrode of each half-cell is placed at the ends.
● The solid vertical line | indicate a phase boundary, with the reduced form on the outside.
● The double lines || represent the salt bridge.
● The concentration of an aqueous ion may be written next to the ion if not at 1 mol dm−3.

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3.2 STANDARD CELL POTENTIAL, Eocell

LO12(b)(ii): define the term standard cell potential

If the two half-cells that make the electrochemical cell are at standard conditions, the cell potential is
the standard cell potential, Eocell.

The standard cell potential is the potential difference between two half-cells measured at standard
conditions (298 K, 1 bar for gases, 1 mol dm–3 for solutions).

LO12(e): calculate a standard cell potential by combining two standard electrode potentials

● The standard cell potential, Eocell, can be calculated by combining two standard electrode
potentials.

Consider the electrochemical cell in Figure 2 (Section 3.1). The standard electrode potentials
of the two half-cells are:
Cu2+(aq) + 2e– ⇌ Cu(s) Eo = +0.34 V
Zn2+(aq) + 2e– ⇌ Zn(s) Eo = –0.76 V

The voltmeter shows a reading of +1.10 V which is equal to the standard cell potential. Notice
that this value is the numerical difference between the Eo values of the two half-cells.

(Reduction) +0.34V

Ecell = +0.34 – (–0.76) = +1.10 V

(Oxidation) –0.76V

Recall from Section 3.1 that reduction occurs in the Cu2+/Cu half-cell and Cu is the cathode
while oxidation occurs in the Zn2+/Zn half-cell and Zn is the anode.

Hence, Eo cell = Eo reduction – Eo oxidation

= Eo cathode – Eo anode

Remember to include the sign (+) or (–) as well as the units (V) for Eocell.

In general, to calculate Eocell of an electrochemical cell, we

● select the two standard electrode potentials from the Data Booklet
● decide which half-cell undergoes reduction and which half-cell undergoes oxidation

In an electrochemical cell, reduction occurs in the half-cell with the more positive Eo value.
Oxidation occurs in the half-cell with a less positive Eo value. The electrode in the reduction
half-cell is the cathode while the electrode in the oxidation half-cell is the anode.
In the above example, since Eo (Cu2+/Cu) is more positive than Eo (Zn2+/Zn), reduction occurs
in the Cu2+/Cu half-cell and Cu is the cathode while oxidation occurs in the Zn2+/Zn half-cell
and Zn is the anode.
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LO12(f)(i): use standard cell potentials to explain/deduce the direction of electron flow from a simple cell

● We can use standard cell potentials to deduce the direction of electron flow in the external
circuit of an electrochemical cell.

Electrons are produced at the anode (by the oxidation half-reaction) and consumed at the
cathode (by the reduction half-reaction). Hence, electrons flow from the oxidation half-cell
to the reduction half-cell, i.e. from the anode to the cathode.

In the electrochemical cell in Figure 2 (Section 3.1), Zn is the anode (less positive Eo value) and
Cu is the cathode (more positive Eo value). Electrons flow from the Zn electrode to the Cu
electrode in the external circuit.

LO12(h): construct redox equations using the relevant half-equations

● We can use half-equations to construct redox equations. The half-equations in the Data
Booklet are shown with an equilibrium arrow (⇌) because each can occur as a reduction or
oxidation, depending on the other half-reaction. A redox reaction must consist of a reduction
half-reaction and an oxidation half-reaction.

For example,
Cu2+(aq) + 2e– ⇌ Cu(s) Eo = +0.34 V
Zn2+(aq) + 2e– ⇌ Zn(s) Eo = –0.76 V

In the electrochemical cell in Figure 2 (Section 3.1), Zn is oxidised to Zn2+ so we need to reverse
the zinc half-equation. In addition, we must use the single forward arrow (→) for both half-
equations to represent the reactions that actually occur.

Oxidation half-reaction: Zn(s) → Zn2+(aq) + 2e–

Reduction half-reaction: Cu2+(aq) + 2e– → Cu(s)

Electron lost must equal to electron gained when combining two half-equations to give the
overall redox equation. Each Zn atom loses 2 electrons while each Cu2+ ion gains 2 electrons.
Hence, one Zn atom reacts with one Cu2+ ion in the overall reaction.

Overall redox reaction: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

To represent redox reactions that actually occur, the single forward arrow must be used.

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Exercise 3.1 (Worked Example)

The voltaic cell below consists of a SO42–/SO2 half-cell connected to a Ag+/Ag half-cell.
(a) Calculate the Ecell.
(b) Indicate on the diagram the polarity of the electrodes and the direction of electron flow.
(c) Write half-equations for the reactions that occur at the cathode and the anode respectively.

electron flow

SO2(g) at 25C
and 1 bar

(−) (+)
Ag electrode
platinum electrode
1 mol dm–3 SO42– (aq) and 1 mol dm–3
1 mol dm–3 H+(aq) Ag+(aq)

(a) SO42– + 4H+ + 2e– ⇌ SO2 + 2H2O E = +0.17 V [O]

+ –
Ag + e ⇌ Ag E = +0.80 V [R]
 Ecell = Ered − Eox = +0.80 − (+0.17) = +0.63 V

(b) Electrons are produced at the anode (by the SO42–/SO2 oxidation half-reaction) and
consumed at the cathode (by the Ag+/Ag reduction half-reaction). Hence, electrons flow
from the Pt electrode to the Ag electrode.

(c) cathode: Ag+ + e– → Ag

anode: SO2 + 2H2O → SO42– + 4H+ + 2e–

3.3 Standard Cell Potential and Gibbs’ Free Energy

LO12(i)part: state and apply the relationship ΔG = –nFEo to electrochemical cells

In Topic 5, we discussed the change in Gibbs free energy, G, that accompanies chemical reactions.
The change in Gibbs free energy of a redox reaction can be converted into electrical energy in an
electrochemical cell.

The following equation shows the relationship between Gibbs’ free energy change and cell potential:

Go= –nFEocell

where Go is the standard Gibbs free energy change in joules per mole (J mol−1),
n is the number of moles of electrons transferred per mole of the cell reaction and
F is the Faraday's constant (96500 C mol−1).

Hence, a spontaneous redox reaction (G < 0) would imply that Ecell > 0.

We will use Go= –nFEocell in calculations in Section 3.5.

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3.4 Predict Spontaneity of a Redox Reaction

LO12(f)(ii): use standard cell potentials to predict the spontaneity of a reaction

We can use standard cell potentials to predict whether a redox reaction will occur between two given
reactants.

● If Eocell is positive, reaction is expected to be spontaneous under standard conditions.

● If Eocell is negative, reaction is expected to be non-spontaneous under standard conditions.
● If Eocell = 0, the reaction is at equilibrium, and there is no net reaction in either direction.
To calculate Eocell, we use Eocell = Eoreduction – Eooxidation. We need to decide which reactant undergoes
reduction and which reactant undergoes oxidation. This depends on the reactants given to you.

Look for the relevant half-equations in the Data Booklet that contains the given reactants. It is useful
to circle the given reactants in the half-equations.
● If both reactants are on the same side of the half-equations, then either both are oxidising agents
or both are reducing agents. The redox reaction cannot occur. In this case, we cannot calculate
the Eocell value.
● If the two reactants are on opposite sides of the half-equations, the redox reaction may occur.
Calculate the Eocell value to predict the spontaneity of the reaction.
If more than one redox pair or reaction are possible, the reaction with the most positive Eocell will
be the most spontaneous.

For example, if Zn metal is placed in a solution containing Cu2+ ions, a spontaneous reaction occurs.

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) Eocell = +0.34 – (–0.76) = +1.10 V > 0

What happens if Cu metal is placed in a solution containing Zn2+ ions? Will the following reaction
occur?
Zn2+(aq) + Cu(s) → Zn(s) + Cu2+(aq) Eocell = ?

The relevant half-equations are:

Cu2+(aq) + 2e– ⇌ Cu(s) Eo= +0.34 V
Zn2+(aq) + 2e– ⇌ Zn(s) Eo = –0.76 V

In this case, Zn2+ needs to undergo reduction and Cu needs to undergo oxidation.

Eocell = Eoreduction – Eooxidation = (–0.76) – (+0.34) = –1.10 V < 0. Hence, no reaction will occur between Zn2+
and Cu.

Note that the reaction between Zn and Cu2+ is spontaneous (Eocell > 0), hence we would expect the
reverse reaction to be non-spontaneous (Eocell < 0).

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Exercise 3.2 (Worked Example)

Predict whether the following pairs of reagents are likely to react when mixed in acidified aqueous
solution. Calculate the Ecell and write a balanced equation for each reaction you predict will occur.

(a) I2(aq) and Cr3+(aq)

(b) H2O2(aq) and MnO4–(aq)

(a) [R] I2 + 2e− ⇌ 2I– +0.54 V

Cr3+ + 3e− ⇌ Cr −0.74 V
Cr3+ + e− ⇌ Cr2+ −0.41 V
[O] Cr2O72– + 14H+ + 6e− ⇌ 2 Cr3+ + 7H2O +1.33 V

Note: I2 can only undergo reduction as there is only one half-equation involving I2 whereby
I2 is on the left side of the half-equation. However, there are 3 half-equations involding
Cr3+. Thus, for Cr3+, you need to choose the half-equation which shows Cr3+ undergoing
oxidation (i.e. Cr3+ on the right side of half-equation).

Ecell = +0.54 − (+1.33) = −0.79 V < 0

Reaction is not spontaneous => No reaction occurs

(b) H2O2 + 2H+ + 2e− ⇌ 2H2O +1.77 V

[O] O2 + 2H+ + 2e− ⇌ H2O2 +0.68 V
[R] MnO4– + 8H+ + 5e− ⇌ Mn2+ + 4H2O +1.52 V

Note: There are 3 half-equations which can represent the reduction of MnO4ˉ. However,
you have learnt under “Redox Reactions” in Topic 04 Reactions and Stoichiometry that
MnO4ˉ is reduced to Mn2+ in acidic medium (MnO4ˉ is reduced to MnO2 instead in alkaline
medium).

Ecell = +1.52 − (+0.68) = +0.84 V > 0

Reaction is spontaneous => Reaction occurs

MnO4– oxidises H2O2 to O2 gas, causing effervescence.

MnO4– is reduced to Mn2+. The purple solution turns colourless.

Overall equation: 2MnO4–(aq) + 6H+(aq) + 5H2O2(aq) → 2Mn2+(aq) + 8H2O(l) + 5O2(g)

Exercise 3.3
Predict whether the following pairs of reagents are likely to react when mixed in acidified aqueous
solution. Calculate the Eocell and write a balanced equation for each reaction you predict will occur.

(a) V3+(aq) and Cu2+(aq)

(b) F2(g) and Cr2O72–(aq)

(a) 0V (b) no value

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3.4.1 Non-Standard Conditions

LO12(j): predict qualitatively how the value of an electrode potential varies with the concentration of the aqueous ion

Changes in concentration, pressure and temperature may affect the values of electrode potentials.
We can predict the effect of these changes on the electrode potential using Le Chatelier’s Principle.

(i) Effect of concentration of aqueous ions on electrode potential

Consider: Cu2+(aq) + 2e– ⇌ Cu(s)

At 298 K and 1.00 mol dm–3 of Cu2+(aq), Eo= +0.34 V
At 298 K and 0.10 mol dm–3 of Cu2+(aq), E = +0.31 V

Explanation: If the concentration of the Cu2+(aq) ions is decreased, the position of the
equilibrium will shift to the left. Hence the tendency for Cu2+ to be reduced is decreased, and
reduction potential becomes less positive (or more negative).

(ii) Effect of pressure of gaseous species on electrode potential

Consider: Cl2(g) + 2e– ⇌ 2Cl–(aq) Eo = +1.36 V

When the pressure of chlorine gas is increased from say 1 bar to 1.5 bar, the equilibrium
position shifts to the right to favour the forward reduction reaction. Hence the reduction
potential becomes more positive (or less negative).

(iii) Effect of temperature

Consider: Na+(aq) + e– ⇌ Na(s)
At 298K and 0.1 mol dm–3 of Na+(aq), E = – 2.77 V
At 398K and 0.1 mol dm–3 of Na+(aq), E = – 2.79 V

The above data shows that at a higher temperature, the position of equilibrium shifts to the
left and the reduction potential becomes more negative (or less positive) for Na+.

Nernst Equation (Background Info)

Electrode potentials under non-standard conditions may be determined using the Nernst equation.
[C]c [D]d
For a reaction: aA + bB ⇌ cC + dD, let Q =
[A]a [B]b
RT
Nernst equation can be written as: Ecell = Eocell − ln Q
nF
where R is the gas constant,
T is the temperature in K,
n is the number of moles of selectrons transferred (per mole of the redox reaction) when
the oxidised species changes into the reduced species and
F is the Faraday's constant, 96 500 C mol−1.
0.0591
At 298K, the Nernst equation can be rewritten in the log form: Ecell = Eocell − lg Q
n

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3.4.2 Limitations of Using Standard Cell Potentials

LO12(g): understand the limitations in the use of standard cell potentials to predict the spontaneity of a reaction

Using Eocell to predict the spontaneity of a reaction may not be correct for two reasons:

● Non-standard conditions
Eocell values apply only to standard conditions (298 K, 1 bar, 1 mol dm–3). Since changes in
concentration, pressure and temperature may affect the values of electrode potentials, they will
also affect the cell potential calculated and hence the prediction.

● High activation energy (energetic vs kinetic feasibility)

Similar to ΔG, Eo values cannot predict the rate of a redox reaction. It only tells us whether a reaction
is thermodynamically feasible i.e. spontaneous. No information is given about the kinetic feasibility,
which is related to activation energy.

For example, Eo values predict that Cu2+(aq) should oxidise H2(g) to H+(aq).

Cu2+(aq) + H2(g) → Cu(s) + 2H+(aq) Eocell = +0.34 V

However, in practice, no reaction occurs when hydrogen is bubbled into copper(II) sulfate solution at
r.t.p. because the reaction rate is effectively zero due to a very high activation barrier.

3.5 Calculation of Eo for combined half reactions

LO12(i)part: apply ΔG = –nFEo to electrochemical cells, including the calculation of Eo for combined half reactions

Eo values cannot be combined directly to evaluate the Eo for another half-reaction.

Consider the following three redox half-equations:

(1) Fe2+ + 2e– ⇌ Fe Eo1 = –0.44 V
(2) Fe3+ + e– ⇌ Fe2+ Eo2 = +0.77 V
(3) Fe3+ + 3e– ⇌ Fe Eo3 = –0.04 V

The sum of half-equations (1) and (2) gives half-equation (3), but Eo3 is not +0.33 V (sum of Eo1 and
Eo2). The number of electrons transferred in each half-reaction must be taken into account. To find
the Eo value of combined half reactions, we use the relationship ΔGo= –nFEo.

Using the above example, we shall first convert the relevant Eo values to ΔG:
(1) Fe2+ + 2e– ⇌ Fe Eo1 = –0.44 V ⇒ ΔGo1 = –(2)(96500)(–0.44) = +84920 J mol–1
(2) Fe3+ + e– ⇌ Fe2+ Eo2 = +0.77 V ⇒ ΔGo2 = –(1)(96500)(+0.77) = –74305 J mol–1

Using Hess’ Law, ΔGo3 = ΔGo1 + ΔGo2 = +84920 + (–74305) = +10615 J mol–1
Since n = 3 for half-equation (3),Eo3 = – ΔGo3 / nF = – 10615/(3 × 96500) = –0.04 V
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Exercise 3.4 (RIJC 2011/ 3/ 1b modified) (Worked Example)

The standard electrode potentials, E, and standard Gibbs free energy changes, G, of different
chlorine-containing species are tabulated below.

Half-equation E / V G / kJ mol−1

1 2ClO3−(aq) + 12H+(aq) + 10e− ⇌ Cl2(aq) + 6H2O(l) +1.47 ?
2 Cl2(aq) + 2e− ⇌ 2Cl−(aq) +1.36 −262

(a) Calculate Go for half-reaction 1.

(b) The standard electrode potential of converting ClO3− to Cl− is not the summation of +1.47 V
and +1.36 V. This is because the number of electrons transferred in each step must be taken
into account.

By writing a half-equation for the conversion of ClO3− to Cl− and using your knowledge of Hess’
Law for G and your answers to (a), show with the aid of an energy cycle that the E for the
conversion of ClO3− to Cl− is +1.45 V.

(a) G = –nFEo = –(10)(96500)(+1.47) = –1420 kJ mol–1

(b) 2ClO3–(aq) + 12H+(aq) + 12 e− ⎯→ 2Cl–(aq) + 6H2O(l)

2ClO3−(aq) + 12H+(aq) + 12 e− ⎯→ 2Cl−(aq) + 6H2O(l)

(a) G = −1420 kJ mol−1 G = −262 kJ mol−1

Cl2(aq) + 2e− + 6H2O(l)

Applying Hess’ Law,

G = –1420 + (–262) = –1682 kJ mol−1

E = – [–1682 x 103 / (12 × 96500)] = +1.45 V (shown)

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4 PRACTICAL APPLICATIONS OF ELECTROCHEMICAL CELLS

LO12(k): state the possible advantages of developing other types of cell, e.g. the H 2/O2 fuel cell and improved batteries (as in
electric vehicles) in terms of smaller size, lower mass and higher voltage

Fuel cells (Section 4.1) and batteries (Section 4.2) are two common examples of electrochemical cells
that provide a portable and convenient way of obtaining energy from chemical reactions.

Hydrogen-oxygen fuel cells have been used for years to provide electricity and pure water during
space flights. Similar ones are being used to supply electric power for transportation (e.g. electric
vehicles), residential and commercial needs.

Advantages of fuel cells

● No pollution
● High efficiency and good energy-to-mass ratio
They convert about 75% of the chemical energy of the fuel
into useable power as compared to 40% for a coal-fired
power plant and 20-25% for a gasoline-powered car engine.

Disadvantages of fuel cells Figure 10. Mercedes-Benz F600

with hydrogen fuel cell
● Expensive
● High temperature to operate
The electrode reactions are slow, even when the electrodes are made of platinum which acts as a
catalyst.
● The alkali may absorb CO2 from air to form carbonates that clog up the porous electrodes.
● Bulky storage of fuel
For cars, the hydrogen must be transported either in cylinders (heavy) or at very low temperatures
as a liquid. Efforts are made to carry the hydrogen in the form of transition metal hydrides but
these are costly and can absorb only a limited amount of hydrogen. As an alternative to
transporting hydrogen to fuel cars, methanol is a fuel that is easy to carry and can be broken down
to produce carbon dioxide and hydrogen (which is then used as the fuel in the H2/O2 fuel cell).
However, there is the danger that some poisonous carbon monoxide may be produced in addition
to the carbon dioxide.

Despite steady progress, the focus of current fuel cell research remains on lowering costs by improving
membrane conductivity and developing more efficient catalysts.

Although the operation of a battery is similar in principle to that of the electrochemical cells described
in Section 3.1, a battery has the advantage of being completely self-contained and required no
auxiliary components such as salt bridges.

The trend in developing improved batteries is to look for batteries with

● smaller size
● lower mass
● higher voltage
● longer shelf-life
● lower production cost

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4.1 Fuel Cells (Background Info and Application Example)

When a fuel is burnt in a power station, the heat is usually used to produce steam to drive a piston or
to turn the blades of a turbine. The overall efficiency is always low no matter how well the plant is
designed.

In order to achieve higher efficiencies, efforts have been made to convert the chemical energy of a
fuel directly into electrical energy by means of a fuel cell. In contrast to batteries, the reactants in a
fuel cell are supplied continuously and the cell is able to operate without theoretical limit as long as
the supply of reactants is maintained.

The fuel (e.g. hydrogen, a hydrocarbon or an alcohol) and an oxidant (usually oxygen) enter the fuel
cell, and the products leave, generating electricity through the controlled oxidation of the fuel. The
fuel does not burn because, as in other batteries, the half-reactions are separated and the electrons
are transferred through an external circuit.

The most common fuel cell is the hydrogen-oxygen fuel cell:

At the anode, H2 diffuses At the cathode, O2 diffuses

through the porous through the porous
graphite electrode and graphite electrode and
comes into contact with Anode Cathode comes into contact with
KOH(aq). KOH(aq).

H2 O2
porous graphite
electrode containing
metal catalyst

H2 O2

Hot, excess aqueous KOH

Figure 11. Hydrogen-oxygen fuel cell

Anode (oxidation): H2(g) + 2OH–(aq) → 2H2O(l) + 2e–

Cathode (reduction): O2(g) + 2H2O(l) + 4e– → 4OH–(aq)
Overall cell reaction: 2H2(g) + O2(g) → 2H2O(l) Eo cell = +1.23 V

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Exercise 4.1 (Worked Example)

The Italian catalyst manufacturer Acta proposed using hydrazine as an alternative to hydrogen in
fuel cells. The chief benefit of using hydrazine is that it can produce more energy than a similar
hydrogen-oxygen cell.

The following diagram shows a typical hydrazine-oxygen fuel cell system incorporated with an anion
exchange membrane between the electrodes.

(i) Write the two ion-electron half equations for the reactions that take place at each
electrode. Hence, write an overall equation for the cell reaction.
(ii) Given that E(N2/N2H4) is −1.16 V, calculate the cell e.m.f. if the process takes place
under standard conditions.
(iii) Based on the physical properties of hydrazine, suggest an advantage of the hydrazine-
oxygen fuel cell over the hydrogen-oxygen fuel cell.
PJC 2013/ 3/ 3b modified

(i) Anode: N2H4 (l) + 4OH– (aq) → N2(g) + 4H2O(l) + 4e–

Cathode: O2(g) + 2 H2O(l) + 4e– → 4OH- (aq)
Overall: N2H4 (l) + O2 (g) → N2 (g) + 2H2O(l)

(ii) EӨcell = EӨ (red) − EӨ (ox)

= + 0.40 V − (− 1.16)
= + 1.56 V

(iii) Hydrazine is a liquid at room temperature and can be handled and stored more easily
than hydrogen gas.

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4.2 Batteries (Application Examples)

(Diagrams of batteries are not required in exams)

(i) Non-rechargeable alkaline battery used in portable radios, toys and flashlights

Insulator

Graphite rod (cathode)

MnO2 in KOH paste

Zn anode with outer steel
casing

Figure 12. Alkaline battery

Anode (oxidation): Zn(s) + 2OH–(aq) → ZnO(s) + H2O(l) + 2e–

Cathode (reduction): MnO2(s) + 2H2O(l) + 2e– → Mn(OH)2(s) + 2OH–(aq)
Overall cell reaction: Zn(s) + MnO2(s) + H2O(l) → ZnO(s) + Mn(OH)2(s) Ecell = +1.5 V

(ii) Non-rechargeable silver button battery used in watches, cameras, heart pacemakers and
hearing aids

Figure 13. Silver button battery

Anode (oxidation): Zn(s) + 2OH–(aq) → ZnO(s) + H2O(l) + 2e–

Cathode (reduction): Ag2O(s) + H2O(l) + 2e– → 2Ag(s) + 2OH–(aq)
Overall cell reaction: Zn(s) + Ag2O(s) → ZnO(s) + 2Ag(s) Ecell = +1.6 V

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(iii) Rechargeable lead-acid battery used to power the starter motor in a car

Figure 14. Lead-acid battery

Anode (oxidation): Pb(s) + H2SO4(aq) → PbSO4(s) + 2H+(aq) + 2e–

Cathode (reduction): PbO2(s) + H2SO4(aq) + 2H+(aq) + 2e– → PbSO4(s) + 2H2O(l)
Overall cell reaction (during discharge):
PbO2(s) + Pb(s) + 2H2SO4(aq) → 2PbSO4(s) + 2H2O(l) Ecell = +2.1 V

When the cell is recharged, it uses electrical energy as an electrolytic cell (electrolysis) and the half-
reactions and overall reaction are reversed.

Overall cell reaction (during recharge):

2PbSO4(s) + 2H2O(l) → PbO2(s) + Pb(s) + 2H2SO4(aq)

(iv) Rechargeable lithium-ion battery used in cell phones, digital cameras and laptops

Figure 15. Lithium-ion battery

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Anode (oxidation): Li(s) → Li+ + e–

Cathode (reduction): Li+ + CoO2(s) + e– → LiCoO2(s)
Overall cell reaction (during discharge):
Li(s) + CoO2(s) → LiCoO2(s) Ecell = +3.4 V

During recharging, the half-reactions and overall reaction are reversed.

The anode (negative electrode) is made of a carbon material (usually graphite) with tiny spaces in its
structure to hold both Li atoms and Li+ ions. The cathode (positive electrode) is made of a transition
metal oxide such as CoO2, which can also hold Li+ ions. Because of the high reactivity of lithium metal,
a non-aqueous electrolyte (organic solvent) must be used. The advantage of the battery is that lithium
has the most negative Eand is the lightest metal. A lithium-ion battery can be recharged literally
hundreds of times without deterioration.

4.3 Rusting (Application Example)

Paint protects iron and steel from corrosion as it prevents them from contacting directly with air.
However, in many instances, part of the paint could be removed due to various reasons and it led to
the bare metal being exposed. This result in the metal directly below the paint to rust as illustrated in
the diagram below.

Figure 16. The corrosion of iron

The relevant equations involved in the cathodic and anodic sites are shown below:

O2 + 4H+ + 4e– ⇌ 2H2O Eo = +1.23 V

Fe2+ + 2e– ⇌ Fe Eo = –0.44 V

The resultant Ecell is greater than 0 V, indicating a spontaneous reaction. The Fe2+ produced will be
further oxidised by oxygen to produce Fe2O3, a form of rust.

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5 THE ELECTROLYTIC CELL

Electrolysis is a process that involves the splitting (or lysing) of a substance, often to its component
elements, by supplying electrical energy. The cell in which electrolysis occurs is called the electrolytic
cell.
The principle of an electrolytic cell (Figure 17) is the opposite of an electrochemical cell: the redox
reaction is non-spontaneous and electrical energy (from an external source) is used to cause the
reaction to occur, i.e. the cell converts electrical energy to chemical energy.
battery
+
flow of electrons
anode (+) () cathode
(oxidation) (reduction)

electrolyte
electrodes

Figure 17. General set-up of an electrolytic cell

The electrolyte in the electrolytic cell is a liquid or an aqueous solution that can conduct electricity
(due to presence of mobile ions). Examples: molten PbBr2 or aqueous CuSO4

Table 4 compares some features of an electrochemical cell and an electrolytic cell.

Electrochemical Cell Electrolytic cell

chemical energy → electricity energy electricity energy → chemical energy
reaction is spontaneous reaction is non-spontaneous
Example:
e e
e e Pt anode Pt cathode
Cu cathode salt bridge Zn anode (+) (–)
(+) (–)

Cu2+(aq) Zn2+(aq) dilute NaCl(aq)

Polarity of electrodes depends on the half- Polarity of electrodes depends on the battery terminal:
reaction: Cathode: negative (reduction)
Ca(t)hode: Positive (Reduction) Anode: positive (oxidation)
Anode: negative (oxidation)
Half-reactions: Anode - oxidAtion, Cathode - reduCtion
Direction of electron flow in the external circuit: Anode to Cathode
Table 4. Comparison of electrochemical cell and electrolytic cell

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In both cells, oxidation takes place at the anode and reduction takes place at the cathode. However,
the polarities of the electrodes are reversed. To understand this, keep in mind the following:

● In an electrochemical cell, electrons are generated at the anode, so the anode is negative (having
excess electrons), and electrons are consumed at the cathode, so the cathode is positive (lack of
electrons).

● In an electrolytic cell, the electrons come from an external power source e.g. a battery, which
supplies electrons to the cathode, so the cathode is negative (excess electrons), and removes
electrons from the anode, so the anode is positive (lack of electrons).

6 PREDICTING THE PRODUCTS OF ELECTROLYSIS

LO12(m)part: 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

In an electrolytic cell the cathode is negative so cations are attracted to the cathode and are reduced.
On the other hand, the anode is positive so anions are attracted to the anode and are oxidised.

When there is more than one species that can be oxidised or reduced, the substance that is liberated
at each electrode is the one that requires the least energy. This is called selective discharge which
depends on:
● electrode potential, E values
➢ At the cathode, the reduction of the species with the more positive (or less negative)
electrode potential occurs.
➢ At the anode, the oxidation of the species with the more negative (or less positive) electrode
potential occurs.
● concentration of the ion (which affects the electrode potential (recall Section 3.4.1)
● nature of the electrode

6.1 Electrolysis of pure molten salts

Predicting the product at each electrode is simple if the salt contains one cation and one anion.

Consider the electrolysis of molten lead(II) bromide

using inert platinum electrodes (Figure 18). The two
flow of
electrons species present are Pb2+ and Br– ions.

The reactions that occur at the electrodes are:

Cathode (reduction): Pb2+(l) + 2e– → Pb(l)
Anode (oxidation): 2Br–(l) → Br2(g) + 2e–
Overall: Pb2+(l) + 2Br–(l) → Pb(l) + Br2(g)

At the cathode, beads of molten Pb will be deposited.

At the anode, brown fumes of Br2 gas will be seen.

molten PbBr2 FYI: m.p. of PbBr2 = 373 C, m.p. of Pb = 327 C, b.p. of Br2 = 58.8 C

Figure 18. Electrolysis of molten PbBr2

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Exercise 6.1
Predict the product formed at the anode, and at the cathode, when MgCl2(l) is electrolysed using
inert electrodes. Explain your reasoning and write equations, including state symbols, for the
electrode reactions.
Given: melting point of MgCl2 = 714 C, Mg = 650 C

6.2 Electrolysis of dilute aqueous solutions

Aqueous salt solutions are mixtures of ions and water, so we have to compare the electrode potentials
of the ions and water to predict the products at each electrode.

Water is a polar molecule so it can also be attracted to the electrodes and be discharged. In aqueous
salt solutions, water is the solvent and present in large excess while the concentrations of H+ and OH–
ions are very low (in pure water at 25 oC, [H+] and [OH–] are 10–7 mol dm–3 each). Hence, we consider
the reduction of H2O (not H+) at the cathode and the oxidation of H2O (not OH–) at the anode. H+ and
OH– ions are discharged only when the electrolyte contains aqueous acid or alkali respectively.

Consider the electrolysis of aqueous NaCl solution using platinum electrodes.

● At the cathode (negative electrode), the possible reduction and their electrode potentials are:
Eo/V
Na+ + e– ⇌ Na –2.71
2 H2O + 2e– ⇌ H2 + 2OH– –0.83

Since Eo (H2O/H2) is more positive than Eo (Na+/Na), H2O has a higher tendency to be reduced than
Na+ so H2O is preferentially reduced.

Reaction at cathode: 2H2O(l) + 2e– → H2(g) + 2OH–(aq)

Note: Cations of highly reactive metals e.g. Na+ are not reduced in aqueous solution. H2O is always
reduced in preference.

● At the anode (positive electrode), the possible oxidation and their electrode potentials are:
Eo /V
Cl2 + 2e– ⇌ 2 Cl– +1.36

O2 + 4H+ + 4e– ⇌ 2 H2O +1.23

Since Eo (O2/H2O) is less positive (or more negative) than Eo (Cl2/Cl–), H2O has a higher tendency
to be oxidised than Cl– so H2O is preferentially oxidised.

Reaction at anode: 2H2O(l) → O2(g) + 4H+(aq) + 4e–

Overall reaction: 2H2O(l) → O2(g) + 2H2(g)

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The above is effectively the electrolysis of water. Pure water is not used because very few ions are
present to conduct the current ([H+] = [OH–] = 10–7 mol dm–3). The electrolyte used is often an aqueous
solution like aqueous sodium chloride.

Exercise 6.2 (N2006/3/1a modified)

Predict the products formed at the anode, and at the cathode, when the following liquids are
electrolysed using inert electrodes.
i) NaBr(aq)
ii) CuF2(aq)
In each case explain your reasoning, using data from the Data Booklet. Write equations, including
state symbols, for the electrode reactions.

Exercise 6.3 (J97/2/3a)

The electrolysis of aqueous sodium sulfate containing litmus indicator was carried out in the
apparatus illustrated. Inert electrodes were used. After some time, the volumes of gas liberated
were as shown in the diagram. The litmus in both electrode compartments had changed colour.

Na2SO4(aq)

a) Write the appropriate ion-electron half-equations, with state symbols, for the changes which
take place in each electrode compartment. Indicate whether oxidation or reduction has
occurred.

The negative electrode: 2H2O(l) + 2e–  H2(g) + 2OH–(aq) reduction

The positive electrode: 2H2O(l)  O2(g) + 4H+(aq) + 4e– oxidation

b) Hence explain why the gas volumes are in the ratio 2:1.

c) State and explain the colour of the litmus around each electrode.

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6.3 Electrolysis of concentrated aqueous solutions

Ions which are present in high concentrations may be preferentially discharged even though its
standard electrode potential suggests otherwise. This is because changes in concentration may affect
the value of the electrode potential.

Consider the electrolysis of concentrated NaCl solution (brine) using platinum electrodes.

● At the anode (positive electrode), the possible oxidation and their electrode potentials are:
Eo /V
Cl2 + 2e– ⇌ 2 Cl – +1.36 ------ (I)
O2 + 4H+ + 4e– ⇌2 H2O +1.23

The high Cl– concentration in brine causes the position of equilibrium (I) to shift to the left.
E(Cl2/Cl–) decreases and becomes less positive than Eo(O2/H2O). Thus, Cl– is preferentially
oxidised at the anode.
∴ Reaction at anode: 2Cl–(aq) → Cl2(g) + 2e–

Recall from Section 6.2 that when aqueous NaCl solution is electrolysed, H2O is preferentially
oxidised at the anode instead to give O2.

● At the cathode (negative electrode), the possible reduction and their electrode potentials are:
Eo /V
Na+ + e– ⇌ Na –2.71
2 H2O + 2e– ⇌ H2 + 2OH– –0.83

Since Eo(H2O/H2) is more positive (or less negative) than Eo(Na+/Na), H2O is preferentially reduced.
∴ Reaction at cathode: 2H2O(l) + 2e– → H2(g) + 2OH–(aq)

In this case, the difference between Eo(Na+/Na) and Eo(H2O/H2) is too large, hence the effects of
concentration is not enough to cause Na+ to be reduced.

Overall reaction: 2Cl–(aq) + 2H2O(l) → Cl2(g) + H2(g) + 2OH–(aq)

The electrolysis of brine is used in the industrial production of chlorine. In addition to chlorine,
sodium hydroxide is also obtained as a useful by-product.

Overvoltage (Background Info)

The production of H2 and O2 by electrolysis often requires a greater voltage than is predicted by the
standard electrode potentials. We say that H2 and O2 need an overvoltage before they are discharged.
This overvoltage is required to overcome the high activation energy. Hence, in the electrolysis of brine,
the overvoltage to form O2 and the high [Cl–] makes it easier to form Cl2.

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6.4 Electrolysis using active electrodes

Platinum and graphite (carbon) are chemically inert. They do not usually take part in the electrode
reactions. However, there are electrodes which can undergo oxidation themselves if used as the
anode. These are known as reactive or active electrodes.

(Note: Although graphite is inert, it may react with O2 gas produced at the anode to form CO2 and CO
gases at high temperatures.)

Consider the electrolysis of CuSO4(aq) using copper anode.

● At the anode (positive electrode), the possible oxidation and their electrode potentials are:
Eo /V
Cu2+ + 2e– ⇌ Cu +0.34
O2 + 4H+ + 4e– ⇌2 H2O +1.23
S2O82– + 2e– ⇌2 SO42– +2.01

Since Eo(Cu2+/Cu) is the least positive among the three, Cu is preferentially oxidised. The copper
anode dissolves and Cu2+ ions enter the solution.
∴ Reaction at anode: Cu(s) → Cu2+(aq) + 2e–

On the other hand, if the electrolysis of CuSO4(aq) is done using Pt electrodes, H2O would be
preferentially oxidised at the anode instead.

Exercise 6.4
a) Predict the reaction that occurs at each electrode when the following aqueous solutions are
electrolysed using platinum electrodes.
(reduction) (oxidation)
electrolyte equation for cathode reaction equation for anode reaction
i) dilute NaOH
ii) dilute H2SO4
iii) AgNO3(aq)
iv) a solution of CaCl2
in dilute HNO3

b) Predict the reaction that occurs at each electrode when dilute H2SO4 is electrolysed using a
platinum cathode and a brass (Cu/Zn alloy) anode.

equation for cathode reaction:

equation for anode reaction:

Remarks: Eo(Zn2+/Zn) –0.76V is less positive than Eo(Cu2+/Cu) +0.34V and Eo(O2/H2O/H2) +0.40V

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7 CALCULATIONS IN ELECTROLYSIS
LO12(n): calculate: (i) the quantity of charge passed during electrolysis; (ii) the mass and/or volume of substance liberated
during electrolysis

The amount of substance produced during electrolysis is directly proportional to the amount of
electrons that is passed through the cell.

For example, if 2 moles of electrons are passed through a cell containing molten PbBr2 (see Section
6.1), 1 mole of Pb and 1 mole of Br2 will be formed at the cathode and anode respectively.

Cathode (reduction): Pb2+(l) + 2e– → Pb(l)

Anode (oxidation): 2Br–(l) → Br2(g) + 2e–

1 mole of electrons carries a charge equals to the Faraday constant, F. Hence, the quantity of charge,
Q, carried by n moles of electrons is equal to:

Q=nF where Q is the quantity of charge in coulombs (C)

n is the number of moles of electrons (mol)
F is the Faraday constant = 96 500 C mol–1

From the above, the amount of substance produced at each electrode during electrolysis is directly
proportional to the quantity of charge that is passed through the cell. This is Faraday's law of
electrolysis.

The quantity of charge passed through the cell depends on the magnitude of the current and the time
the current flows:

Q=It where Q is the quantity of charge in coulombs (C)

I is the current in amperes (A)
t is the time in seconds (s)

Hence, we can determine n (the number of moles of electrons passed through the cell) using I, t and
F, and then use n and the half-equation to determine the mass or volume of substance produced at
each electrode during electrolysis.

The mass or volume of substance produced only depends on the magnitude of current (I) and the
duration the current is passed (t). The mass or volume of substance produced does not depend on
the concentration of the ions.

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Exercise 7.1 (Worked Example)

Calculate the quantity of charge (in coulombs) required to liberate 44.8 dm3 of chlorine at s.t.p. in
the electrolysis of molten sodium chloride using inert electrodes.

2Cl– → Cl2 + 2e–

44.8
n(e–) passed = 2  n(Cl2) liberated = 2  = 3.95 mol
22.7
Q = 3.95  96500 = 3.81  105 C

Exercise 7.2
A technician needs to plate a bathroom fixture with 0.86 g of chromium from an electrolytic bath
containing aqueous Cr2(SO4)3. If he is expected to complete the job in 10 min, what would be the
minimum current needed? (Assume the electroplating process is 100% efficient.)
[7.98A]

Exercise 7.3
A current of 0.025 A is passed through a solution of sulfuric acid for 4 hours using inert electrodes.
Write equations for the electrode reactions and calculate the volume of gas formed at each
electrode at r.t.p.
[0.0448 dm3 H2, 0.0224 dm3 O2]

Exercise 7.4
An electric current is passed through solutions of copper(II) sulfate, silver nitrate and dilute sulfuric
acid, connected in series for 20 min. Platinum electrodes are used. If 0.21 g of copper is deposited
in the first cell, calculate the
a) mass of silver deposited in the second cell,
b) volume of hydrogen liberated, at r.t.p., in the third cell,
c) current passed.

d.c.
supply

Cell 1 Cell 2 Cell 3

electrolyte CuSO4(aq) AgNO3(aq) H2SO4(aq)
product at cathode Cu(s) Ag(s) H2(g)
product at anode O2(g) O2(g) O2(g)

[0.714g, 0.0794 dm3, 0.532A]

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Hwa Chong Institution 2024 20 – Electrochemistry

LO12(l): state the relationship, F = Le, between the Faraday constant, the Avogadro constant and the charge on the electron

The relationship between the Faraday constant, the Avogadro constant and the charge on an electron
is: F = Le

where L is Avogadro constant = 6.02  1023 = no. of electrons in 1 mol

e is the charge on one electron = 1.60  10–19 C

The above relationship allows us to determine a value for L or e by conducting an experiment to find
a value for the Faraday constant.

Exercise 7.5
A current of 0.50 A was passed for 1 hour and 40 seconds, into an electrolytic cell containing aqueous
silver nitrate as the electrolyte and silver as the electrodes. 2.0 g of silver was deposited on one of
the electrodes. (Ar of Ag = 108; electronic charge, e = –1.60  10–19 C)

a) At which electrode was the silver deposited? What is the polarity of this electrode?

b) i) Calculate the quantity of charge passed (in coulombs).

ii) Using only the data provided and your answer in b(i), calculate a value for the Avogadro
number.
[1820 C, 6.14 1023]

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Hwa Chong Institution 2024 20 – Electrochemistry

Quantitative electrolysis and Generic Procedure for an Electrolysis experiment

Scenario:
To construct an electrolytic cell and determine a value for Avogadro constant, L, or Faraday constant, F.
Approach:
Set up the electrolytic cell using an external power source (usually a 6 V d.c. battery) and an ammeter. Measure the
amount of substance discharged (by gas collection or by titration), or the change in mass of an electrode. Make
sure the polarities of the electrodes are correct!
Below shows a generic procedure for an electrolysis experiment where the change in mass of electrode is
measured.

Figure 19. Set up for the electrolysis of CuSO4 (aq) Figure 20. Set up for the electrolysis of water
(acidified with sulfuric acid)

Generic procedure for an electrolysis experiment

1. Clean the _(metal)_ electrode(s) with sand paper to remove the oxide layer.
2. Wash the anode with water and then with ethanol, dry it and weigh it accurately. Record its initial
mass, mi. (The cathode is usually not used because some of the discharged metal may fall off from
its surface).
3. Set up the electrolytic cell as shown in the diagram in Figure 2 (the electrodes must not come into
contact with each other).
4. Close the circuit and start a stopwatch at the same time.
5. Record the initial current, Ii, shown on the ammeter.
6. At the end of _ (30 min)__, record the final current reading, If, and break the circuit.
7. Remove the anode, wash it with water and then ethanol, dry it and reweigh it. Record its final mass,
m f.
● From the loss in mass of the anode, the mass and moles of metal lost can be deduced.
● From the average current and time, the charge which flowed through the circuit can be calculated
using Q (in coulombs) = I (in A) x t (in s).
● From Q, the no of moles of electrons can be calculated, and this is linked to the Faraday constant by
Q = n(e–) x F; and the Avogadro constant by F = L x e (the electronic charge).
● The amount of substance produced can also be measured by gas collection if a gas is produced (see
Figure 3), or by titration of the electrolyte if the product enters the electrolyte. In the case of the
latter, the electrolyte should be stirred thoroughly if a sample is to be withdrawn for titration.
● Sources of errors should be identified (e.g. high measurement error due to small changes in mass, or
fluctuation in current) and suggestions made to limit / eradicate them. (e.g. use a longer time to get
more mass loss to lower the percentage error, or use a variable resistor to fix the current throughout
the duration of the experiment)

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8 APPLICATIONS OF ELECTROLYSIS

8.1 Electrolytic purification of copper

LO12(o)(ii): explain, in terms of the electrode reactions, the industrial process of: (ii) the electrolytic purification of copper

Copper is a good conductor of electricity, and is used extensively to make electrical wiring and
components. The extraction of copper from copper ore is done by reduction with carbon. However,
the copper produced is not pure enough for use as a conductor, so it is purified using electrolysis.
– +

(small strip of) impure Cu anode

pure Cu cathode

CuSO4(aq)

anode sludge
Figure 21. Set up for the electrolytic purification of copper

Electrolyte: CuSO4(aq)
Anode: impure copper
Cathode: pure copper

During electrolysis, the voltage used is such that copper at the anode will be oxidised into Cu2+ ions.

Reaction at anode: Cu(s) → Cu2+(aq) + 2e–

• Metal impurities that have Eo values less positive than Eo(Cu2+/Cu) are more readily oxidised than
Cu. They will also be oxidised and enter the electrolyte as the metal ions.
• Metal impurities that have Eo values more positive than Eo(Cu2+/Cu) will not be oxidised at the
anode. These metals will stay as solid metal and eventually drop off as anode sludge.

At the cathode, the Cu2+ ions in the electrolyte are preferentially reduced. Hence more copper
deposits onto the pure copper cathode.

Reaction at cathode: Cu2+(aq) + 2e– → Cu(s)

● The metal ions that came from the metal impurities which dissolved at the anode have Eo values
that are less positive than Eo (Cu2+/Cu). These ions are less easily reduced than Cu2+ ions. They are
not reduced and remain in the electrolyte.

Overall, there is a net transfer of copper from the impure copper anode to the cathode. The anode
decreases in mass and the cathode increases in mass. Metal impurities that are above copper in the
electrochemical series (e.g. Zn, Fe) will remain in the electrolyte as ions while those below copper in
the series (e.g. Ag, Au) will form the anode sludge.

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Hwa Chong Institution 2024 20 – Electrochemistry

Exercise 8.1: Electrolytic purification of copper

The conductivity of copper increases tenfold when it is more than 99.9% pure. Copper minerals
often contain copper sulfide mixed with the sulfides of silver and zinc. After roasting in air to
produce the oxides and reduction to the crude metals with carbon, the solid impure copper is
purified by electrolysis.

With reference to Eo data, explain in detail the electrode reactions that take place during this
electrolysis and how each of the two impurity metals (zinc and silver) is removed from the copper.

8.2 Anodising of Al
LO12(o)(i): explain, in terms of the electrode reactions, the industrial process of: (i) the anodizing of aluminium

Aluminium is a reactive metal that oxidises easily. However, aluminium objects are usually resistant
to corrosion because when exposed to air, aluminium forms a layer of Al2O3 (about 10–6 cm thickness)
on its surface. This oxide layer is resistant to corrosion and it acts as a protective layer which seals off
the aluminium beneath it from further reaction.

Anodising of aluminium is a surface treatment to increase the thickness of the corrosion resistant
Al2O3(s) layer on the surface of an aluminium object by electrolysis.
+ –

(+) (–)

Al anode Pt cathode

dilute H2SO4

Figure 22. Anodising of aluminium

Electrolyte: dilute H2SO4

Anode: aluminium object to be anodised
Cathode: Pt or graphite

The reactions occurring at each electrode are:

Reactions at anode : 2Al(s) + 3H2O(l) → Al2O3(s) + 6H+(aq) + 6e–

Reaction at cathode : 2H+(aq) + 2e– → H2(g)

The Al2O3 layer formed this way is porous. The pores are then sealed by dipping the aluminium object
in hot water. Because of the way it is formed, the oxide coating is porous enough to accept and hold
dyes that would not otherwise stick to aluminium. Since
the thickness of the deposit of aluminium oxide
increases with electrolysis time, the amount of dye
deposited and the intensity of colour developed also
increase with electrolysis time. Anodised objects can
therefore be decorative. Anodised aluminium can be
used to make window frames, drink cans and iPad
cases.

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Exercise 8.2: Manufacture of NaOH and NaClO by electrolysis of brine [modified from N05/2/2]
The diagram below shows the diaphragm cell used for the electrolysis of concentrated sodium
chloride solution (brine). This is a commercially important industrial process used to manufacture
chlorine gas, hydrogen gas and aqueous sodium hydroxide. The overall process is represented by
the equation:
electrolys is
2NaCl(concentrated) + 2H2O(l) ⎯⎯ ⎯ ⎯ ⎯ ⎯
⎯→ 2NaOH(aq) + Cl2(g) + H2(g)

Cl2(g)
H2(g)
purified
concentrated
NaCl solution
(brine)

steel cathode (–)

graphite or titanium
anode (+)

NaOH(aq)

a) With reference to Eo data, explain why the electrolysis of dilute NaCl produces mainly
oxygen gas at the anode, whereas the electrolysis of concentrated NaCl solution produces
mainly chlorine gas.

b) The sodium hydroxide made in the diaphragm cell is formed in aqueous solution. Suggest
with the aid of an appropriate half-equation, how sodium hydroxide is obtained in the
process.

c) In the diaphragm cell, the anode is made of titanium and the cathode is made of steel.
Suggest why steel is never used for the anode.

d) The Asbestos diaphragm prevents a negative ion produced in the cathode compartment
from moving into the anode compartment, because that negative ion may be oxidised in
preference over Cl– at the anode.
(i) Using the Data Booklet, write an equation that shows how this negative ion may be
oxidised.
(ii) Explain why this negative ion may be more readily oxidised than Cl–.

e) Suggest one large-scale use for each of the following products.

f) The Asbestos diaphragm is removed and the contents of the cell are stirred so that Cl2 reacts
with NaOH to form NaCl and NaClO (bleach). The cell is kept cold. Construct a balanced
equation for this disproportionation reaction.

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Hwa Chong Institution 2024 20 – Electrochemistry

Exercise 8.3: Electroplating

a) In silver plating, an aqueous solution containing
[Ag(CN)2]– ions is used. This is a stable complex
and produces a very low concentration of Ag+(aq)
ions.

[Ag(CN)2]–(aq) ⇌ Ag+(aq) + 2CN–(aq)

i) Write an equation, including state symbols,

for the cathode reaction.
pure
ii) Suggest why a very low concentration of Ag+ Ag
is used.
object
to be
plated

b) (J99/1/3c) In order to replace the worn silver coating on a trophy, it is estimated that 0.50 g of
silver needs to be electroplated onto it. Calculate the length of time that a current of 0.20 A has
to be passed through the electrolysis bath in order to achieve this.
[2240s (3 sf)]

LOOKING AHEAD
In this topic, you learnt how the standard electrode potential, Eo, is a measure of the ease of
reduction of an atom or ion. The difference between two electrode potentials gives rise to a cell
potential, Eocell, the magnitude and sign of which indicates the spontaneity of a reaction. In
electrolysis, we can control the products obtained by choosing appropriate conditions such as
concentration and electrodes used. In the next few topics such as Group 2 and Group 17, we will
use Eo values to explain the relative reactivity of Group 2 elements as reducing agents and Group
17 elements as oxidising agents. In the topic of Transition Elements, we will use the position of the
ion or substance in the electrochemical series to select a suitable homogeneous catalyst. We will
also use Eo values to explain redox processes in QA experiments.

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21 Periodicity

GUIDING QUESTIONS
 What are the trends and variations in physical and chemical properties in elements and compounds?
 How can the trends and variations in atomic / physical / chemical properties be explained?
 How can we predict the properties of elements and their compounds?

LEARNING OUTCOMES
Students should be able to:
5(a) recognise variation in the electronic configurations across a Period and down a Group.
(Refer to Topic 1 Atomic Structure & Physical Periodicity)
5(b) describe and explain qualitatively the trends and variations in atomic radius, ionic radius, first
ionisation energy and electronegativity,
i. across a Period in terms of shielding and nuclear charge,
ii. down a Group in terms of increasing number of electronic shells and nuclear charge
(Refer to Topic 1 Atomic Structure & Physical Periodicity)
5(c) interpret the variation in melting point and in electrical conductivity across a Period in terms
of structure and bonding in the elements (metallic, giant molecular, or simple molecular)
(Refer to Topic 2 Chemical Bonding)
5(d) describe and explain the trend in volatility of the group 17 elements in terms of instantaneous
dipole-induced dipole attraction (Refer to Topic 2 Chemical Bonding)
5(e) for elements across the third period:
(i) state and explain the variation in the highest oxidation number of the elements in oxides
(for Na2O; MgO; Al2O3; SiO2; P4O10; SO3) and chlorides (for NaCl; MgCl2; AlCl3; SiCl4; PCl5)
(ii) state and explain the variation in bonding in oxides and chlorides in terms of
electronegativity (with the exception of AlCl3)
(iii) describe the reactions of the oxides with water (for Na2O; MgO; Al2O3; SiO2; P4O10; SO3)
(iv) describe and explain the acid/base behaviour of oxides (for Na2O; MgO; Al2O3; SiO2;
P4O10; SO3) and hydroxides (for NaOH; Mg(OH)2; Al(OH)3), including, where relevant,
amphoteric behaviour in reaction with sodium hydroxide (only) and acids
(v) describe and explain the reactions of the chlorides with water (for NaCl; MgCl2; AlCl3;
SiCl4; PCl5)
(vi) suggest the types of structure and bonding present in the oxides and chlorides from
observations of their chemical and physical properties
5(f) describe and deduce from Eo values the relative reactivity of elements of:
(i) Group 2 as reducing agents;
(ii) Group 17 as oxidising agents
5(g) describe and explain the trend in thermal stability of:
(i) Group 2 carbonates in terms of the charge density of the cation and the polarisability of
the large anion
(ii) Group 17 hydrides in terms of bond energies
5(h) predict the characteristic properties of an element in a given Group by using knowledge of
chemical periodicity
5(i) deduce the nature, possible position in the Periodic Table, and identity of unknown elements
from given information of physical and chemical properties

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Hwa Chong Institution 2024 21 – Periodicity

REFERENCES
1. Peter Cann & Peter Hughes (2015), Chemistry, Hodder Education, Chapters 10 and 11.
2. Martin S. Silberberg, Chemistry – The Molecular Nature of Matter and Change, 6th Edition,
McGraw-Hill, Chapter 8

LOOKING BACK
In this topic, we will study the trends in chemical properties of elements and their compounds. It is essential
to recall knowledge from earlier topics on Atomic Structure & Physical Periodicity and Chemical Bonding:
ionisation energy trends and electronegativity have an impact on the types of the bonding found in
compounds, and this will in turn affect their physical properties. To explain chemical properties and trends,
concepts on redox reactions, electrode potential and acid-base behaviour are also relevant.

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Hwa Chong Institution 2024 21 – Periodicity

1 INTRODUCTION
LO 5(a): Recognise variation in the electronic configurations across a Period and down a Group.

Periodicity is the study of repeating patterns in the physical

and chemical properties of the elements in the periodic
table.

The arrangement in the periodic table is closely related

to the electronic configuration of the elements.

 In the periodic table, elements are arranged in order

of increasing proton number.

Prior to 1913, Mendeleev’s Periodic Table, which

arranged elements according to atomic mass, was
widely accepted by chemists though there were
inconsistencies. Then in 1913, Henry Moseley, using Figure 1. Dalton’s original table of
new technology (X-ray electron gun) at that time, elements

showed the link between atomic number and element’s

position in the table, which addressed the
inconsistencies and led to the Periodic Table we use
today.

Table 1. Some trends in Period 3 elements

Element Na Mg Al Si P S Cl Ar
non- non- non- non-
metal metal metal metalloid
metal metal metal metal
Electronic [Ne] [Ne] [Ne] [Ne] [Ne]
[Ne] 3s1 [Ne] 3s2 [Ne] 3s2 3p2
structure 3s2 3p1 3s2 3p3 3s2 3p4 3s23p5 3s2 3p6
No. of
valence 1 2 3 4 5 6 7 8
electrons
Group 1 2 13 14 15 16 17 18
Period 3 3 3 3 3 3 3 3
Electrical semi-
good conductors non-conductors
conductivity conductor

 Elements in the same group resemble one another in their chemical properties due to their similar
outer electronic configuration. The group number of groups 1 and 2 is the same as the number of
valence electrons. The group number of groups to the right of the d-block elements can be
remembered by adding 10 to the number of valence electrons in each group.

 The period number is the same as the number of quantum shells. Elements in the same period
show a periodic change in their chemical and physical properties across the period.

Thus, knowledge of periodicity is useful in understanding and predicting the physical and chemical
behaviour of elements.

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Hwa Chong Institution 2024 21 – Periodicity

2 CHEMICAL PROPERTIES OF THE ELEMENTS (Background Info)

The following table describes the chemical properties of Period 3 elements and their common uses:

Na Mg
Sodium Magnesium
Soft silvery metal Often cut into
Must be stored in oil to magnesium ribbon
prevent oxidation by air strips (left)

Tarnishes (forms
oxide) in air, but much
Sodium stored in oil Roll of magnesium ribbon less readily than
sodium

outer layer of sodium oxide

Magnesium burns with
a bright white light,
fresh sodium
and hence is often used
to make fireworks.
In air, sodium quickly forms a
layer of oxide Magnesium fireworks

Al Si
Aluminium Silicon
The metal instantly Shiny black
protects itself in air by metalloid solid
forming a thin, but tough,
layer of aluminium oxide, Does not react with
Al2O3, which is harder air at room
Aluminium foil than the metal itself. Crystalline silicon has a shiny
temperature.
reflective surface
The toughness of the
oxide layer, and the
relatively low density of
the metal combine to
give it an unbeatable Lightweight sunglasses frame
made from aluminium
strength to weight ratio.
Structure of silicon

Aluminium is tough and lightweight, making it Because silicon is a

perfect for use in the transport and packaging semiconductor, one of
industries. The silicon chip
revolutionised electronics its most important uses
is in electronics.

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Hwa Chong Institution 2024 21 – Periodicity

P S
Phosphorus Sulfur
Phosphorus exists as several Bright yellow crystalline
allotropes. The most common solid
are white and red phosphorus. Pure sulfur is an
White phosphorus with a corner sliced odourless non-metal.
off
The characteristic smell
White Phosphorus, P4, is a very associated with sulfur is due to its compounds
reactive waxy solid which rather than pure sulfur itself.
generally must be stored under
water. Elemental sulfur has many different allotropes,
Due to bond but cyclic S8, is the most common.
White phosphorus
angle strain (as stored under water
the P-P-P bond
angle is more acute), it catches
fire spontaneously in air.
Structure of white Structure of S8
phosphorus, P4

Sulfur burns with a blue flame, to form sulfur

Red Phosphorus, P, is dioxide
polymeric and appears as
a red powder.
blue flame

Because of the network of linked P atoms, it is yellow sulfur

much more stable than white phosphorus.
Sulfur combusting

However, it still reacts with

air when given enough
energy (heating or striking).
A common use of red Elemental sulfur can be found near hot springs and
volcanoes.
phosphorus is in matches!

Note: In this chapter, we will concentrate on

the reactions of white phosphorus P4.
Cl Ar
Chlorine Argon
Chlorine is a yellow-green toxic Argon is a colourless inert gas.
gas with a distinctive "bleach" It appears violet when placed
smell. in a high voltage electric field
It exists as diatomic Cl2 molecules. Plasma globe with (as in the plasma globe to the
a pure argon
Chlorine is a strong oxidising agent that reacts left).
atmosphere
with almost every element to form chlorides.
However, it does not react directly with oxygen.

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Hwa Chong Institution 2024 21 – Periodicity

Exercise 2.1

1 Which of the following statements about the properties associated with ionic and covalent
compounds is correct?
A The only covalent compounds with high melting points are those in which
hydrogen bonding occurs.
B Any compound that contains both hydrogen and oxygen atoms in its molecule
can form hydrogen bonds.
C Ionic bonds and covalent bonds cannot both occur in the same compound.
D Ionic compounds differ from metals in that ionic compounds do not conduct
electricity in the solid state.
[PromoHCI09/P1/Q5]

2 The bond in the compound XY is likely to be ionic rather than covalent if

1 X is a large cation
2 Y is a small anion
3 X has a large positive charge
[PromoTJC12/P1/Q17]

3 W, X, Y and Z are elements in Period 3.

W has greater electrical conductivity than Y but lower first ionisation energy than X. Y has higher
melting point than W, and Z has a greater atomic radius than W.

Based on this information, which of the following is a possible arrangement of these elements
in increasing proton number?

A W, X, Y, Z
B X, Y, W, Z
C Y, X, Z, W
D Z, W, Y, X
[PrelimDHS12/P1/Q14]

4 State and explain the trend in the electrical conductivity across Period 3 elements, from Na to Al.

5 State and explain the trend in the melting point across Period 3 elements, from P to Ar.

melting decreases. So S8 has the highest melting point, followed by P4, then Cl2, then Ar.

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Hwa Chong Institution 2024 21 – Periodicity

3 VARIATION IN OXIDATION NUMBER OF PERIOD 3 OXIDES AND CHLORIDES

LO 5(e)(i): for elements across the third period: state and explain the variation in the highest oxidation number of the elements
in oxides (for Na2O; MgO; Al2O3; SiO2; P4O10; SO3) and chlorides (for NaCl; MgCl2; AlCl3; SiCl4; PCl5)

The following diagram and table summarise the oxidation numbers that are found in the oxides and
chlorides of Period 3 elements.

Period 3 element Na Mg Al Si P S
Oxide Na2O MgO Al2O3 SiO2 P4O6 P4O10 SO2 SO3

O.N. in oxides +1 +2 +3 +4 +3 +5 +4 +6
Chloride NaCl MgCl2 AlCl3 SiCl4 PCl3 PCl5
O.N. in in chlorides +1 +2 +3 +4 +3 +5
Note: Sulfur chlorides and chlorine oxides are not in the syllabus.

A few trends can be observed across the period:

 Oxidation numbers of the elements in their oxides are always positive (except for fluorine, where
O.N. of F is −1 in F2O) as oxygen is the most electronegative element other than fluorine.
 From Na to Cl, there is a regular increase in the number of O and Cl atoms that can combine with
an atom of the element.
 The maximum positive oxidation number shown by an element often corresponds to the number
of valence electrons in an atom of the element.
o e.g. phosphorus has 5 valence electrons and thus has a maximum oxidation number of +5
 From left to right, the elements show increasing variation in possible oxidation numbers: e.g.
o In their oxides and chlorides, the metals Na, Mg and Al display only one possible oxidation
number each, corresponding to the loss of all their valence electrons.
o P, S and Cl exhibit a wider range of oxidation numbers because they can expand their
octets (by utilising their vacant d-orbitals, which are close enough in energy to their
valence electrons to be used for chemical bonding as well). The oxidation number thus
depends on the number of electrons used for bonding.

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Hwa Chong Institution 2024 21 – Periodicity

4 PROPERTIES OF THE OXIDES

4.1 Structure and bonding of the oxides

LO 5(e)(ii): state and explain the variation in bonding in oxides in terms of electronegativity

The trends in physical properties of the oxides can be explained by the gradual change in their
structures and bonding.

Formula of oxide Na2O MgO Al2O3 SiO2 P4O10 SO3

giant
giant ionic lattice structure
molecular simple, discrete covalent
Structure (with increasing covalent character from
lattice molecules
left to right)
structure
strong
covalent
strong electrostatic forces of attraction weak intermolecular
Bonding bonds
between oppositely-charged ions forces between molecules
between
atoms

As we move across the period, the bonding of the oxides changes from ionic to covalent.
 This is because the difference in electronegativity between each element and oxygen decreases
across the period, hence bonding becomes increasingly covalent. Recall from Topic 2 Chemical
Bonding that covalent bonds usually form between atoms of similar electronegativity while atoms
with a great difference in electronegativity tend to form ionic bonds. The difference in
electronegativity can help us predict if the compound is predominantly ionic or covalent.

4.2 Trend in melting points of the oxides

The trend in melting points of the oxides across the period can be explained by the structure and
bonding involved in each oxide.

Formula of oxide Na2O MgO Al2O3 SiO2 P4O10 SO3

Physical state at 25 °C solid solid solid solid solid liquid

sublimes at
Melting point (°C) 1130 2850 2070 1700 17
360

 Na2O, MgO and Al2O3 are all ionic oxides:

o (Structure) giant ionic lattice with
o (Bonding) strong electrostatic forces of attraction between oppositely charged ions
o A large amount of energy is required to overcome the strong ionic bonds  high m.p.

Recall in Topic 2 Chemical Bonding that lattice energy gives an indication of the strength of the ionic
bonding – the larger the magnitude of L.E., the stronger the ionic bonding. For ionic compounds, this
means a higher m.p.
𝐪+ × 𝐪−
Lattice energy 
𝐫+ + 𝐫−

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Hwa Chong Institution 2024 21 – Periodicity

 Melting point of MgO is higher than that of Na2O:

o Mg2+ has smaller ionic radius and higher charge than Na+
o Thus, lattice energy of MgO is much greater in magnitude than that of Na2O.
o More energy is required to overcome the electrostatic forces of attraction between Mg2+
and O2– than in the Na2O lattice.

 Melting point of Al2O3:

o Although the lattice energy expression predicts the L.E. of Al2O3 to be larger in magnitude
than that of MgO, m.p. of Al2O3 is actually lower than that of MgO.
o Possible reason for Al2O3 having lower m.p. than MgO:
 Al3+ has very high charge density which can polarise the O2– ion (even though
O2– is small and normally not easily polarized)  this confers covalent
character to Al2O3, which causes magnitude of L.E. to differ from expected.

 Melting point of silicon dioxide (also called silicon(IV) oxide), SiO2:

o (Structure) giant molecular structure (resembling that of diamond) with
o (Bonding) strong covalent bonds between Si and O atoms. Each Si atom is bonded to four
O atoms, and each O atom is bonded to two Si atoms.
o A large amount of energy is required to break the strong covalent bonds  high m.p.

 Oxides of phosphorus and sulfur:

o (Structure) simple discrete covalent molecules with
o (Bonding) relatively weak intermolecular dispersion forces between molecules
o Comparatively less energy is required to overcome these weaker dispersion forces 
lower m.p.

Structure of P4O10

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Hwa Chong Institution 2024 21 – Periodicity

4.3 Acid-base behaviour of the oxides and hydroxides

LO 5(e)(iii): describe the reactions of the oxides with water
(iv): describe and explain the acid/base behaviour of oxides, including, where relevant, amphoteric behaviour in reaction
with sodium hydroxide (only) and acids
(vi): suggest the types of structure and bonding present in the oxides from observations of their chemical and physical
properties
LO 5(h): predict the characteristic properties of an element in a given Group by using knowledge of chemical periodicity
LO 5(i): deduce the nature, possible position in the Periodic Table, and identity of unknown elements from given information
of physical and chemical properties

From their structure and bonding, the oxides of Period 3 elements can be classified into ionic oxides
and covalent oxides. Ionic oxides tend to act as bases whereas covalent oxides act as acids. Oxides of
elements that are near the ionic/covalent boundary tend to form amphoteric oxides - i.e. oxides that
can act as acids or bases depending on the conditions.

This section will also cover the acid-base behaviour of the three metal hydroxides, NaOH, Mg(OH)2 and
Al(OH)3.

 Ionic oxides contain the O2– ions in their ionic lattice. The O2– ions readily hydrolyse in water to
form OH– ions. Hence, ionic oxides tend to be basic in nature:
O2– (aq) + H2O (l)  2OH– (aq)

 Covalent oxides are usually classified as acidic oxides because they form acidic solutions when
reacted with water, producing H3O+ and an oxo-anion (i.e. a negatively charged ion containing the
element covalently bonded to a number of oxygen atoms, e.g. SO42⁻ and PO43⁻). [Refer to section
4.3.5 on the acidic oxides]

 Aluminium oxide is the only amphoteric oxide in Period 3. [Refer to section 4.3.3 for definition of
‘amphoteric’]

Table 2. Summary list of Period 3 oxides, their bonding and their acid-base nature
Na Mg Al Si P S
Oxide Na2O MgO Al2O3 SiO2 P4O10 SO3
*P4O6 *SO2
Bonding ionic covalent
Nature basic amphoteric acidic
*Note: The behaviour and reactions of P4O6 and SO2 are not in the syllabus.

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4.3.1 The basic oxides

Sodium oxide and magnesium oxide both react with water and acids, as shown in the table below.

Oxide Reaction with water Reaction with acids

Na2O Observation Observation
 appears to dissolve completely in water  dissolves in acids
 vigorous and exothermic reaction, even  reaction is exothermic
in cold water  reaction produces a salt solution
 forms a strongly alkaline colourless
solution around pH 13 (depending on
concentration)

Equation Equation
Na2O(s) + H2O(l)  2Na+(aq) + 2OH−(aq) Na2O(s) + 2H+(aq)  2Na+(aq) + H2O (l)

MgO Observation Observation

 very slow reaction and limited solubility  dissolves in acids
in water, may appear as though nothing  reaction produces a salt solution
is happening
 some magnesium hydroxide is formed
but it is only sparingly soluble, so not all
hydroxide ions formed are released into
the solution  pH is lower than for
Na2O, around pH 9

Equations
MgO (s) + H2O(l)  Mg(OH)2 (s) Equation
MgO(s) + 2H+(aq)  Mg2+(aq) + H2O (l)
Mg(OH)2 (s) ⇌ Mg2+(aq) + 2OH− (aq)

4.3.2 The basic hydroxides

Both sodium and magnesium hydroxides contain the hydroxide ion, OH−, which is a strong base. Thus,
they are basic hydroxides, and can react with acids to form salt solutions in a classic neutralisation
reaction.

Reaction with acids (e.g. dil. hydrochloric acid)

Hydroxide Appearance Observation Equation for the neutralisation
NaOH White pellets Solid dissolves NaOH(s) + HCl(aq)  NaCl(aq) + H2O(l)
when solid exothermically to give
a colourless solution
Colourless No visible change, but NaOH(aq) + HCl(aq)  NaCl(aq) + H2O(l)
solution when resultant mixture
dissolved in water becomes warmer
(exothermic reaction)
Mg(OH)2 White solid/ppt Solid/ppt dissolves in Mg(OH)2 (s) + 2HCl(aq)  MgCl2(aq) +
only sparingly acids to give a 2H2O(l)
soluble in water colourless solution

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4.3.3 The amphoteric oxide – Aluminium oxide

Aluminium oxide is an ionic oxide containing Al3+ and O2– ions. However, the high charge density of the
Al3+ ion gives it great polarizing power, allowing the O2– ion to be slightly polarized, despite its small
size. This confers some covalent character to the oxide.
This mixture of ionic and covalent character allows Al2O3 to display both basic and acidic properties -
i.e. it is amphoteric.

Oxide Reaction with Reaction with acids Reaction with strong bases
water (sodium hydroxide)
Al2O3 Observation Observation Observation
No reaction in  dissolves in acids to form a salt  dissolves in excess base to form
water solution, with Al3+ as the cation a salt solution with the Al being
(insoluble) part of the anion, the colourless
aluminate complex ion,
[Al(OH)4]−.

Equation Equation
when reacting as a basic oxide: when reacting as an acidic oxide:
Al2O3 (s) + 6H+(aq) Al2O3 (s) + 2OH−(aq) + 3H2O(l)
 2Al3+(aq) + 3H2O(l)  2[Al(OH)4]−(aq)
aluminate ion

4.3.4 The amphoteric hydroxide – Aluminium hydroxide

Just like aluminium oxide, aluminium hydroxide is also amphoteric.
 With acids, it reacts just like sodium and magnesium hydroxides, dissolving to form a colourless
salt solution of the metal cation, Al3+.
 With strong bases like sodium hydroxide, the hydroxide shows its acidic nature and reacts to form
the aluminate anion.

Hydroxide Appearance Reaction with acids Reaction with strong bases (sodium
hydroxide)
Al(OH)3 White Observation Observation
solid/ppt  dissolves readily in acids to  dissolves in excess strong base to
insoluble in form a colourless salt form the colourless aluminate
water solution, with Al3+ as the complex ion, [Al(OH)4]−.
cation

Equation Equation
Al(OH)3 (s) + 3HCl(aq) Al(OH)3 (s) + NaOH(aq)  Na[Al(OH)4](aq)
 AlCl3(aq) + 3H2O(l) salt solution
salt solution

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4.3.5 The acidic oxides

As we move across the period, the electronegativity difference between each element and oxygen
becomes too small for ionic bonds to form. The remainder of the oxides in Period 3 are thus all covalent
in nature.

 Silicon dioxide, SiO2, is a macromolecular (i.e. giant covalent) oxide that does not contain the O2–
ion and hence shows no basic properties at all. It is, however, weakly acidic in nature, and may
react with strong bases, usually requiring more vigorous conditions (e.g. higher concentrations,
temperatures, or pressures) to help in breaking up the macromolecular lattice.

Oxide Reaction with water Reaction with strong bases

SiO2 Observation Observation
 does not dissolve in/react with water  no reaction with hot aqueous bases (e.g.
NaOH) under laboratory conditions
 usually requires hot and concentrated
strong bases before reaction proceeds
 a solution of the silicate salt, SiO32−, is
formed

Equation
SiO2 (s) + 2 OH−(conc)  SiO32− (aq) + H2O (l)
∆ silicate ion
(colourless)

 The oxides of phosphorus and sulfur (and even those of chlorine, though not in the syllabus), are
all simple covalent oxides which readily react with water to form acidic solutions.

Oxide Reaction with water Reaction with strong bases

P4O10 phosphorus(V) oxide
Observation Observation
 reacts violently with water to give an  dissolves in strong bases to form a salt
acidic solution of H3PO4 solution
 forms a fairly strongly acidic solution
around pH 2 (depending on
concentration)

Phosphoric(V) acid, H3PO4, is a triprotic acid,

slightly weaker than H2SO4.

Structure of an
undissociated
molecule of
H3PO4:
Equation
if excess OH− is added:
P4O10 (s) + 12 OH−(aq)  4 PO43−(aq) + 6 H2O(l)
Equation
P4O10 (s) + 6 H2O(l)  4 H3PO4 (aq)

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Oxide Reaction with water Reaction with strong bases

SO3 Sulfur trioxide
Observation Observation
 violent and very exothermic reaction in  reacts directly with bases to form salt
water, producing a very acidic mist of solutions
H2SO4 droplets
 forms a strongly acidic solution around
pH 1 (depending on concentration)

The sulfuric acid formed, also known as

sulfuric(VI) acid, is a strong dibasic acid,
which ionises completely in water.

Structure of an
undissociated molecule
of H2SO4:
Equation
SO3 (l) + 2 OH−(aq)  SO42−(aq) + H2O(l)
Equation
SO3 (l) + H2O(l)  H2SO4 (aq)
strongly acidic solution

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4.4 Summary of the properties of oxides across Period 3

The following table summarises the trends in the Period 3 oxides (in their highest oxidation states):

Formula of oxide Na2O MgO Al2O3 SiO2 P4O10 SO3

Oxidation number +1 +2 +3 +4 +5 +6

Physical state at 25
solid solid solid solid solid liquid
°C
sublimes at
Melting point (°C) 1130 2850 2070 1700 17
360
giant ionic lattice structure with strong giant
simple, discrete covalent
electrostatic forces of attraction molecular
molecules with relatively
Bonding & structure between oppositely-charged ions structure,
weak dispersion forces
(with increasing covalent character from covalent
between molecules
left to right) bonding
ampho-
Acidic/basic nature basic acidic
teric
soluble sparingly Insoluble in water soluble soluble
soluble

reacts to reacts to large amount of energy reacts to reacts to

Reaction with water
form form required to break lattice form fairly form
strongly weakly structures acidic H3PO4 strongly
basic NaOH basic acidic
Mg(OH)2 H2SO4

Approx. pH of
13 9 7 7 2 1
aqueous solution

Exercise 4.1 (Worked Example)

1 Describe how the bonding in the oxides of the elements changes across Period 3. Explain the change
in terms of the electronegativities of the element.

The bonding changes from ionic to ionic with covalent character to covalent across period 3. Across
period 3, the electronegativity of the element increases. A large difference in electronegativity
between the element and oxygen results in an ionic oxide while a small difference in
electronegativity results in a covalent oxide.

2 Describe how the acid-base behaviour of the oxides changes across period 3. Explain the trend in
terms of structure and bonding.

Across period 3, the oxide behaviour changes from basic to amphoteric to acidic.
The basic oxides, Na2O and MgO have giant ionic structures while the covalent oxides, P4O10 and SO3,
have simple molecular structure. Al2O3 is an amphoteric oxide (has both acidic and basic properties)
as it has giant ionic structure with covalent character.

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Exercise 4.2
1 Based on your knowledge of periodicity and Period 3 elements, predict the nature of Cl2O7, an
oxide of chlorine.
A Basic B Acidic C Amphoteric D Neutral

2 A mixture of the oxides of two elements of the third period is dissolved in water. The solution
remained approximately neutral.
What could be the constituents of the mixture?
A Al2O3 and MgO C Na2O and P4O10
B Na2O and MgO D SO3 and P4O10
[J03/P1/Q13]

3 Consider the sequence of oxides Na2O, SiO2, P4O10. Which of the following factors decreases from
Na2O to SiO2 and also from SiO2 to P4O10?
A melting point C pH when mixed with water
B covalent character D solubility in aqueous alkali

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5 PROPERTIES OF THE CHLORIDES

LO 5(e)(ii): state and explain the variation in bonding in chlorides in terms of electronegativity (except for AlCl3)
(v): describe and explain the reactions of the chlorides with water (for NaCl; MgCl2; AlCl3; SiCl4; PCl5)
(vi): suggest the types of structure and bonding present in the chlorides from observations of their chemical and physical
properties
LO 5(h): predict the characteristic properties of an element in a given Group by using knowledge of chemical periodicity
LO 5(i): deduce the nature, possible position in the Periodic Table, and identity of unknown elements from given information
of physical and chemical properties

5.1 Structure and bonding of the chlorides

The trends in physical properties of the chlorides can also be explained by the gradual change in their
structure and bonding. Like the oxides, the bonding of the chlorides changes from ionic to covalent
across the period.

Formula of
NaCl MgCl2 AlCl3 SiCl4 PCl5
chloride
simple simple
discrete discrete
simple discrete
covalent covalent
Structure giant ionic lattice structure covalent
molecules molecules
molecules
(in vapour (in vapour
phase) phase)
strong electrostatic forces of
Bonding attraction between weak dispersion forces between molecules
oppositely-charged ions

Again, this is because the electronegativity difference between each element and chlorine decreases
across the period, hence bonding becomes increasingly covalent.

5.2 Trend in melting points of the chlorides

As for the oxides, the trend in melting points of the chlorides across the period can be explained by
their structure and bonding.

Formula of chloride NaCl MgCl2 AlCl3 SiCl4 PCl5

Physical appearance at
solid solid solid liquid solid
25 °C
sublimes at sublimes at
Melting point (°C) 801 714 –70
~180 ~160

 NaCl and MgCl2:

o white crystalline solids at room temperature
o (Structure) giant ionic lattice with
o (Bonding) strong electrostatic forces of attraction between oppositely charged ions
o A large amount of energy is required to overcome the strong ionic bonds  high m.p.

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 Aluminium chloride:
o very pale yellow powder at room temperature
o In the vapour phase, aluminium chloride is simple molecular in structure, forming gaseous
Al2Cl6 dimers (which involve dative bonding):

o In the vapour phase, there exists an equilibrium between Al2Cl6 dimers and AlCl3
monomers. As the temperature increases, the position of the equilibrium shifts more to
the right, favouring the monomers.
Al2Cl6 (g) ⇌ 2AlCl3 (g)

Is aluminium chloride really a simple covalent compound? (Background Info)

In the solid state, AlCl3 actually has an ionic lattice structure with a large amount of covalency.
This covalency is due to the very high charge density of the Al3+ ion (small ionic radius and high
charge) which is able to polarise the large electron cloud of nearby Cl− ions.

Just below 180 °C, the solid expands and AlCl3 loses all ionic character, converting to discrete
Al2Cl6 gas molecules with comparatively weaker dispersion forces between them, causing the
solid to suddenly vaporise (i.e. it sublimes).
Aluminium chloride is said to have a borderline type of bonding, somewhere in between that of
purely ionic and purely molecular compounds.

 Silicon tetrachloride, SiCl4:

o It is a colourless fuming liquid at room temperature
o (Structure) simple discrete covalent molecules with
o (Bonding) relatively weak intermolecular forces between molecules
o Comparatively less energy is required to overcome these weaker forces  lower m.p.

 phosphorus(V) chloride, PCl5:

o off-white to pale yellow powder at room temperature
o PCl5 is considered to have a simple molecular structure and can largely be treated as such
in the context of A-level chemistry.

Why is PCl5 a solid at room temperature? (Background Info)

At room temperature, when in the solid state, PCl5 self-ionises, causing it not to melt as expected
due to stronger ionic interactions:
PCl5 + PCl5  PCl4+ + PCl6−
At around 160 °C, the ions convert back to simple molecular PCl5 with relatively weaker
intermolecular dispersion forces. Because these attractions are easier to overcome, PCl5 then
sublimes.

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Inorganic Synthesis – Preparation of Inorganic Compounds: e.g. Aluminium chloride

You may be required to plan experiments to prepare and purify inorganic substances. The
separation and purification techniques used in Organic Chemistry are also applicable for
inorganic compounds: filtration, extraction, distillation, recrystallization, and melting point
determination.

Using aluminium chloride as an example, here is a fully labelled diagram of a laboratory set
up used to produce, purify and collect an inorganic compound. Of course, the physical state
and properties of the desired compound should be considered when designing the
experiment.

Ensuring a moisture-free environment

Drying the chlorine gas before feeding it through the system, and adding a calcium chloride
guard tube at the exit point help to ensure that the environment in which the aluminium
chloride is prepared is free from water. This is particularly important because aluminium
chloride reacts very readily with water.

Anhydrous calcium chloride is very hygroscopic (i.e. easily absorbs moisture from air), hence
very useful as a desiccant (i.e. a drying agent). Placing some in a guard tube allows for
absorption of any moisture from the air, particularly when the set-up cools (which causes
some air to enter the set up via contraction).

How are gases like chlorine ‘dried’?

It is possible to dry chlorine gas by bubbling the supply of chlorine through concentrated
sulfuric acid, which readily absorbs any moisture in the gas supply.

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5.3 Reactions of the chlorides with water

On the whole, all chlorides of Period 3 elements appear to dissolve in water.
 In the case of the ionic chlorides, their ions get solvated, and form favourable ion-dipole
interactions with the polar water molecules. We refer to the solvated ions as hydrated ions.
 Recall that the chloride ion, being the conjugate base of the strong acid HCl, is a very poor base
which does not react with water. Hence, it will not be responsible for any deviations from neutral
pH.
 Depending on their charge density, the hydrated metal cations formed may undergo partial
hydrolysis in water.

Chloride Reaction with water

NaCl Observation with equation
 dissolves in water to form a colourless solution of neutral pH
NaCl(s) + aq  Na+(aq) + Cl−(aq)

Explanation
 Na+ has low charge density, and hence does not react with water molecules (no
hydrolysis). The solution thus remains neutral at pH 7.

water
Na+ Cl−(s)

MgCl2 Observation with equation

 dissolves in water to form a colourless solution of slightly acidic pH
MgCl2(s) + 6 H2O(l)  [Mg(H2O)6]2+(aq) + 2 Cl−(aq)
[Mg(H2O)6]2+(aq) + H2O(l) ⇌ [Mg(H2O)5OH]+(aq)` + H3O+(aq)

Explanation
 Due to the higher charge density of Mg2+ compared to Na+, the hydrated magnesium
ion undergoes slight hydrolysis to form a very weakly acidic solution of around pH
6.5.
 The above equilibrium lies very much to the left. Nonetheless, enough H3O+ is
produced to lower the pH away from neutral.

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Chloride Reaction with water

AlCl3 Observation with equations

1. Reaction in a limited amount of water

When a few drops of water are added to solid AlCl3, steamy white fumes of HCl are
evolved and a white solid remains, which is insoluble in water.
AlCl3 (s) + 3 H2O(l)  Al(OH)3(s) + 3 HCl(g)
white solid steamy white fumes

2. Reaction in a large amount of water

In an excess of water, AlCl3 dissolves to form a colourless solution of acidic pH.
Al3+ forms a complex ion with 6 water molecules, as shown below.
AlCl3(s) + 6 H2O(l)  [Al(H2O)6]3+(aq) + 3 Cl−(aq)

[Al(H2O)6]3+(aq) + H2O(l) ⇌ [Al(H2O)5OH]2+(aq) + H3O+(aq)

Due to the very high charge density of Al3+, the O−H bonds in the H2O ligands are
sufficiently polarised, weakened and break readily to donate a proton.
The hydrated aluminium complex can undergo hydrolysis to a further extent than for
Mg2+(aq), resulting in a distinctly acidic solution around pH 3.

3. Acidic behaviour of Al3+(aq)

 Adding a controlled amount of OH− ions to an aqueous solution of Al3+ can further
deprotonate the water ligands, until a white ppt of aluminium hydroxide is formed:

[Al(H2O)5OH]2+(aq) + OH−(aq) ⇌ [Al(H2O)4(OH)2]+(aq) + H2O(l)

[Al(H2O)4(OH)2]+(aq) + OH−(aq) ⇌ [Al(H2O)3(OH)3](s) + H2O(l)

white ppt

 If an excess of OH− ions is added, the white ppt dissolves to form a colourless
solution with the formation of the aluminate ion:

[Al(H2O)3(OH)3](s) + OH−(aq) ⇌ [Al(OH)4]−(aq) + 3 H2O(l)

aluminate

N.B. The aluminate complex is sometimes written as [Al(H2O)2(OH)4]−, the octahedral complex. However,
this is rather unstable, quickly forcing out the 2 water molecules and converting to the tetrahedral
[Al(OH)4]−.

 A solution of Al3+ is usually acidic enough to react with sodium carbonate and
produce effervescence of CO2 gas and the white ppt of aluminium hydroxide.
2 [Al(H2O)6]3+(aq) + 3 CO32−(aq)  2 [Al(H2O)3(OH)3](s) + 3 H2O(l) + 3 CO2(g)
white ppt effervescence

Refer to Section 3.5 in Topic 14 Acid-Base Equilibria for more details on hydrolysis caused by metal ions
with high charge density.

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 The remainder of the chlorides undergo complete hydrolysis in water to form strongly acidic
solutions due to the HCl formed.

Chloride Reaction with water

SiCl4 / Observation
PCl5  violent reaction with water producing fumes of HCl gas
Note that even if left exposed to moist air, fumes of HCl will be observed.
∴ these chlorides must be kept in air-tight containers
 If water is added in large excess, the HCl fumes may not be observed as they mostly
dissolve in the water, forming a strongly acidic solution (pH 1) containing hydrochloric
acid.

Equations
Complete hydrolysis occurs in each case, i.e. these chlorides react with water
irreversibly.
SiCl4(l) + 4 H2O(l)  SiO2.2H2O(s) + 4 HCl (aq)
hydrated silicon dioxide*

PCl5(s) + 4 H2O(l)  H3PO4(aq) + 5 HCl (aq)

phosphoric(V) acid

 Upon dropwise addition of water (or when exposed to moist air), phosphorus(V)
chloride tends to produce phosphorus oxychloride, POCl3, instead:

PCl5(s) + H2O(l)  POCl3(l) + 2 HCl (g)

Recall: This is similar to the reaction when PCl5 is used as a test for the −OH group in
organic chemistry!
PCl5(s) + ROH(l)  POCl3(l) + HCl (g) + RCl (l)

*Note: Hydrated silicon dioxide is sometimes written as Si(OH)4, a misleading notation that leads some to believe it is basic (it’s not!),
or as H4SiO4, in which it looks more like the molecular formula of an acid, which is more accurate here (orthosilicic acid, H4SiO4, has
pKa1=9.84, pKa2=13.2 at 25 °C from Wikipedia). However, silicic acids such as H4SiO4 readily lose water to form randomly polymeric silica
gel, a form of silicon dioxide, hence the use of the formula SiO2.2H2O.

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5.4 Summary of the properties of chlorides across Period 3

The following table summarises the trends in the Period 3 chlorides (in their highest oxidation states):

Formula of
NaCl MgCl2 AlCl3 SiCl4 PCl5
chloride
Oxidation
+1 +2 +3 +4 +5
number
Physical
appearance at solid solid solid liquid solid
25 °C
sublimes at sublimes at
Melting point (°C) 801 714 –70
~180 ~160

Boiling point (°C) 1413 1412 - 58 -

giant ionic lattice structure

with relatively strong simple discrete covalent molecules with
Bonding &
electrostatic forces of relatively weak dispersion forces between
structure
attraction between molecules
oppositely-charged ions
soluble soluble soluble
Effect of adding
chloride to water does not hydrolyses hydrolyses in water to form acidic solutions;
hydrolyse slightly HCl fumes may be observed
Approx. pH of
7 6.5 3 1 1
resulting solution

Exercise 5.1 (Worked Example)

1 Describe how the bonding in the chlorides of the elements changes across Period 3. Explain the
change in terms of the electronegativities of the element.

The bonding in the chlorides changes from ionic to covalent across period 3. Across period 3, the
electronegativity of the element increases. A large difference in electronegativity between the
element and chlorine results in an ionic chloride while a small difference in electronegativity
results in a covalent chloride.

2 Describe briefly how the reaction of the chlorides with water changes across period 3. Explain the
trend in terms of structure and bonding.

In general, the chlorides with giant ionic structure dissolve in water to give ions while the chlorides
with simple covalent structure hydrolyse to give acidic solutions.
As the bonding changes from ionic to covalent, the tendency to hydrolyse increases.

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Exercise 5.2

For the following questions, you may select more than one correct option.

1 Which of the following pairs of compounds contains one that is giant ionic and one that is
simple molecular?
1 Al2O3 and Al2Cl6
2 SiO2 and SiCl4
3 P4O10 and PCl5

2 Why is a solution of aluminium chloride acidic?

1 Chloride ions react with water to form hydrochloric acid.
2 Aluminium ions have a large charge to surface area ratio.
3 The H−O bonds are weaker in [Al(H2O)6]3+ than in H2O.

3 Which of the following are correct descriptions of the properties of anhydrous aluminium
chloride?
1 It dissolves in benzene to give a solution which conducts electricity.
2 It fumes in moist air due to the formation of hydrogen chloride.
3 In the vapour phase, it has a covalent molecular structure.

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6 SUMMARY OF PERIOD 3 TRENDS

 Variations in physical properties of the Period 3 elements

melting point (in C) electrical conductivity

Refer to Topic 2 Chemical Bonding for the explanations of melting point and electrical conductivity
variation using concepts of structure and bonding.

 Variations in properties of the Period 3 oxides

m.p/ K pH
Reaction of the oxides with water

Na2O MgO Al2O3 SiO2 P4O10 SO3 Na2O MgO Al2O3 SiO2 P4O10 SO3

 Variations in properties of the Period 3 chlorides

Reaction of the chlorides with water

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7 GROUP 2
LO 5(f)(i): describe and deduce from Eo values the relative reactivity of elements of Group 2 as reducing agents
LO 5(g)(i): describe and explain the trend in thermal stability of Group 2 carbonates in terms of the charge density of the
cation and the polarisability of the large anion

7.1 Relative strength of Group 2 metals as reducing agents

Reactivity of the Group 2 metals increases down the group. As atomic radii increase, the metal atoms
lose their electrons more readily (1st and 2nd ionisation energies decrease) going down the group. So,
they form M2+ cations more easily.

Therefore, reducing power of the group 2 metals increases (tendency to be oxidised increases) down
the group.

This is illustrated in the increasingly negative Eo values down the group.

Table 3. Standard electrode potential values of Group 2 metals

Element Standard electrode potential, Eo / V

Mg2+(aq) + 2e− ⇌ Mg(s) −2.38

Ca2+(aq) + 2e− ⇌ Ca(s) −2.87
Sr (aq) + 2e ⇌ Sr(s)
2+ − −2.89
Ba2+(aq) + 2e− ⇌ Ba(s) −2.90

7.2 Thermal stability of Group 2 carbonates

Group 2 carbonates are unstable towards heat. Thermal decomposition gives stable oxides.

MCO3(s)  MO(s) + CO2(g)

Table 4. Decomposition temperatures of Group 2 carbonates

Decomposition Temperature
Element
of carbonate / oC

Mg 400
Ca 900
Sr 1280
Ba 1360

Group 2 carbonates become more thermally stable down the group. The ones lower in the group need
to be heated more strongly before they will decompose, i.e. the ease of decomposition decreases
down the group, hence they will have a higher decomposition temperature.

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7.2.1 Factors affecting thermal stability of Group 2 carbonates

The thermal stability of the Group 2 carbonates is affected by the polarising power of the cation and
the polarisability of the large anion.

 Polarising power of the cation

Polarising power refers to the ability of a cation to distort the electron cloud of another ion, atom
or molecule. In general, the higher the charge density of the cation, the greater the polarising
power of the cation and the lower the thermal stability of the compound.

The small and highly charged M2+ cation in these Group 2 compounds polarises the anion’s larger
electron cloud, weakening the covalent bonds within the anion. Hence these compounds
decompose on heating as the weakened covalent bonds within the anion are easily broken.

The delocalised
electrons are pulled
towards the positive O
ion.
2− HEAT

M2+
M2+ O2
−
+ C

metal carbonate metal oxide carbon

dioxide
This oxygen atom is
well on the way to This end of the ion is
becoming an oxide on its way to breaking
ion. away and becoming
carbon dioxide.

For Group 2 carbonates,

 Cationic radius increases down the group while charge remains the same
 Therefore charge density of cation decreases down the group
 Polarising power of the cation decreases down the group and is less able to distort the
electron cloud of the carbonate, weakening the C–O bonds within the carbonate anion to a
smaller extent
 Covalent bonds within the carbonate anion are less likely to be broken down the group
 The ease of decomposition decreases (or thermal stability increases) down the group so
higher temperature is required to decompose the compound

 Polarisability of large anion

Polarisability refers to the ease with which an anion, atom or molecule’s electron cloud can be
distorted by another. The greater the polarisability of the anion, the lower the thermal stability of
the compound.

 Larger anions are more susceptible to polarisation of their electron cloud.

 Only polyatomic anions are susceptible to decomposition as monoatomic anions (e.g. O2,
Cl ) cannot be broken down further.

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Decomposition of other Group 2 Compounds (Application Example)

Other group 2 compounds that are susceptible to decomposition include nitrates and hydroxides, as
these also have polarisable polyatomic anions and are thus also unstable towards heat.

Nitrates : M(NO3)2(s)  MO(s) + 2NO2(g) + ½O2(g)

Hydroxides : M(OH)2(s)  MO(s) + H2O(g)

O O

C N 
O H
- -
O O O O-

carbonates nitrates hydroxides

The following table shows the products of decomposition of other polyatomic anions.

There are also other factors that may contribute to ease of decomposition of these compounds. One
factor is the way the ions are packed in the lattice structure, as well as the ratio of cations to anions in
the solid structure.

Comparison with thermal stability of Group 1 carbonates (Application Example)

The Group 1 carbonates are resistant to decomposition except for Li2CO3. The charge density of Li+ is
high enough to distort the carbonate’s electron cloud so that the compound decomposes on heating.

Li2CO3(s)  Li2O(s) + CO2(g)

The other Group 1 metal cations have low charge density due to their larger radii and so are unable to
sufficiently distort the carbonate’s electron cloud. Therefore the carbonates after lithium do not
decompose on heating.

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8 GROUP 17
8.1 Trend in volatility of Group 17 elements
LO 5(d): describe and explain the trend in volatility of the group 17 elements in terms of instantaneous dipole-induced dipole
attraction

Table 5. Physical states, melting and boiling points of halogens

Element No. of electrons Melting point/ C Boiling point/ C Physical state at 20 C
F2 18 −220 −188 Gas
Cl2 34 −101 −35 Gas
Br2 70 −7 59 Liquid
I2 106 114 184 Solid

The following table on the colour of halogens can be found in the Data Booklet:
Halogen Colour of element Colour in aqueous solution Colour in hexane
Chlorine, Cl2 Greenish yellow gas Pale yellow Pale yellow
Bromine, Br2 Reddish brown gas/liquid Orange Orange-red
Iodine, I2 Black solid/purple gas Brown Purple

The Group 17 elements, also known as the halogens, exist as simple, non-polar diatomic molecules
with dispersion forces existing between molecules.

Down the group, the size of the electron cloud and hence, the polarisability of the halogen molecule
increases. More energy is needed to overcome the stronger dispersion forces between the molecules.
Hence, the volatility of the halogens decreases down Group 17, and the melting and boiling points
increase down the group.
*The volatility of a substance refers to how easily the substance in the liquid phase may be converted to the gas phase.

The increase in strength of dispersion forces down the group explains the change in physical state of
the elements down Group 17.

8.2 Relative strength of Group 17 elements as oxidising agents

LO 5(f)(ii): describe and deduce from Eo values the relative reactivity of elements of Group 17 as oxidising agents

The outermost electron shell of halogens contains 7 electrons, i.e. ns2 np5. As such, their chemistry is
dominated by a tendency to gain a completely filled outermost electron shell. Hence, halogens tend
to be reduced in a redox reaction, and their oxidising power can be measured by the value of the
standard reduction potential Eo for the process:

X2(std) + 2e− ⇌ 2X−(aq)

The Eo values become less positive down the group, as shown in Table 6. Hence, the oxidising power
of the halogens decreases down the group and they become less likely to be reduced in a redox
reaction.

Table 6. Standard reduction potentials of the halogens

Element F2 Cl2 Br2 I2
Eo/ V +2.87 +1.36 +1.07 +0.54

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8.3 Redox reactions of Group 17 elements

LO 5(f)(ii): describe and deduce from Eo values the relative reactivity of elements of Group 17 as oxidising agents

This section describes some of the redox reactions that Group 17 elements undergo. In each of these
reactions, the relative oxidising abilities of the halogens are further emphasised.

8.3.1 Displacement reactions

In general, a halogen higher in the group can oxidise a halide below it. A more reactive halogen will
hence displace a less reactive one from its compounds.

Exercise 8.1 (Worked Example)

Describe the observations in each of the following. Explain your answer with the aid of chemical
equations, where appropriate.

(a) Aqueous chlorine is added to a solution of KI.

Pale yellow Cl2(aq) solution turns brown.

Chlorine is a stronger oxidising agent than iodine. Hence, it displaces I– to form Cl– and I2.
Cl2(aq) + 2I–(aq)  2Cl–(aq) + I2(aq)

The brown solution is due to a reaction between I2 and the excess I– to form I3–.
I2 + I–(aq) I3– (aq)

(b) Potassium bromide solution is added to hexane (colourless liquid with a density of 0.659 g/cm3 at
25 °C) in a test tube. Chlorine is bubbled through the potassium bromide layer.
Chlorine is a stronger oxidising agent than bromine, and hence it displaces Br– to form Cl– and Br2.
Cl2 + 2Br–  2Cl– + Br2
The Br2 formed may dissolve in the top organic layer to form an orange-red liquid, or in the bottom
aqueous layer to form an orange solution.

8.3.2 Reactions with aqueous solutions containing iron(II) ions

In the presence of a halogen oxidising agent, an aqueous solution of Fe2+ ions can be oxidised to Fe3+.

Exercise 8.2
By calculating the Eocell for the reaction between Fe2+ and the halogen, show that only chlorine and
bromine are able to oxidise Fe2+ while iodine will not oxidise Fe2+. (Given Eo(Fe3+/Fe2+) = +0.77V)

Equation Eocell
Cl2(aq) + Fe2+(aq)  2Cl−(aq) + 2Fe3+(aq) +1.36 – 0.77 = +0.59 V (spontaneous)

Br2(aq) + Fe2+(aq)  2Br−(aq) + 2Fe3+(aq) +1.07 – 0.77 = +0.30 V (spontaneous)

I2(aq) + 2Fe2+(aq)  2I−(aq) + 2Fe3+(aq) +0.54 – 0.77 = –0.23V (not spontaneous)

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8.3.3 Reactions with thiosulfate, S2O32−

The decrease in oxidising power of the halogens can also be illustrated by their reaction with an
aqueous solution of thiosulfate.

Chlorine and bromine would oxidise thiosulfate to sulfate, SO42− while iodine oxidises thiosulfate to
tetrathionate, S4O62−.

4Cl2(aq) + S2O32–(aq) + 5H2O(l)  8Cl(aq) + 2SO42(aq) + 10H+(aq)

+2 +6

4Br2(aq) + S2O32–(aq) + 5H2O(l)  8Br(aq) + 2SO42(aq) + 10H+(aq)

+2 +6

I2(aq) + 2S2O32–(aq)  2I(aq) + S4O62–(aq)

+2 +2.5

Iodine is a weaker oxidising agent than chlorine and bromine, and hence the oxidation number of sulfur
only increases from +2 to +2.5, as compared to from +2 to +6 in the reactions with chlorine or bromine.

8.4 Thermal stability of Group 17 hydrides

LO 5(g)(ii): describe and explain the trend in thermal stability of Group 17 hydrides in terms of bond energies

Upon heating, the Group 17 hydrides (also called “hydrogen halides”), HX, can decompose to give
hydrogen and the corresponding halogen.

2HX(g)  H2(g) + X2(g)

The thermal stability of the hydrogen halide depends on the strength of the H–X bond.
Table 7. Relationship between decomposition behaviour and H–X bond energy
Compound HF HCl HBr HI
Violet fumes of I2
Does not Does not Strong heating obtained when
Decomposition
decompose even decompose even yields brown red-hot rod is
behaviour
on strong heating on strong heating fumes of Br2 plunged into jar
of HI
H–X bond
562 431 366 299
energy/ kJ mol1

 Down the group, as atomic radius increases from F to I, the bond length of the H–X bond
increases and thus bond strength decreases.
 Hence, less energy is needed to break the H–X bond. Thus, the thermal stability of the
hydrogen halides decreases down the group.

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9 APPLYING THE PRINCIPLES OF CHEMICAL PERIODICITY

LO 5(h) predict the characteristic properties of an element in a given Group by using knowledge of chemical periodicity
LO 5(i) deduce the nature, possible position in the Periodic Table, and identity of unknown elements from given information
of physical and chemical properties

The principles of chemical periodicity discussed in this topic can be used to predict characteristic
properties of an element in a given Group. Given the physical and chemical properties, we can also
deduce the nature and position of unknown elements in the Periodic Table.

Exercise 9.1
Use of Data Booklet is relevant to this question

Indium, 49In, is used in solar cells and transistors, and to coat high-speed bearings.

From its position in the Periodic Table, which properties will it be expected to possess?

1 In the vapour phase, the chloride has the formula In2Cl6.

2 Its oxide dissolves in aqueous acid.
3 Its ionic salts are highly coloured.
N13/P1/36

Diagonal Relationships in the Periodic Table (Useful Tool)

In the periodic table, certain pairs of diagonally adjacent elements in Period 2 and Period 3 (shown
below) show similarities in their properties. They are said to have a diagonal relationship. As a result,
the first element of some groups can be seen to have slightly different properties to the rest of the
group.
Group 1 2 13 14

Period 2 Li Be B C

Period 3 Na Mg Al Si

K Ca Ga Ge

Examples of diagonal relationships:

 Li is the only Group 1 element that can form a nitride salt; all Group 2 elements form nitrides; etc.
 BeO and Al2O3 are both amphoteric; aqueous solutions of Be2+ and Al3+ are both weakly acidic due
to hydrolysis; etc.
 B and Si tend to form covalent compounds rather than forming cations; both B and Si are
semiconductors; etc.

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Hwa Chong Institution 2024 21 – Periodicity

Explanation
As we move across the period and down the group, the properties tend to have opposite trends:
For example, moving across the period, atomic radius decreases, but down the group, atomic radius
increases. Similarly, moving across the period, electronegativity increases, while down the group, it
decreases.
 Thus, moving simultaneously across the period and down the group by one element results in
the combined effects of the opposing trends "cancelling out".

Note that diagonal relationships become less noticeable as we move beyond the B/Si pair, or below
Period 3.

Exercise 9.2 (Worked Example)

Which element is likely to have an electronegativity similar to that of aluminium?
A barium B beryllium C carbon D chlorine

Answer: B
In general, electronegativity increases across the period and decreases down the group. Recall
diagonal relationship. Electronegativity: Cl(3.0) > C(2.5) > Be=Al(1.5) > Ba(0.9)

LOOKING AHEAD
You have seen both physical and chemical trends of the elements and their compounds across Period 3.
Moving on to the next topic on Transition Elements, it is helpful to bear in mind the properties of the metals
in Group 1, 2 and 13 (e.g. Na, K, Mg, Ca, Al etc.) and to compare them to the properties of transition metals.

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Hwa Chong Institution 2024 22 – An Introduction to the Chemistry of Transition Elements

An Introduction to the
22 Chemistry of Transition Elements
GUIDING QUESTIONS
• What are transition elements?
• What are the characteristic properties of transition elements? How are these properties similar or
different from a typical s-block element?
• Are there any trends/patterns in the properties of transition elements?
• What are some examples/applications of transition elements/their compounds?

LEARNING OUTCOMES
Students should be able to:
For the first set of transition elements, titanium to copper
13 (a) explain what is meant by a transition element, in terms of d-block elements forming one or
more stable ions with partially filled d subshells
13 (b) state the electronic configuration of a first row transition element and its ion (Refer to Topic 1
Atomic Structure and Physical Periodicity)
13 (c) explain why atomic radii and first ionisation energies of the transition elements are relatively
invariant (Refer to Topic 1 Atomic Structure and Physical Periodicity)
13 (d) contrast, qualitatively, the melting point and density of the transition elements with those of
calcium as a typical s-block element
13 (e) describe the tendency of transition elements to have variable oxidation states
13 (f) predict from a given electronic configuration, the likely oxidation states of a transition element
13 (g) describe and explain the use of Fe3+/Fe2+, MnO4−/Mn2+ and Cr2O72−/Cr3+ as examples of redox
systems (Refer to Topic 20 Electrochemistry)
13 (h) predict, using E values, the likelihood of redox reactions (Refer to Topic 20 Electrochemistry)
13 (i) define the terms ligand and complex as exemplified by the complexes of copper(II) ions with
water, ammonia and chloride ions as ligands (including the transition metal complexes found
in the Qualitative Analysis Notes)
13 (j) explain qualitatively that ligand exchange may occur, as exemplified by the formation of the
complexes in (i), including the colour changes involved, and CO/O2 exchange in haemoglobin
13 (k) describe, using the shape and orientation of the d orbitals, the splitting of degenerate d orbitals
into two energy levels in octahedral complexes
13 (l) explain, in terms of d orbital splitting and d-d transition, why transition element complexes are
usually coloured [knowledge of the relative order of ligand field strength is not required]
13 (m) explain how some transition elements and/or their compounds can act as catalysts (Refer to
Topic 6 Reaction Kinetics)
REFERENCES
1. P. Cann & P. Hughes, Chemistry, 2nd Edition, Hodder Education, Chapter 24.
2. P. W. Atkins, M. T. Weller, T. L. Overton, J. P. Rourke & F. A. Armstrong, Inorganic Chemistry,
6th Edition, Oxford University Press, Chapter 7, 20 and 21.
3. P. Amateis & M. Silberberg, Chemistry: the molecular nature of matter and change, 7th Edition,
McGraw-Hill Education, Chapter 23.

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Hwa Chong Institution 2024 22 – An Introduction to the Chemistry of Transition Elements

LOOKING BACK
In this topic, you will learn about the chemical and physical properties of the first row transition elements and
compare them with the main group metals, applying knowledge from earlier topics such as Atomic Structure,
Chemical Bonding, Physical Periodicity, Equilibria and Electrochemistry.

1 INTRODUCTION

1.1 Definition of Transition Elements

LO 13(a): explain what is meant by a transition element, in terms of d-block elements forming one or more stable ions with
partially filled d subshells

Transition elements are d-block elements that form one or more stable ions with
partially filled d subshell.

By this definition, both scandium and zinc are excluded from the class of transition elements, even
though they are part of d-block elements. This is because:
• Scandium forms only Sc3+ ion, which has no electron in the 3d subshell (3d0).
• Zinc forms only Zn2+ ion which has 10 electrons in the 3d subshell (3d10).

1.2 Electronic Configurations of First Row Transition Elements and its ions (covered in Topic 1
Atomic Structure and Physical Periodicity)
LO 13(b): state the electronic configuration of a first row transition element and its ion

No. of Full electronic Electron-in-box representation

Atom
electrons configuration 3d 4s
Sc
21 1s2 2s2 2p6 3s2 3p6 3d1 4s2 [Ar]
Scandium ^
Ti
22 1s2 2s2 2p6 3s2 3p6 3d2 4s2 [Ar]
Titanium
V
23 1s2 2s2 2p6 3s2 3p6 3d3 4s2 [Ar]
Vanadium
Cr
24 1s2 2s2 2p6 3s2 3p6 3d5 4s1 [Ar]
Chromium*
Mn
25 1s2 2s2 2p6 3s2 3p6 3d5 4s2 [Ar]
Manganese
Fe
26 1s2 2s2 2p6 3s2 3p6 3d6 4s2 [Ar]
Iron
Co
27 1s2 2s2 2p6 3s2 3p6 3d7 4s2 [Ar]
Cobalt
Ni
28 1s2 2s2 2p6 3s2 3p6 3d8 4s2 [Ar]
Nickel
Cu
29 1s2 2s2 2p6 3s2 3p6 3d10 4s1 [Ar]
Copper*
Zn
30 1s2 2s2 2p6 3s2 3p6 3d10 4s2 [Ar]
Zinc ^
Table 1. Electronic configuration of first row elements from d-block.

^ Sc and Zn are not transition elements.

* Cr and Cu atoms are two exceptions to the general pattern of electronic configurations.

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Hwa Chong Institution 2024 22 – An Introduction to the Chemistry of Transition Elements

No. of Full electronic Electron-in-box representation

Ion
electrons configuration 3d 4s
Sc3+ 18 1s2 2s2 2p6 3s2 3p6 3d0 [Ar]

Ti2+ 20 1s2 2s2 2p6 3s2 3p6 3d2 [Ar]

V3+ 20 1s2 2s2 2p6 3s2 3p6 3d2 [Ar]

Cr3+ 21 1s2 2s2 2p6 3s2 3p6 3d3 [Ar]

Mn2+ 23 1s2 2s2 2p6 3s2 3p6 3d5 [Ar]

Fe2+ 24 1s2 2s2 2p6 3s2 3p6 3d6 [Ar]

Co2+ 25 1s2 2s2 2p6 3s2 3p6 3d7 [Ar]

Ni2+ 26 1s2 2s2 2p6 3s2 3p6 3d8 [Ar]

Cu2+ 27 1s2 2s2 2p6 3s2 3p6 3d9 [Ar]

Zn2+ 28 1s2 2s2 2p6 3s2 3p6 3d10 [Ar]

Table 2. Electronic configuration of selected ions of first row d-block elements.

1.3 Physical Properties of Transition Elements

LO 13(c): explain why atomic radii and first ionisation energies of the transition elements are relatively invariant (Refer to
Topic 1 Atomic Structure and Physical Periodicity)
LO 13(d): contrast, qualitatively, the melting point and density of the transition elements with those of calcium as a typical
s-block element

The atomic radii and first ionisation energies of the transition elements are relatively invariant. These
concepts have been covered in Topic 1 Atomic Structure and Physical Periodicity.

The melting points of transition elements are higher than s-block elements, as both 3d and 4s
electrons are involved in the metallic bonding in transition element.

The densities of transition elements are higher than s-block elements because the atomic radii of
transition elements are smaller than s-block elements.

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Hwa Chong Institution 2024 22 – An Introduction to the Chemistry of Transition Elements

Exercise 1.1
Calcium is a fairly soft, silvery-grey metal which quickly tarnishes in air. Vanadium is a hard grey
metal which is resistant to corrosion at ordinary temperatures. Metallic calcium has no commercial
uses; vanadium is widely used as an alloying element in steels. Data about calcium and vanadium
are given below.
calcium vanadium
2
electronic configuration [Ar] 4s [Ar] 3d3 4s2
atomic radius/nm 0.197 0.135
melting point/C 843 1710
−3
density/g cm 1.54 6.07

(Worked Example)
a) The melting point of vanadium is significantly higher than that of calcium. Explain this in terms
of the type and strength of bonding in each metal. (Worked Example)

Answer:
Both metals contain metallic bonding.
In Ca, only the 2 valence electrons (from 4s subshell) are contributed to the ‘sea’ of delocalised
electrons.
For V, the 4s and 3d electrons are close in energy, therefore all these electrons could be
involved in metallic bonding. In addition, vanadium cation has higher charge and smaller radius
than Ca2+. Hence, metallic bonding in V is significantly stronger than that in Ca.
More energy is needed to overcome the metallic bonding in V during melting and thus it has
higher melting point.

Comments:
This question is asking about the physical properties of metals. You should now recall relevant
knowledge of metallic bonding from the Chemical Bonding chapter and the structure and
bonding affects specifically melting point of the metal. The relevant properties are the charge
density of the cations and the number of delocalised electrons.

The firs part of your answer should be to describe the metal structure and bonding within
vanadium and calcium, followed by linking the relevant properties to the melting point.

b) Explain why the density of vanadium is significantly higher than that of calcium.

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Hwa Chong Institution 2024 22 – An Introduction to the Chemistry of Transition Elements

1.4 Chemical Properties of Transition Elements

The transition elements and their compounds display the following chemical properties that are
different from s-block elements and their compounds.

Properties Examples
Tendency to have • Manganese: +2 in Mn , +4 in MnO2, +7 in MnO4–
2+

variable oxidation • Iron: +2 in Fe2+; +3 in Fe3+

states
• Iron, Fe, in the Haber process (manufacturing of ammonia)
Catalytic properties • Nickel, Ni, in hydrogenation of alkene
(Heterogeneous and • Vanadium(V) oxide, V2O5, in the Contact process
homogeneous) (manufacturing of sulfuric acid)
• Fe2+ ion in I–/S2O82– reaction

Formation of complex • [Cu(NH3)4(H2O)2]2+, [Fe(CN)6]3–, [Ag(NH3)2]+

ions

Formation of • Cu2+(aq): pale blue, Cr2O72–(aq): orange

coloured ions • Fe3+(aq): yellow

Table 3. Chemical properties of transition elements.

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Hwa Chong Institution 2024 22 – An Introduction to the Chemistry of Transition Elements

2 VARIABLE OXIDATION STATES

LO 13(e): describe the tendency of transition elements to have variable oxidation states

The transition elements show variable oxidation states due to the close similarity in energy of the 4s
and 3d electrons. Hence, once the 4s electrons are removed, some or all the 3d electrons may also be
removed without requiring much more energy.

In contrast, the s-block elements are limited to form compounds with oxidation states of +1 (Group 1)
or +2 (Group 2). This is because once the outermost electrons in the s orbital are removed, subsequent
removal of electrons would be from the inner quantum shell which requires too much energy.

+7
+6 +6 +6
+5 +5 +5 +5 +5
+4 +4 +4 +4 +4 +4 +4
+3 +3 +3 +3 +3 +3 +3 +3 +3
+2 +2 +2 +2 +2 +2 +2 +2 +2
+1 +1 +1 +1 +1 +1 +1 +1
Sc Ti V Cr Mn Fe Co Ni Cu Zn
scandium titanium vanadium chromium manganese iron cobalt nickel copper zinc
Table 4. Known oxidation states of d-block metals. The more familiar oxidation states are shaded. Other oxidation states can
only be stabilised under special conditions.

Scandium and zinc, which are not part of transition elements, can only form one oxidation state, as
shown in Table 4 above.

2.1 General trends in oxidation states of transition elements

LO 13(f): predict from a given electronic configuration, the likely oxidation states of a transition element

• In their elemental states, the elements are assigned an oxidation number of zero.
• The value of the maximum oxidation number for the elements suggests that in each element, all
the available 3d and 4s electrons may be used for bonding to form various compounds (either
ionic bond by losing electrons or covalent bond by sharing electrons).
• The lower oxidation state metals are usually found in ionic compounds, e.g. FeSO4 and MnCl2.
• The higher oxidation state metals tend not to exist as free ions, e.g. Mn7+ or Cr6+ do not exist.
However, they are involved in covalent bonds, such as TiO2, V2O5, Mn2O7 and oxo-anions
(e.g. VO3–, CrO42–, Cr2O72–, MnO4–).
• The number of available oxidation states of the elements increases from Ti to Mn and decreases
from Mn to Cu. After Mn (3d5), pairing of d-electrons occurs such that there is a decrease in the
number of electrons available for bond formation. This results in the decrease in the number of
oxidation states exhibited by the elements with more than five d-electrons (from Fe to Cu).

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Hwa Chong Institution 2024 22 – An Introduction to the Chemistry of Transition Elements

Exercise 2.1

(Worked Example)
1. The table shows the possible oxidation states of five d-block elements in the Periodic Table.
(The elements are represented by letters which are not their symbols.)

element possible oxidation numbers

P – – 3 – – – –
Q – 2 3 4 – – –
R 1 2 3 4 5 – –
S – – 3 4 5 6 –
T – 2 – 4 5 6 7

Which of the following ions is likely to exist?

A PO2+ B QO3– C RO42– D TO22+

Students should work out the oxidation states of P, Q, R, T in the options given and compare
them to the possible oxidation numbers given in the table.
This can be done by using the overall charge of the ion and assuming the oxidation state of
Oxygen is –2.
Option A: For the anion to have an overall charge of +2, with 1 oxygen atom, P needs to have
an oxidation state of +4.
Using this same logic, we can work out that Q has a +5 oxidation state, R and T has +6 oxidation
state. Hence only Option D is correct, where T has a possible oxidation state of +6 in the table
given.

2. Titanium has the electronic structure 1s2 2s2 2p6 3s2 3p6 3d2 4s2. Which of the following
compounds does not exist?
A K2TiO4 B K3TiF6 C TiCl3 D TiO

3. The electronic configuration of vanadium is [Ar] 3d3 4s2. Which of the following ions does not
exist?
A VO2+ B VO2+ C VO32– D VO42–

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Hwa Chong Institution 2024 22 – An Introduction to the Chemistry of Transition Elements

2.2 Redox reactions involving transition elements

LO 13(g): describe and explain the use of Fe3+/Fe2+, MnO4−/Mn2+ and Cr2O72−/Cr3+ as examples of redox systems
LO 13(h): predict, using Eo values, the likelihood of redox reactions

One of the applications of transition metal compounds is in the field of redox chemistry. In general,
ions that have the transition metal in a high oxidation state tend to be oxidising agents (e.g. Cr2O72–,
MnO4–) while transition metal in low oxidation state tends to be reducing agents (e.g. Cr2+, V2+). When
transition metal ions undergo redox reactions, a colour change is usually observed.

Common redox systems involving transition elements include:

Fe3+(aq) + e– ⇌ Fe2+(aq) As a homogeneous catalyst in the redox reaction between
yellow pale green iodide ions and peroxodisulfate ions.

MnO4− + 8H+ + 5e– ⇌ Mn2+ + 4H2O As an oxidising agent for organic compounds such as
purple colourless oxidation of primary alcohols to carboxylic acids.

Cr2O72− + 14H+ + 6e– ⇌ 2Cr3+ + 7H2O

orange green

To predict whether a redox reaction is feasible, or to explain colour changes due to redox reactions,
we can make use of Eo values of the relevant species to find overall Ecell, as learnt in Topic 20
Electrochemistry.
If Ecell > 0, redox reaction is feasible.

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Hwa Chong Institution 2024 22 – An Introduction to the Chemistry of Transition Elements

Exercise 2.2
By quoting and using relevant Eo values from the Data Booklet, explain each of the following
observations. Write balanced equations for the reactions.

(Worked Example)
(i) The green precipitate obtained when aqueous sodium hydroxide is added to aqueous iron(II)
sulfate rapidly turns brown on exposure to air.

Answer:
The green precipitate is Fe(OH)2.
Fe2+ + 2OH– → Fe(OH)2

O2 + 2H2O + 4e– ⇌ 4OH– E = +0.40 V

Fe(OH)3 + e– ⇌ Fe(OH)2 + OH– E = –0.56 V

Fe(OH)2 is oxidised by O2 in the air to form brown Fe(OH)3

O2 + 2H2O + 4Fe(OH)2 → 4Fe(OH)3 Ecell = +0.40 – (–0.56) = +0.96 V > 0

Comments:
Students should first recall their QA knowledge and realise the green precipitate is iron(II) hydroxide
and give the relevant equation for precipitation.

Students should then consider what would cause the green ppt to turn brown on standing, in this case
it would be atmospheric oxidation. Hence to show this, students need to extract the relevant electrode
potentials from the Data Booklet to prove that this is the case. In this case, oxygen is the oxidising
agent.

Students should then use this information to formulate the overall balanced equation, AND calculate
the standard cell potential.

(ii) The blue solution, containing Cr2+(aq), obtained by dissolving chromium metal in dilute sulfuric
acid slowly turns green even in the absence of air.

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3 CATALYTIC PROPERTIES
LO 13(m): explain how some transition elements and/or their compounds can act as catalysts

Transition elements, both in the elemental form and in their compounds, are important catalysts. We
have learnt about catalysts and their mode of action in Topic 6 Reaction Kinetics. In this section, pay
attention to the part played by transition elements and why they are able to act as catalysts. Also learn
to apply your knowledge of E values to explain the mechanism of homogeneous catalysis.

A catalyst is a substance that increases the rate of a reaction by providing an alternative reaction
pathway that requires lower activation energy than the uncatalysed reaction. The catalyst does not
undergo any permanent chemical change during the process.

Transition elements and their compounds can act as heterogeneous catalysts as well as homogeneous
catalysts:

Type Homogeneous Catalyst Heterogeneous Catalyst

Catalyst operates in a different
phase of catalyst
Catalyst operates in the same phase phase as the reactants (most
vs. phase of
as the reactants commonly the catalysts are solids,
reactants
and the reactants are gases)

Availability of partially filled 3d

reason why the
orbitals to accept electron pairs
transition metal or
Variable oxidation states of the from, or donate electrons pairs to
its compound
transition metal in its ions reactant molecules, for adsorption
could act as this
of reactant molecules onto the
type of catalyst
surface of the catalyst.

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3.1 Heterogeneous Catalysis

In heterogeneous catalysis, the catalyst and the reactants are in different physical phases.
• The catalyst is usually in the solid phase and it provides active sites at which the reaction can take
place.
• The reactants are usually gases or liquids.

Example: Haber process (manufacturing of ammonia)

Reaction: N2(g) + 3H2(g) 2NH3(g)

Catalyst: finely divided Fe(s) or Fe2O3(s)

Figure 1. Heterogeneous catalysis in the Haber Process

Mode of action of the catalyst

• Adsorption: Gaseous reactant molecules, N2 and H2, diffuse towards surface of the Fe catalyst.
N2 and H2 adsorb onto the active sides of Fe catalyst by formation of weak attraction forces.
• The adsorption process brings reactant molecules closer together, thus increasing their
concentration on the catalyst surface, increasing frequency of collisions; the process also weakens
the NN and H–H covalent bonds within the molecules; and allows these molecules to be
orientated in the right positions for reaction to form new bonds between N and H. All these lower
the activation energy of the reaction.
• Desorption: Product molecule, NH3, desorbs and diffuses away from catalyst surface so that active
sites are exposed for further reaction.
Energy / kJ mol–1

Figure 2. Energy profile diagrams for the catalysed and uncatalysed reactions.

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Figure 2 shows the energy profile diagram for the catalysed and uncatalysed reactions.
Important points to note:
• A catalyst speeds up the forward and the reverse reactions.
• A reaction with a catalyst does not yield more product than one without a catalyst, but it yields
the product more quickly.
• A catalyst provides a different mechanism for the reaction, with a new, lower activation energy
pathway.
• A catalyst does not alter the enthalpy change of reaction.

Other heterogeneous catalysts used in the chemical industry

Heterogeneous catalyst Reaction catalysed
Contact process
V2O5
2SO2(g) + O2(g) 2SO3(g)
Hydrogenation of vegetable oils to make margarine
Ni
RCH=CH2 + H2(g) → RCH2CH3
Polymerisation of ethene to poly(ethene)
TiCl3, Al2(C2H5)6
Ziegler-Natta catalyst

3.2 Homogeneous Catalysis

In homogeneous catalysis, the catalyst and the reactants are dispersed in the same phase (either liquid
or gaseous).

The relative ease of inter-conversion between the different oxidation states of transition metals
enables them to act as homogeneous catalysts, typically for redox reactions. Overall, the transition
metal ions act as intermediaries for the electron(s) transfer between the oxidising and reducing
agents.

We shall use the same example of homogeneous catalyst given in Topic 6 Reaction Kinetics: the
oxidation of iodide ion, I–, by peroxodisulfate ion, S2O82–.

Reaction: S2O82–(aq) + 2I–(aq) → 2SO42–(aq) + I2(aq)

Catalyst: aqueous iron(III) ions

I2 + 2e– ⇌ 2I – E = +0.54 V
S2O82– + 2e– ⇌ SO42– E = +2.01 V

Based on the data above, the reaction is found to have Ecell = +1.47 V, which is expected to occur
spontaneously. However, the electrostatic repulsion between the two negatively charged ions causes
the reaction to have a high activation energy and hence to proceed at a very slow rate.

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Aqueous iron(III) ions can catalyse this reaction via an alternative pathway involving 2 steps:

Step 1: Fe3+ oxidises iodide, itself reduced to Fe2+, taking electrons from the I –

2Fe3+ + 2I – → 2Fe2+ + I2 Ecell = Ered – Eox = +0.77 – (+0.54) = +0.23 V

Step 2: Fe2+ transfer electrons to, and reduces peroxodisulfate, itself oxidised to Fe3+, thus Fe3+ is
regenerated

2Fe2+ + S2O82– → 2Fe3+ + 2SO42– Ecell = Ered – Eox = +2.01 – (+0.77) = +1.24 V

This 2-step alternative pathway requires a lower activation energy because both steps involve collision
between two oppositely charged ions. Fe3+ is regenerated at the end of the reaction.

If Fe2+ were present at the start instead, the two steps above will take place in the reverse order and
the net effect will still be the same.

Note that the Ecell value for both steps must be positive, because:
Fe3+ + e– ⇌ Fe2+ E = +0.77 V

Other redox couples of transition metal cations could also be used as catalysts in this reaction as long
as their E values were between +0.54 V and +2.01 V, such that each of the two steps in the alternative
pathway are feasible.

Energy
/ kJ mol−1 uncatalysed reaction

Ea (uncatalysed)

catalysed
reaction

Ea(step 2)
Ea(step 1) intermediate (catalysed)
(catalysed)

reactants

H < 0
products

Progress of reaction
Figure 3. Energy profile diagrams for a catalysed and uncatalysed reaction

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Exercise 3.1

The rate of the reaction between iodide and peroxodisulfate(VI) ions

S2O82–(aq) + 2I–(aq) → 2SO42–(aq) + I2(aq)

is increased by the presence of small concentrations of Co2+(aq). Suggest how Co2+(aq) ions are able
to participate in this reaction.

Hint: In this question, students need to demonstrate that the Co 2+ is acting as a homogeneous
catalyst to aid the transfer of electrons from the I– ions to the S2O82– ions. Extract 3 relevant half
equations and their electrode potential from the Data Booklet and construct 2 balanced equations
for each step of the homogeneous catalyst mechanism. The standard cell potential for each step
should be positive.

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4 TRANSITION ELEMENT COMPLEXES

LO 13(i): define the terms ligand and complex as exemplified by the complexes of copper(II) ions with water, ammonia and
chloride ions as ligands (including the transition metal complexes found in the Qualitative Analysis Notes)

4.1 Introduction

Transition elements and their ions tend to form complexes.

A complex is a molecule or ion formed by a central metal atom or ion surrounded by one or more
*ligands.
*Refer to Section 4.2 for the meaning of ligands

When white anhydrous CuSO4 solid is dissolved in water, a pale blue solution is formed. In water,
Cu(II) exists as the aqua complex, with formula [Cu(H2O)6]2+. When we write “Cu2+(aq)”, it refers to
[Cu(H2O)6]2+(aq).
CuSO4(s) + 6H2O(l) → [Cu(H2O)6]2+(aq) + SO42–(aq)
pale blue solution

Figure 4. Copper(II) complex with water

• In this complex, the central metal ion is Cu2+, with six H2O molecules acting as ligands.
• Each H2O molecule bonds to the Cu2+ ion by forming a coordinate (dative) bond.
• Notice that the formula of a complex ion is usually written with a square bracket, the charge of
the complex is indicated outside the square bracket.
• This complex is called the ‘aqua complex’ since its ligands are water.

A complex can be neutral, cationic or anionic. The net charge on the complex is the sum of the
oxidation number of the central metal ion and the total charges of the ligands that surround it. The
charge on the central metal is the oxidation number of the metal in that complex ion.

Type of complex Central ion / atom Ligands Complex

Neutral Ni CO Ni(CO)4
Cationic Cu2+ H2O [Cu(H2O)6]2+
Anionic Fe2+ CN– [Fe(CN)6]4–

To maintain charge neutrality, complex ion is typically associated with counter ions, as in the case of
the compound [Co(NH3)6]Cl3, in which the complex ion is [Co(NH3)6]3+, the six NH3 molecules acting as
ligands, and the three Cl– ions are counter ions. So the whole compound is like a salt.

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When [Co(NH3)6]Cl3 dissolves in water, the complex ion and counter ions separate from each other.
The complex ion behaves like a polyatomic ion with the ligands remaining attached to the central
metal ion/atom.

The tendency of transition metal ions to form complex ions rather than simple ions is due to two main
factors:
• The “bare” cations of transition elements, with their incomplete 3d subshells are relatively small
and highly charged. The resulting high charge density and hence high polarising power of the
transition metal cations, produces a strong tendency towards covalent bond formation with
ligands.
• The transition metal cations have vacant 3d orbitals (as well as 4s and 4p orbitals) which can be
used to accommodate the lone pair of electrons from the ligands, resulting in dative bond
formation.

4.2 Ligands

A ligand is an ion or molecule with one or more lone pairs of electrons available to be donated into
the vacant orbitals of transition metal atom or ion.

Ligands can be classified according to the number of dative bonds that it forms with the central metal
atom or ion.
• Monodentate ligands bond using the electron pair of a single donor atom.
• Bidentate ligands bond using electron pairs on two donor atoms.
• Polydentate ligands bond using electron pairs on more than one donor atom (which includes
bidentate ligand).

Polydentate ligands are sometimes called chelating agents (pronounced as key-late-ting) because of
their ability to hold a metal ion like a claw. Chelating ligands form a stable complex ion with the central
metal ion as the pincer-like grip of these polydentate ligands are able to hold the cation more securely.
They typically form rings in the complex ion.

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Monodentate Ligands
It is a ligand that forms one dative covalent bond to a central metal atom or ion.

Bidentate Ligands
It is a ligand that forms two dative bonds to a central metal atom or ion.

Hexadentate Ligands
It is a ligand that forms six dative bonds to a central metal atom or ion.

Ethylenediaminetetraacetate ion (EDTA4−)

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4.3 Coordination Number and Geometry

The coordination number indicates the number of dative bonds around the central atom or ion. The
most common values are 4 and 6, but 2 is also observed and is particularly important in the chemistry
of copper(I) and silver(I) compounds.

Coordination
Formula Geometry Shape
number

[Ag(NH3)2]+ 2 linear

[Ni(CN)4]2– 4 square planar

[CuCl4]2– 4 tetrahedral

[Fe(CN)6]3– 6 octahedral

Table 5. Coordination number and shape of some complex ions

The shape (geometry) of the complex ion depends on the coordination number.

For coordination number of 4, the geometry can be square planar or tetrahedral depending on the
transition metal and ligands involved. The determination and reasons for this is not in syllabus.

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Exercise 4.1

1. Complete the missing information in the table below.

Oxidation no. of No. of ligands Coordination

Complex ion Net charge
central metal ion per complex ion number
(Worked Example)
+3 6 6 –3
[Cr(CN)6]3–
[Cu(Cl)4]x +2 4
[Fe(C2O4)3]3– +3 –3
[Cu(EDTA)]x +2 6

There are 6 monodentate CN– ligands in the complex, so a total of 6 dative bonds formed. Hence
the coordination number is 6. The overall charge of the complex is –3, so to balance out the 6
CN– ligands, the Cr must have an oxidation number of +3.

2. A complex is obtained by reacting aqueous cobalt(III) chloride with ammonia. It is found that
the co-ordination number of cobalt is 6 and that only one third of the total chloride is
precipitated as AgCl when the complex is treated with an excess of aqueous silver nitrate. What
is the formula of the compound?
A Co(NH3)6Cl3 C Co(NH3)4Cl 3
B Co(NH3)5Cl3 D Co(NH3)3Cl3

4.4 Acidity of aqua complexes

In aqueous solution, the transition metal ions exist as aqua complexes. Aqua complexes containing
high charge density transition metal cations like Fe3+ and Cr3+, undergo hydrolysis in water to give a
mildly acidic solution.

[Fe(H2O)6]3+(aq) + H2O(l) ⇌ [Fe(H2O)5(OH)]2+(aq) + H3O+(aq)

[Cr(H2O)6]3+(aq) + H2O(l) ⇌ [Cr(H2O)5(OH)]2+(aq) + H3O+(aq)

This is due to the high charge density on the central transition metal cation and these aqua complexes
undergo appreciable hydrolysis in a similar fashion to the [Al(H2O)6]3+ ion. The mechanism for this
reaction was covered in the salt hydrolysis section in Topic 15 Acid-Base Equilibria.

However, for oxidation states higher than +3, the polarising power of the central metal cation is so
great that the release of protons and loss of water molecules results in the formation of oxoanions.

For instance, [Cr(H2O)6]6+ ions do not exist in aqueous solution. Instead, Cr(VI), occurs in two well-
known oxoanions, the chromate (VI) ion, CrO42–, and the dichromate (VI) ion, Cr2O72–.

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4.4.1 Chromium complexes and oxoanions

When aqueous sodium hydroxide or aqueous ammonia is added dropwise to aqueous solution of
chromium(III) ion, a grey-green ppt is formed. This is due to the formation of Cr(OH)3. This is an acid-
base reaction as chromium(III) ion is acidic.
[Cr(H2O)6]3+(aq) + 3OH–(aq) → [Cr(H2O)3(OH)3](s) + 3H2O(l)
or
Cr (aq) + 3OH (aq) → Cr(OH)3(s)
3+ –

When aqueous sodium hydroxide is added in excess, a dark green solution is formed. This is due to
the formation of [Cr(OH)6]3– complex ion.
[Cr(H2O)3(OH)3](s) + 3OH–(aq) → [Cr(OH)6]3–(aq) + 3H2O(l)
dark green solution

When acid is added to yellow solution of chromate(VI) ion, an orange solution of dichromate(VI) is
formed. Notice that the oxidation state of the chromium ion remains the same.
2CrO42–(aq) + 2H+(aq) ⇌ Cr2O72–(aq) + H2O(l)
yellow orange

4.5 Ligand exchange reaction

LO 13(j): explain qualitatively that ligand exchange may occur, as exemplified by the formation of the complexes in (i),
including the colour changes involved, and CO/O2 exchange in haemoglobin

The ligands in a complex ion can be exchanged for other ligands. This reaction is known as
ligand exchange reaction. This reaction will happen readily if the new complex formed is more stable
than the original complex. A change in colour of the solution is usually observed.

Ligand exchange reactions are largely reversible reactions, and therefore, are represented by the
equilibrium sign ‘⇌’. For example, the ligand exchange reaction between the water ligands in
[Fe(H2O)6]3+ and SCN− (thiocyanate) ions is represented by:

[Fe(H2O)6]3+(aq) + SCN–(aq) ⇌ [Fe(SCN)(H2O)5]2+(aq) + H2O(l)

yellow blood-red

A colour change from yellow to blood-red will be observed in this ligand exchange reaction.
2+
The equilibrium constant of this reaction is given by Kc = [Fe(SCN)(H
3+
2 O)5 ] .
-
[Fe(H2O)6 ] [SCN ]

Note that although water is a reacting species (in the reverse reaction), it is also a solvent. Hence,
[H2O] is almost constant and excluded from the Kc expression.

If the new complex formed is much more stable than the original complex, Kc would be large, the
equilibrium position will lie very much to the right, and a single arrow may be used in the equation.
[Fe(H2O)6]3+(aq) + SCN–(aq) → [Fe(SCN)(H2O)5]2+(aq) + H2O(l)
yellow solution blood red solution

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4.5.1 Ligand exchange reactions involving copper complexes

This section concerns some common complexes of Cu(II) and the reactions in which they can be
formed (often seen in Inorganic QA tests).

• To a solution of Cu2+(aq), add aqueous ammonia dropwise then in excess.

Observation: pale blue ppt formed, which dissolves in excess ammonia to give dark blue solution.
Explanation:
Cu(OH)2 is first precipitated when aqueous ammonia is added dropwise.
Cu2+(aq) + 2OH–(aq) → Cu(OH)2(s)
pale blue ppt

When excess ammonia is added, ligand exchange reaction takes place, with NH3 ligands replacing
H2O ligands to form a dark blue solution. The Cu2+(aq) is equivalent to the hexaaqua cation
[Cu(H2O)6]2+(aq).
[Cu(H2O)6]2+(aq) + 4NH3(aq) → [Cu(NH3)4(H2O)2]2+(aq) + 4H2O(l)
dark blue solution

This causes the concentration of Cu2+(aq) to drop, thus the equilibrium below will shift to the right.
Thus the ppt will dissolve to give a dark blue solution.
Cu(OH)2(s) ⇌ Cu2+(aq) + 2OH–(aq)

• To a solution of Cu2+(aq), add concentrated hydrochloric acid dropwise.

Observation: solution turns from pale blue to green then yellow
Explanation:
When conc. HCl is added, ligand exchange reaction takes place, with Cl– ligands replacing H2O
ligands.
[Cu(H2O)6]2+(aq) + 4Cl−(aq) → [CuCl4]2–(aq) + 6H2O(l)
pale blue solution yellow solution

The green colour is observed due to the mixture of both the blue aqua complex and the yellow
chloro complex present.

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4.5.2 Effects of ligand exchange on reduction potential (Application Example)

Ligands interact differently with the central metal ion, which will result in some change in reduction
potential. For example, when water (H2O) ligands are replaced by cyanide ligands (CN–) for Fe3+, we
can see that there is a change in redox potential for the complex ions.
E/V
[Fe(H2O)6]3+ + e– ⇌ [Fe(H2O)6]2+ +0.77
3– – 4–
[Fe(CN)6] + e ⇌ [Fe(CN)6] +0.36

With the replacement of water ligands by cyanide ligands, E for the reduction of Fe(III) to Fe(II)
becomes less positive. This is significant in the reaction with iodide ions.

I2 + 2e– ⇌ 2I– +0.54V

[Fe(H2O)6]3+ is able to oxidise I– to I2 and a dark brown solution is obtained.

2[Fe(H2O)6]3+ + 2I – → 2[Fe(H2O)6]2+ + I2 Ecell = +0.23 V

On the other hand, [Fe(CN)6]3– is unable to oxidise I– to I2.

Ecell = Ered – Eox

= +0.36 – 0.54
= –0.18 V (not feasible)

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4.5.3 Ligand exchange reaction in haemoglobin

Haemoglobin is the iron-containing protein in red blood cells that transports oxygen in blood. It
consists of four protein chains loosely held together in a cluster. Each chain has a haem molecule
within its folds. Iron (in the +2 oxidation state) is located in the centre of a plane of four nitrogen
atoms. A haemoglobin molecule in the lungs picks up an O2 molecule, which forms a dative bond with
the iron to form a species called oxyhaemoglobin. This binding is reversible and enables haemoglobin
to carry oxygen around the body and release it where it is needed.
Carbon monoxide, CO, can replace O2 as the ligand attached to the iron(II). This is a ligand exchange
reaction. The new complex is called carboxyhaemoglobin. The binding between CO and the iron(II) is
irreversible, thus making carboxyhaemoglobin a very stable complex. The affinity of human
haemoglobin for CO is about 210 times greater than that for O2. As a result, a relatively small quantity
of CO can inactivate a substantial fraction of the haemoglobin for oxygen transport. If the
concentration of CO is high and the level of carboxyhaemoglobin becomes too high, oxygen transport
is effectively shut down and death occurs.

(a)

(a)

(b)
haem group

Figure 5
(a) Structure of the haem group. (b) Haem,
haemoglobin and oxygen transport. The central
iron(II) exhibits hexa co-ordination. Four of the
co-ordination sites are taken up by nitrogen
from a ring system called a porphyrin that acts
as a tetradentate ligand. Below the plane of
(c) this ring is a fifth nitrogen atom from a
histidine side-chain on a protein molecule
called globin. The O2 molecule may be
reversibly bonded at the sixth site. (c) O2
molecules bind to the deoxyhaemoglobin,
forming oxyhaemoglobin that is transported
around the circulatory system in red blood
cells. The O2 molecules bind reversibly with the
iron, thus allowing easy release of O2 for
cellular respiration

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5 COLOURED COMPOUNDS AND COMPLEXES

Transition metal compounds are frequently coloured, both in the solid state and in solution. This is
due to absorption of part of the visible spectrum by the solution. The reason behind the observed
colour can be explained using crystal field theory.

5.1 Light and Colour

White light is an electromagnetic radiation consisting of all wavelengths in the visible range. It can be
dispersed into a spectrum of colours, each of which has a narrower range of wavelengths. For
example, it can be dispersed into seven colours commonly known as the rainbow by using a prism.

Each colour has a complementary colour. For example, green and red are complementary colours.
This is shown as opposite wedges in the colour wheel diagram below.

Figure 6. A diagram of the colour wheel, with approximate wavelength ranges (in nm), shown as wedges.

The energy of the light is inversely proportional to its wavelength. Therefore, red colour, with longer
wavelength is lower in energy as compared to blue light, which is shorter in wavelength.

Objects appear coloured in white light because they absorb certain wavelengths and reflect or
transmit others: an opaque object reflects light, whereas a clear one transmits it. The reflected or
transmitted light enters the eye and the brain perceives a colour. If an object absorbs all visible
wavelengths, it appears black; if it reflects all, it appears white.

5.2 Crystal Field Theory

The crystal field theory was first developed to account for the properties of transition metal ions in
solids. In this theory, the lone pair on ligand is modelled as a point negative charge that attracts the
positive central metal ion, which provides the stability to the complex. They also repel the electrons
in the d orbitals of the metal ion.

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Recall from Topic 1 Atomic Structure that the d orbitals have five different orientations and they are
degenerate (same energy level).

Figure 7. The shapes and orientations of the 3d orbitals

5.2.1 Splitting of degenerate d orbitals in octahedral complex

LO 13(k): describe, using the shape and orientation of the d orbitals, the splitting of degenerate d orbitals into two energy
levels in octahedral complexes
• In a free transition metal ion, all five orbitals are degenerate (have the same energy).
• In the presence of ligands in an octahedral field, the ligands approach the metal ion along the
mutually perpendicular x, y, and z axes.

Figure 8. Ligands approach along the mutually perpendicular axes.

• As the ligands approach, their electron pairs repel electrons in the five d orbitals of metal ions,
causing all five d orbitals to increase in energy.
• However, the d electrons are repelled unequally due to the different orientations of d orbitals. As
the ligands move along the x, y and z axes, they approach directly toward the lobes of the
dx2– y2 and dz2 orbitals but between the lobes of the dxy, dyz and dxz orbitals. Thus, the electrons in
dx2– y2 and dz2 orbital experienced stronger repulsion, which causes the energy of these orbitals to
be higher than the dxy, dyz and dxz orbitals.
• The five d orbitals therefore are no longer degenerate, but are split into two groups with an energy
gap (E) between them.

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Energy

E

Figure 9. Splitting of d orbitals by an octahedral field of ligands.

5.2.2 Electronic d-d transition

• Let us consider the [Ti(H2O)6]3+ ion, which appears purple in aqueous solution. Ti3+(aq) is a d1 ion,
with the d electron in one of the three lower energy orbitals.

Figure 10. Orbital diagram depicting d-d electron transition.

• When white light shines on the solution, the electron at the lower energy level will absorb energy
from the light and jump to one of the higher energy orbitals. Since the electron jumps from one
d-orbital to another d-orbital, this movement is called a d-d transition.
• The energy gap (E) between the two levels corresponds to the energy of photons with a range
of wavelength in the visible spectrum. For Ti3+(aq), it happens to be in the green and yellow range.
• The complementary colours red, orange, blue and violet lights are transmitted, thus the solution
looks purple.

LO 13(l): explain, in terms of d orbital splitting and d-d transition, why transition element complexes are usually coloured
[knowledge of the relative order of ligand field strength is not required]
In the presence of ligands, the partially filled degenerate 3d orbitals of a transition metal ion are split
into two different energy levels with a small energy gap E between them. There are vacancies in the
higher energy d orbitals. The promotion of an electron from the lower to the higher of these d orbitals
requires the absorption of radiation in the visible spectrum with energy corresponding to the energy
gap. Such a d-d transition is responsible for the colour of the complex ion. The colour observed is the
complement of the colours absorbed.

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5.3 Factors affecting the colour of complexes

5.3.1 Oxidation state of the metal

Different number of electrons in the d orbitals of the transition metal ion will result in different
interactions with the electrons from the ligands. This will give rise to different energy gap (E) thus
the wavelengths of light absorbed will also be different. The table below shows the example of
vanadium complexes.

Formula of ion V3+(aq) V2+(aq)

Oxidation state of vanadium +3 +2
Electronic configuration [Ar] 3d2 [Ar] 3d3
Colour green violet

The absence of colour in Sc3+, Ti4+, Cu+ and Zn2+ is due to them having either no d electrons (3d0 for
Sc3+ & Ti4+) or fully filled d orbitals (3d10 for Cu+ & Zn2+). In such cases, no d-d electronic transition is
possible.

5.3.2 Nature of ligand

Different ligands have different effects on the splitting of the d orbitals. The difference in magnitude
of E will lead to different colours observed. The diagram below shows the example of some nickel
octahedral complexes.

Figure 11. Size of d orbital splitting – the energy gap between the two groups of d orbitals depends on the ligand

Note: Other splitting patterns exist (and may appear as application questions) but student are only expected to be able to
recall splitting of d-orbitals for octahedral complexes.

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5.4 Common transition metal ions/compounds and their corresponding colours

Oxidation number of
Transition metal Formula Colour
transition metal
+3 [Cr(H2O)6]3+ green
Chromium +6 CrO42– yellow
+6 Cr2O72– orange
+2 Mn2+ faint pink / colourless if dilute
+4 MnO2 dark brown ppt
Manganese
+6 MnO42– dark green
+7 MnO4– purple
+2 [Fe(H2O)6]2+ pale green
+2 Fe(OH)2 green ppt
Iron +3 [Fe(H2O)6]3+ yellow
+3 [Fe(SCN)(H2O)5]2+ blood red
+3 Fe(OH)3 reddish brown ppt
+2 [Cu(H2O)6]2+ pale blue
2+
+2 [Cu(NH3)4(H2O)2] dark blue
Copper
+2 [CuCl4]2– yellow
+2 Cu(OH)2 pale blue ppt

Not all colours of transition metal compounds originate from d-d transition. Some colours in the
table above can be due to other electronic transitions which are not in the A Level syllabus (only d-d
transition is required).

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5.5 Using colorimetry in experiments

5.5.1 Determining the concentration of complex ions by colorimetry

To determine the concentration of a coloured complex using colorimetry

Example: N2013/P2/Q1 (Planning Question)

Approach:
A calibration graph is first obtained by measuring the absorbance of a series of solutions containing
the coloured complex at various known concentrations. Then measure the absorbance of the
unknown solution and read its concentration off the calibration graph.

Generic procedure
1. A suitable filter (of a complementary colour) is selected.
2. A ‘blank’ absorbance reading is taken using water as a reference.
3. A series of solutions of known concentrations of (the coloured complex)_ are made up (usually
by dilution from a stock solution).
4. The absorbance of the solutions are measured in turn with the colorimeter.
5. A calibration graph of absorbance against concentration is plotted.
6. The absorbance of the test solution is now measured, and the calibration curve is used to
determine the unknown concentration.
Absorbance of test solution

Concentration of
coloured complex
in test solution /
mol dm−3

• If the UV-VIS spectrophotometer is used instead of the colorimeter, the absorbance readings
are measured at a fixed wavelength (usually at the wavelength where absorbance is the
greatest or the complementary colour), instead of using a filter in Step 1.

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5.5.2 Investigating the stoichiometry of complex ions by colorimetry

The formula of a complex ion can be determined by measuring the colour intensity of the complex
ion, provided the colour of the complex is quite different from the colours of the separate aqueous
ions.

E.g. When Fe3+(aq) react with thiocyanate ions SCN− (aq), a deep red (blood red) colour is produced:
Fe3+(aq) + x SCN−(aq) → [Fe(SCN)x]3 – x (aq)

The stoichiometry of the complex can be determined by the method of continuous variation.
Mixtures of Fe3+ and SCN− with Fe3+ : SCN− in molar proportions of 10:0, 9:1, 8:2, 7:3, 6:4, etc. is made.
In other words, the relative proportions of Fe3+ : SCN− are continuously varied from 10:0 to 0:10.

Clearly, the mixture with the most intense coloured solution corresponds to molar proportions of Fe3+
and SCN− which just react completely leaving neither in excess. In some cases, it might be possible to
tell by eye which mixture contains the darkest-coloured solution, but the judgment can be done much
more reliably and accurately using a spectrophotometer. The spectrophotometer measures the
absorbance of the test solution, which is proportional to the concentration of the complex.

The table below shows a typical set of results for the Fe3+ / SCN− investigation.
Tube number 1 2 3 4 5 6 7 8 9 10 11
Volume of
10 9 8 7 6 5 4 3 2 1 0
5.00  10−3 mol dm−3 Fe(NO3)3 /cm3
Volume of
0 1 2 3 4 5 6 7 8 9 10
5.00  10−3 mol dm−3 KSCN /cm3
Absorbance 8 20 32 40 48 52 45 36 24 16 0

The results are represented graphically below.

Extrapolate the two straight lines to find the maximum absorbance (which corresponds to the highest
concentration of the complex).
• In what molar proportions do Fe3+ and SCN− react to form the blood red complex ion?
• Write the balanced equation for the formation of the complex ion by ligand exchange.

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Planning an experiment involving qualitative analysis

You may be asked to propose a sequence of test-tube reactions to identify inorganic ions. This means
you need to review your Inorganic Chemistry Qualitative Analysis notes. Inorganic QA tests are based
on four main types of chemical reactions that produce precipitates, gases, and colour changes. Try to
identify these four main types of inorganic reactions in your QA notes:
• Ionic precipitation reactions
• Acid-base reactions
• Redox reactions
• Complex forming reactions including ligand exchange

When planning a qualitative analysis experiment, you may be asked to:

• Present the sequence of tests. You may use a flowchart or table.
• Write the procedure with essential details of quantities and conditions for each test.
• State the expected observations for both positive and negative tests.
• Explain the chemistry underlying each test e.g. type of reaction, identity of species responsible for
precipitate / gas / colour change.

The unknown ions might be present in a mixture, and you might be required to plan a filtration to
separate the ions or precipitates. For example, FA1 contains two cations (Fe2+ and Zn2+). NaOH(aq)
and NH3(aq) are common test reagents for cations: Fe2+ forms an insoluble basic hydroxide while Zn2+
forms a soluble amphoteric hydroxide, which can be separated by filtration. A sample plan is shown
below.

Test Observations Location of ions

To 1 cm3 of FA1 in a test Green ppt insoluble in excess Fe2+ ─ Fe(OH)2 ppt
tube, add excess NaOH
NaOH(aq).

Filter the mixture and Colourless filtrate Zn2+ ─ in the filtrate as [Zn(OH)4]2−
collect the filtrate in a
separate test tube. Green residue turns reddish Fe(OH)2 oxidised to Fe(OH)3
brown on contact with air
You may also present your plan as a flowchart.

LOOKING AHEAD
You have completed the last topic in 9729 H2 Chemistry. Do spend some time to consolidate all that you have
learned and be able to see how basic chemistry principles are applied in different topics throughout the
syllabus. All the best!

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