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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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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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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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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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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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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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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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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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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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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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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