YISHUN INNOVA JUNIOR COLLEGE

2020 JC1 H2 CHEMISTRY

ATOMIC STRUCTURE

GUIDING QUESTIONS

 What makes up an atom?

 How has the understanding of atomic structure developed and evolved?
 What is the evidence showing that the 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 are the arrangement of an element’s electrons and its position in the Periodic Table related?

LEARNING OBJECTIVES

At the end of the lesson, students should be able to:

(a) identify and describe protons, neutrons and electrons in terms of their relative charges and relative masses

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

(c) describe the distribution of mass and charges within an atom

(d) deduce the numbers of protons, neutrons and electrons present in both atoms and ions given proton and
nucleon numbers (and charge)

(e) (i) describe the contribution of protons and neutrons to atomic nuclei in terms of proton number and
nucleon number

(ii) distinguish between isotopes on basis of different numbers of neutrons present

(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

(g) describe the shapes of s, p and d orbitals

[knowledge of wave functions is not required]

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

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

(j) deduce the electronic configurations of elements from successive ionisation energy data

(k) interpret successive ionisation energy data of an element in terms of the position of that element within the
Periodic Table
Atomic Structure

REFERENCES

 Peter Cann and Peter Hughes (2015), Cambridge International AS and A Level Chemistry
 Kim Seng Chan and Jeanne Tan (2017), Understanding Advanced Physical Inorganic Chemistry,
The Learner’s Approach, Revised Edition
 http://www.khanacademy.org/science/chemistry/electronic-structure-of-atoms

CONTENTS PAGE

1 Introduction
1.1 John Dalton’s Atomic Theory (1803)
1.2 The Discovery of Sub-atomic Particles and Development of the Structure of the Atom
1.3 A Modern Reassessment of the Atomic Theory

2 Properties of The Three Sub-Atomic Particles

2.1 The Relative Charges and Masses
2.2 Isotopes
2.3 Behaviour of Beams of the Sub-atomic Particles in an Electric Field

3 Quantum Mechanical Model of the Atom

3.1 Evidence of Energy Levels
3.2 Evidence for the Electronic Configuration: Ionisation energies
3.3 Principal Quantum Shells, Sub-shells and Orbitals
3.3.1 Principal Quantum Shells
3.3.2 Sub-shells
3.3.3 Atomic Orbitals
3.4 Characteristics of Orbitals
3.5 Energy of the Principal Quantum Shells, Sub-shells and Orbitals

4 Electronic Configurations
4.1 Writing Electronic Configurations
4.2 Writing Electronic Configuration of Ions
4.3 Types of Notation
4.3.1 ‘Electron-in-box’ Diagram
4.3.2 spdf Notation
4.3.3 Noble Gas Core Configuration

5 Ionisation Energy
5.1 Definition
5.2 Factors Influencing the Magnitude of Ionisation Energy
5.3 Successive Ionisation Energies

6 Applications In The Real World Context

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Atomic Structure

1. INTRODUCTION (SELF-READ)

Matters are anything that has a mass and volume. Thus, almost everything around us (except vacuum)
is matter. But what makes up matters? Why is one matter so different both in appearance and property
compared to another matter?

Chemistry is the study of the properties of matter. Chemists are actively inquisitive scientists. We seek
to understand why matter has properties it does, and how to modify these properties by changing one
substance into another through chemical reactions.

Chemistry as a modern science began a few hundred years ago, when chemists started to relate the
observations they made about the substance they were investigating to theories of the structure of
matter. One of the most important of these theories was the Atomic Theory. It is more than 200 years
since John Dalton put forward his idea that all matter was composed of atoms.

5th century Democritus Held that all matter is composed of the smallest
BC indivisible bodies called atoms

Proposed a fifth element, aether, from which stars

4th century Aristotle and planets were made, in addition to the four
BC elements, earth water, air and fire, described
earlier by Empedocles

Sought Aristotle’s fifth element to effect the

Middle Ages Alchemy transformation of other base metals into precious
gold; helped developed many apparatus and
experimental techniques still in use today

Referred to as ‘The Father of Chemistry’; defined

1661 Robert Boyle elements as substances which could not be
broken down into nor formed from simpler
substances

Discovered the law of conservation of mass;

1774 Antoine defined elements as a basic substance that could
Lavoisier not be further broken down by the methods of
chemistry

1704 Isaac Newton Proposed a mechanical universe with small solid

masses in motion

Proposed that each element consists of atoms of

1805 John Dalton a single, unique type, and that chemical
compounds are formed by combinations of these
atoms

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Atomic Structure

1.1 John Dalton’s Atomic Theory (1803)

In the Atomic Theory, John Dalton postulated that,

(a) All matter consists of atoms, tiny indivisible particles of an element that cannot be created nor
destroyed.
(b) Atoms of one element cannot be converted into atoms of another element. In chemical reactions,
the original substance separates into atoms, and recombine to form different substances.
(c) Atoms of an element are identical in mass and other properties and are different from atoms of any
other element.
(d) Compounds result from the chemical combination of a specific ratio of atoms of different elements.

1.2 The Discovery of Sub-atomic Particles and Development of the Structure of The Atom

For most of the nineteenth century the idea of atoms being indivisible fitted in well with chemists’ ideas
of chemical reactions, and was readily accepted. However, this idea was overruled with the discovery
of subatomic particles in the atoms by various scientists and the idea of the structure of the atom began
to evolve and change over time.

Discovery of Electrons (by Joseph John Thomson) (1897)

The electrons were discovered by J.J. Thomson using the Cathode Ray Experiment. He found that the
electron was much lighter than the lightest atom (hydrogen atom), and had a negative electrical charge.
What is more, he found that under the conditions of his experiment, atoms of different elements
produced the same electron particles.

Thomson’s discovery overruled Dalton’s first point, that atoms are indivisible, as the existence of sub-
atomic particles (in this case, electrons) was proven.

On the basis that atoms have no overall charge; they are neutral, so
there must be a part of the atom that is positively charged, to balance the
negative charge of the electrons, J.J. Thomson proposed a model that
described atoms as negatively charged electrons embedded in a sphere
of positive charge. It was known as the ‘plum pudding’ model because the
electrons were spread randomly throughout the positive charge like the
dried fruit in a pudding.

Discovery of the Nucleus and Protons (by Ernest Rutherford) (1909)

In 1909, Ernest Rutherford and his colleague carried out the Gold Foil Experiment and showed that
the positive charge in the atom is concentrated into an incredibly small nucleus right in the middle of
it. Rutherford was able to chip away from this nucleus small positively charged particles and called
them protons. It was much heavier than the electron, having the mass of the hydrogen atom.

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Atomic Structure

Rutherford Model
A new model of the atom was needed to account for the
results of the Gold Foil Experiment. Rutherford
proposed a model in which all the positively charged
protons and most of the masses of an atom were
concentrated in the nucleus which is small and the rest
of the atom is mostly empty space. Sufficient electrons
surround the nucleus of an atom to balance the charge
of the nucleus and to make the atom neutral overall.

Discovery of the Neutrons (by James Chadwick) (1932)

Having discovered the proton, Rutherford was immediately faced with another problem: there were
always (except in the case of hydrogen) too few protons to explain the mass of the nucleus.

In 1932, James Chadwick discovered the missing particle found in the nucleus and named it as
neutron. This particle could pass through many centimetres of solid lead and was not deflected by
electric or magnetic field. Chadwick decided that the stream must consist of particles with almost the
same mass as protons but with no charge.

Bohr’s Model (1913)

Niels Bohr proposed that electrons can only have certain, specific amounts of energy (called energy
level) and their orbits have certain radii around the nucleus. In other words, electrons occupying an
orbit of a certain radius around the nucleus will have a certain amount of energy. Similarly, electrons
in the same orbit will have the same amount of energy.

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Atomic Structure

The Modern Theory – The Quantum Mechanical (Wave) Model (1927)

In 1927, German physicist Werner Heisenberg postulated that it is impossible to know the exact
position and momentum of the electrons at a given time. This is called the Heisenberg’s Uncertainty
Principle.
In the study of chemical reactions, we are more concerned with the energy levels of the electrons
(which allows us to predict whether a reaction can proceed or not). Therefore, we only consider the
probability of finding an electron at a given position in space.
Using the Schrödinger’s wave equation, we map the probability of the position, in 3-dimensional space,
of the electron. This probability in the three-dimensional space of finding an electron is known as an
atomic orbital.

For more information on

Dalton’s Atomic Theory Rutherford’s Atomic Rutherford’s Atomic Bohr’s Model of an atom
Model Part 1 Model Part 2
https://www.youtube.com/w https://www.youtube.com/w
atch?v=syi3pXJNe58 https://www.youtube.com/w https://www.youtube.com/w atch?v=S1LDJUu4nko
atch?v=1EdTw4I6L0U atch?v=B-k_kMwB1zM

Scan the QR code to find out more.

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Atomic Structure

1.3 A Modern Reassessment of the Atomic Theory

We began discussing the atomic basis of matter with Dalton’s model, which proved inaccurate in
several respects. Let’s re-examine the Atomic Theory in light of what we know now.

John Dalton’s Atomic Theory Reassessment

 All matter consists of atoms, tiny indivisible  Atoms are divisible and composed of
particles of an element that cannot be smaller, sub-atomic particles (electrons,
created nor destroyed. protons, and neutrons).

 Atoms of one element cannot be converted  In nuclear reactions, atoms of one element
into atoms of another element. In chemical often change into atoms of another, but this
reactions, the original substance separate never happens in a chemical reaction.
into atoms, and recombine to form different
substances.

 Atoms of an element are identical in mass  There is the existence of isotopes, which
and other properties and are different from differ in the number of neutrons, and thus in
atoms of any other element. mass number, but a sample of the element is
treated as though its atoms have an average
mass.

 Compounds result from the chemical  This postulate remains essentially

combination of a specific ratio of atoms of unchanged.
different elements.

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Atomic Structure

2. PROPERTIES OF THE THREE SUB-ATOMIC PARTICLES

2.1 The Relative Charges and Masses ( Recall O level – SELF READ )

Learning outcomes
(a) identify and describe protons, neutrons and electrons in terms of their relative charges and relative masses
(c) describe the distribution of mass and charges within an atom

 An atom is the smallest component of an element that can take part in a chemical reaction.
 Atoms are made up of sub-atomic particles – protons, neutrons, electrons.

relative charges relative masses location in an atom

proton +1 1 in the nucleus

neutron 0 1 in the nucleus
1 surrounding the nucleus
electron −1
1840 (in orbitals)

 Protons and neutrons (collectively known as nucleons) are found in the nucleus. The nucleus is
very dense and makes up most of the mass, but very little volume of the atom.
 Most of the atom is empty space, with electrons revolving around the nucleus in the empty space
(orbitals).
 An atom has the same number of protons and electrons, hence atoms are electrically neutral as
the positive and negative charges cancel off each other.

It is convenient to identify an atom or its isotope using the following convention:

A
Z XB where:

X symbol of the element

B charge of an ion of X
A atomic mass (nucleon number) total number of protons and neutrons in the nucleus
of an atom
Z atomic number (proton number) number of protons in the nucleus of an atom
(A – Z) neutron number number of neutrons in the nucleus of an atom

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Atomic Structure

2.3 Behaviour of Beams of the Sub-Atomic Particles in an Electric Field

Learning outcome
(b) deduce the behaviour of beams of protons, neutrons and electrons in an electric field

Due to their relative masses and charges, the three sub-atomic particles behave differently in an
electric field.

electron

beam of protons,
neutrons and
electrons with the neutron
same velocities
proton

 Neutrons are electrically neutral and hence not deflected.

 Positively charged protons are deflected towards the negatively charged plates.
 Negatively charged electrons are deflected towards the positively charged plates.
 Electrons are deflected by a larger extent as they have charge of the same magnitude as
protons but are much lighter than protons. Thus,  a >  b.

When drawing ion pathway in the electric field, deflection of ion should only start when the ion is in (not before) the
region between the positive and negative potential.

The angle of deflection of particles in these fields depends on their mass and charges. Hence, the
charge
bigger the ratio, the larger the angle of deflection.
mass

charge
angle of deflection ∝ of the particle
mass

charge
angle of deflection = k × mass
of the particle

where k is the proportionality constant

The value of k is the same for all ions in the same electric field.

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Atomic Structure

CHECKPOINT 1

Plasma is a gaseous mixture in which the atoms have been completely stripped of their electrons,
leaving the bare nuclei. Due to its possible use in controlled nuclear fusion reactions, plasma behaviour
has been intensively studied. When passed between two plates carrying a certain electric charge,
plasma of 1H+ and 4He2+ nuclei are deflected as follows.

1H+
A
4He2+
2o
2o

(a) Suggest the polarity of plate A.

(b) Show why 1H+ is deflected twice as much as 4He2+?

(c) Calculate the angles of deflection of

 2H+ nuclei,
 3He2+ nuclei.

(a)

(b)

(c)

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Atomic Structure

3. QUANTUM MECHANICAL MODEL OF THE ATOM

3.1 Evidence of Energy Levels

Electronic configuration refers to a particular arrangement of electrons in the orbitals of an atom or ion.
When atoms (either of the same elements or different elements) react, electrons are redistributed.
These electrons may be transferred from one atom to another (forming ionic bonds) or they may be
shared between the reacting atoms (forming covalent bonds). Only electrons are involved in the
chemical reaction. Protons and neutrons take no part.

As chemical reactions involve only electrons, the similarities in chemical properties of certain elements
suggest that these elements may have similar electronic configurations.

The electronic structure of an atom of an element can be obtained by studying the atomic spectra of
an element (adsorption or emission lines obtained when electrons transit from lower to higher energy
level or vice versa) and its ionisation energies.

3.2 Evidence for the Electronic Configuration: Ionisation energies

Ionisation is the removal of electron(s) completely from an atom or ion.

The energy required for this process is termed as ‘ionisation energy’. It has a unit of kJ mol−1.
It is an endothermic process because energy is required to overcome the electrostatic force of
attraction between the nucleus and the electrons.

First ionisation energy is the energy required to remove one mole of the outermost electrons from
one mole of gaseous M atoms to form one mole of gaseous M+ cations.

M(g)  M+(g) + e−

More than one electron may be removed from an atom if sufficient energy is applied.

Second ionisation energy is the energy required to remove one mole of the outermost electrons
from one mole of gaseous M+ cations to form one mole of gaseous M2+ cations.

M+(g)  M2+(g) + e−

Taking sodium as an example,

Na(g)  Na+(g) + e− 1st I.E. = +494 kJ mol−1
Na+(g)  Na2+(g) + e− 2nd I.E. = +4560 kJ mol−1

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Atomic Structure

The graphical representation of the energy required in the removal of all the eleven electrons from Na
atom is shown below.

Log IE

Electrons are located in

different principal
quantum shells
Electrons are located in different
subshells within the same
principal quantum shell
Electrons are located in
different principal quantum
shells

1 2 3 4 5 6 7 8 9 10 11 Electrons removed

 The trend in the successive ionisation energies for the sodium atom suggests that the 11
electrons of sodium fall into 3 groups. Notice that the first electron is relatively easy to remove,
followed by a group of 8 electrons which require more energy to remove and then the final 2
electrons which require even more energy to remove.

 Thus, sodium has 2 electrons in the 1st shell closest to the nucleus, 8 electrons in the 2nd shell from
the nucleus and 1 electron in the 3rd shell from the nucleus (this is also the valence electron). These
are known as the principal quantum shells.

 We can also conclude that the electrons in an atom occupy different energy levels.

 A further study of the successive ionisation energies shows that the group of 8 electrons (2nd to 9th
electron being removed) is divided into a “sub-group” of 2 and a “sub-group” of 6. These are known
as the sub-shells.

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Atomic Structure

In summary, electronic configuration is determined by the principal quantum shell, subshell

and orbital which the electron occupies.

Atom

contains

(1) Principal Quantum Shell

contains

(2) Subshells

contain

(3) Orbitals

contain

Electrons

3.3 Principal Quantum Shells, Sub-shells and Orbitals

3.3.1 Principal Quantum Shells

 Takes integral values called the principal quantum number n, where n = 1, 2, 3… in ascending
order of distance from the nucleus.
 n determines the energy level of the electron shell. The closer the quantum shell is to the nucleus,
the greater the attraction between the electrons occupying it and the nucleus, the lower the energy
of the electrons. For example, n = 1 has a low energy than n = 2.
 Each principal quantum shell is subdivided into one or more subshells labeled s, p, d, f.
 The maximum number of electrons that can occupy each principal quantum shell (n) can be
obtained by using the formula 2n2.

principal quantum shell (n) 1 2 3 4

maximum number of electrons, 2n2 2 8 18 32

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Atomic Structure

3.3.2 Sub-shells

 These are shells organised within each principal quantum shell. Each principal quantum shell
contains n number of subshells.
 These subshells are denoted by the letters, s, p, d, f, and g and so on.

principal
types of subshells labeled as
quantum number
n=1 s 1s
n=2 s, p 2s, 2p
n=3 s, p, d 3s, 3p, 3d
n=4 s, p, d, f 4s, 4p, 4d, 4f

 Sub-shells within the same quantum shell have slightly different energy levels.

s (lowest)  p  d  f and so on

Example: energy of 4s < 4p < 4d < 4f

3.3.3 Atomic Orbitals

 An orbital is defined as the region of space within which there is a 95% probability of locating a
particular electron in an atom. Each orbital has a characteristic energy level and shape.
 The number of orbital in each subshell depends on the type of subshell.
type of subshell number of orbitals type of orbital
s 1 s
p 3 px, py, pz
d 5 dxy, dxz, dyz, dz2, dx2y2

 Orbitals in the same sub-shell are equivalent in energy (degenerate) but they differ in their
orientation in space.
 Each orbital can hold a maximum of 2 electrons of opposite spin.

principal quantum number of name of number of orbitals maximum number

shell subshell subshell of electrons (2n2)
n=1 1 1s 1 2
n=2 2 2s, 2p 1+3=4 8
n=3 3 3s, 3p, 3d 1+ 3 + 5 = 9 18
n=4 4 4s, 4p, 4d, 4f 1 + 3 + 5 + 7 = 16 32
.
.
( n=7 discovered thus
far)

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Atomic Structure

3.4 Characteristics of Orbitals

Learning outcome
(g) describe the shapes of s, p and d orbitals

s-orbitals
characteristics shape sketch
 s-orbitals are spherical in
shape and they are non-
directional.

1s
 as n increases, the size of
the orbital also increases (or
we say that the orbital
becomes more diffused) 1s
size of 1s orbital < 2s
orbital < 3s orbital 2s

 distance of electrons from

the nucleus in 1s orbital < 2s
orbital < 3s orbital

3s 2s

3s

When drawing orbitals, the x, y and z-axis must be shown to illustrate the 3-dimensional
property of the orbitals

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Atomic Structure

p-orbitals

characteristics shape sketch

 p-orbitals are dumb-bell in
shape.

 The 3 types of p orbitals, px,

py, pz, all have the same
size and shape but different
orientation in space (along
the three x, y and z axes).
2px
 as n increases, the size of
the orbital also increases.
size of 2p orbital < 3p
orbital (i.e. 3p orbital is
more diffuse than 2p orbital)

 The p-orbitals with the

same principal quantum
number, n, have the same 2py
energy (i.e. they are
degenerate).

2pz

The three p orbitals in a particular subshell are identical in size and shape except for their
orientations.

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Atomic Structure

d-orbitals

characteristics shape sketch

 each d subshell consists of
five orbitals which are
degenerate.

 dxy, dxz, dyz orbitals has two

dumb-bell shapes in a plane
pointing between two of the
axes. 3dxy
E.g. the two dumb-bell
shapes of dxy orbital in a
plane pointing between the
x- and z-axis.

3dxz

3dyz
 dx2  y2 orbital has two
dumb-bell shapes in a plane
pointing between along the
x- and y axes.

 dz2 orbital consists of one 3dx2  y2

dumb-bell shape along the
z-axis and a torus
(‘doughnut’) of electron
density around its middle.

3dz2

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Atomic Structure

CHECKPOINT 2

Determine if the following statements are true (T) or false (F).

(a) 1s and 2s orbitals are found in the same principal quantum shell. T/F

(b) 3s, 3px and 3d orbitals are in the same principal quantum shell. T/F

(c) 2s and 2px orbitals are in the same subshell. T/F

(d) 2px and 3px orbitals are in the same subshell. T/F

(e) 2px, 2py and 2pz orbitals are in the same subshell. T/F

(f) The 3rd principal quantum shell consists of 9 orbitals. T/F

(g) 1p orbitals exist. T/F

(h) There are two 2s orbitals. T/F

(i) 2px and 3px orbitals have the same shape. T/F

(j) 2px and 2py orbitals are of the same size. T/F

CHECKPOINT 3

Draw and label the py and dyz orbitals.

py dyz

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Atomic Structure

To summarise, the electrons in an atom are arranged in the following hierarchy:

Atom

contains

(1) Principal Quantum Shell

contains
1s, 2s, 3s 2p 3p 3d
(2) Subshells

contains

(3) Orbitals
1s, 2s, 3s 2px, 2py, 2pz
contain 3dxy, 3dxz, 3dyz,
3px, 3py, 3pz 3dx2 - y2, 3dz2
Electrons

3.5 Energy of the Principal Quantum Shells, Sub-shells and Orbitals

Learning outcome
(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

The diagram below shows the energy associated with the principal quantum shell, sub-shells and
orbitals in the atom.

4p 4px 4py 4pz

N (n=4)
3d 3dxy 3dyz 3d xz 3d z2 3dx2-y2
Increasing
energy 4s 4s

3p 3px 3py 3pz

M (n=3)

3s 3s

2p 2px 2py 2pz

L (n=2)
2s 2s

1s 1s
K (n=1)

SHELLS SUBSHELLS ORBITALS

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Atomic Structure

The further away the principal shell, sub-shell and orbital from the nucleus, the higher its energy.
Generally, for the same value of n, the relative energies of the orbitals increase in the following order:
s < p < d < f.

However, that there are some cases of overlapping in the energy level of the orbitals. For example,
when empty the 4s orbital has a lower energy level than the 3d orbitals.

4 ELECTRONIC CONFIGURATIONS

4.1 Writing Electronic Configurations

Learning outcome
(h) state the electronic configuration of atoms and ions given the proton number (and charge)

The electronic configuration of an element describes how the electrons of its atoms are arranged in
their quantum shell, subshells and orbitals.

number of electrons
principal quantum number in the subshell
(energy level) 1s2
subshell

There are 3 rules which should be applied to work out the electronic configurations.
Rule 1: The Aufbau Principle (Building – Up Principle)
Electrons are placed in the orbital of the lowest energy, then the orbital of the next lowest energy and
so on.
The diagram below shows the order in which orbitals are filled.

Recall that the energy level of 4s is lower than 3d.

So when filling the orbitals, electrons must go into
4s before 3d.

Hence, the filling order is: 1s, 2s, 2p, 3s, 3p, 4s,
3d, 4p, 5s, 4d …

However, the writing order is in order of

increasing principal quantum number.

When the electrons in the atom occupy the

lowest energy levels, the atom is said to be in its
ground state.

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Atomic Structure

EXAMPLE 1

Boron has 5 electrons

electronic configuration: 1s2 2s2 2p1

electron-in-box diagram: ↿⇂ ↿⇂ ↿
1s 2s 2px 2py 2pz

Rule 2: The Pauli Exclusion Principle

An orbital can only accommodate a maximum of 2 electrons, which must have opposite spins.

↿⇂ ↿↿ ⇂⇂
allowed: opposite spin not allowed: same spin in the orbital

When 2 electrons are in the orbital, they are referred to as paired electrons. ↿⇂
When there is only 1 electron in the orbital, it is referred to as an unpaired electron. ↿

The symbols ↿ and ⇂ are used to represent electrons of opposite spins.

EXAMPLE 2

Helium has 2 electrons.

electronic configuration: 1s2

electron-in-box diagram: ↿⇂ correct

1s
Correct

↿↿ or ⇂⇂ incorrect
1s 1s
Incorrect

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Atomic Structure

Rule 3: Hund’s Rule

When electrons are added to the same subshell, electrons occupy degenerate orbitals singly and with
the same spin before pairing occur. This minimises inter-electronic repulsion.

↿ ↿ ↿ ⇂ ⇂ ⇂ ↿⇂ ↿ ↿ ↿ ⇂
allowed: not allowed: not allowed:
singly filled with same spins in the same pairing without filling different spin
subshell all orbitals first

EXAMPLE 3

(a) Nitrogen has 7 electrons.

electronic configuration: 1s2 2s2 2p3

electron-in-box diagram: ↿⇂ ↿⇂ ↿ ↿ ↿ correct

1s 2s 2px 2py 2pz
Correct

↿⇂ ↿⇂ ↿ ↿ ⇂ incorrect
1s 2s 2px 2py 2pz
Incorrect

↿⇂ ↿⇂ ↿⇂ ↿ incorrect
1s 2s 2px 2py 2pz
Incorrect

(b) Oxygen has 8 electrons

electronic configuration: 1s2 2s2 2p4

electron-in-box diagram: ↿⇂ ↿⇂ ↿⇂ ↿ ↿
1s 2s 2px 2py 2pz

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Electronic Configuration of Elements with Atomic Number ≥ 19 and Transition Elements

Fe (atomic number: 26)

electronic configuration of Fe: 1s2 2s2 2p6 3s2 3p6 3d6 4s2

According to Aufbau Principle,

 Fill the 4s orbital before filling the 3d orbital.
Reason: when empty the 4s orbital is lower in energy than 3d orbital.

 After the 4s and 3d orbitals are filled, their energy level will be reversed, with 3d orbital in lower
energy than 4s orbital.

Orbitals are written in order of increasing principal quantum number, NOT in the order in which
they are filled

Exceptions to the rules

The rules, which we use work generally well for predicting electronic configurations, but there are
exceptions. Aufbau Principle does not apply to Cr and Cu and elements in the same group.

electronic configuration
expected actual
Cr 1s 2s 2p6 3s2 3p6 3d4 4s2
2 2
1s 2s 2p6 3s2 3p6 3d5 4s1
2 2

↿ ↿ ↿ ↿ ↿ ↿
3d 4s

Cu 1s2 2s2 2p6 3s2 3p6 3d9 4s2 1s2 2s2 2p6 3s2 3p6 3d10 4s1

↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿
3d 4s

When the filling of d orbitals is involved, a half filled and fully filled d subshell tends to be more stable
(only applies to d orbitals).

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4.2 Writing Electronic Configuration of Ions

 Cations are positively charged ions formed when electrons are lost.
 Anions are negatively charged ions formed when electrons are gained.

CATIONS
E.g. Fe3+

Step 1: Write the electronic configuration of the atom.

Fe : 1s2 2s2 2p6 3s2 3p6 3d6 4s2

Step 2: Remove the number of electrons corresponding to the charge of the ion from the
outermost shell of the ground state configuration of its atom.

i.e. Fe3+ has a charge of +3. Remove 3 electrons where the first and second electrons are
removed from 4s orbital and the third electron is removed from the 3d orbital.

Fe3+: 1s2 2s2 2p6 3s2 3p6 3d5

ANIONS
E.g. O2–

Step 1: Write the electronic configuration of the atom.

O: 1s2 2s2 2p4

Step 2: Add the number of electrons corresponding to the charge to the next available orbital in
the atom according to Aufbau Principle.

i.e. O2– has a charge of –2. Add 2 electrons to the 2p orbitals.

O2–: 1s2 2s2 2p6

CHECKPOINT 4

Ga has the electronic configuration of [Ar] 3d10 4s2 4p1. Write down the full electronic configuration of
4+
31Ga ion?

full electronic configuration 31Ga4+:

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4.3 Types of Notation

4.3.1 ‘Electrons-in-box’ Diagram

Each box represents an orbital.

Boxes are drawn in order of increasing principal quantum number.
Electrons are represented by half-arrows.

16S: ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿ ↿
1s 2s 2p 3s 3p

Remember to:
 fill orbitals singly first before pairing occurs.
 label subshells.

4.3.2 spdf Notation

16S: 1s2 2s2 2p6 3s2 3p4

Sum of superscripts = Total number of electrons present

e.g. Total number of electrons in 16S = 2 + 2 + 6 + 2 + 4 = 16

 superscript for electrons

 no commas
 lowercase letters for subshell

4.3.3 Noble Gas Core Configuration

16S: [Ne] 3s2 3p4 (where [Ne]: 1s2 2s2 2p6)

 do not give the electronic configurations in Noble Gas Core format unless being asked for.

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CHECKPOINT 5

For each of the element below, write the electron configuration using the ‘electrons-in-box’ diagram,
the spdf notation and the noble gas core configuration.

(a) 20Ca

‘electrons-in-box’ diagram

spdf notation: ………………………………………………………………………………..

noble gas core configuration: ………………………………………………………………

(b) 23V

‘electrons-in-box’ diagram

spdf notation: ………………………………………………………………………………

noble gas core configuration: …………………………………………………………….

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5. IONISATION ENERGY

5.1 Definition

First ionisation energy is the energy required to remove one mole of the outermost
electrons from one mole of gaseous M atoms to form one mole of gaseous M+ cations.

M(g)  M+(g) + e– 1st I.E. of M

Second ionisation energy is the energy required to remove one mole of the outermost electrons
from one mole of gaseous M+ cations to form one mole of gaseous M2+ cations.

M+(g)  M2+(g) + e– 2nd I.E. of M

CHECKPOINT 6

The third ionisation energy of aluminium is 2740 kJ mol−1.

Which of the following correctly represents this statement?

A Al(g)  Al(g)3+ + 3e− 3rd I.E. = +2740 kJ mol−1

B Al2+(s)  Al(g)3+ + e− 3rd I.E. = +2740 kJ mol−1

C Al2+(g)  Al(g)3+ + e− 3rd I.E. = −2740 kJ mol−1

D Al2+(g)  Al(g)3+ + e− 3rd I.E. = +2740 kJ mol−1

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5.2 Factors Influencing the Magnitude of Ionisation Energy

Learning outcome
(i) explain the factors influencing the ionisation energies of elements (with the Data Booklet)

Ionisation energies are used to overcome the electrostatic forces of attraction between the valence
electrons to be removed in an atom and the nucleus. Ionisation energy is influenced mainly by the
following 4 factors.

1. The size of the positive nuclear charge (attractive forces) and shielding effect of inner
electrons (repulsive forces)

Shielding effect
most
Nuclear charge effect

Shielding electron

(i) Nuclear Charge (attractive force)

The attractive forces exerted by the nucleus on the valence electrons in an atom are dependent on the
number of protons in the nucleus. As the number of protons increases, the nuclear charge of the
particle gets more and more positive and hence the attraction of the nucleus for the electron
increases and consequently, the ionisation energy increases.

For example, 11Na (11 protons) has a lower nuclear charge than 13Al (13 protons).

(ii) Shielding Effect (repulsive force)

The presence of electrons in the inner shells between the outermost electron and the nucleus
shields the outermost electron from the attraction from the nucleus and consequently reduces the
attraction between them. The greater the number of inner shells electrons, the greater will be the
shielding effect and consequently, the ionisation energy decreases.

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For example, 11Na (1s2 2s2 2p6 3s1) has a lower shielding effect since it only has 10 inner electrons (or
2 inner electronic shells) than 19K (1s2 2s2 2p6 3s2 3p6 4s1) which has 18 inner electrons (or 3 inner
electronic shells).

Electrons within the same shell (for example: 2s and 2p as well as 3s and 3p) exert a negligible
shielding effect on one another.

For example, 11Na (1s2 2s2 2p6 3s1) has approximately the same shielding effect as 13Al (1s2 2s2 2p6
3s2 3p1) since both of them have 10 inner electrons.

(iii) Effective Nuclear Charge – a combination of (i) and (ii)

An electron in the atom faces both the attractive forces exerted by the positively charged nucleus and
the repulsive forces by the inner electrons. Hence, the net attractive force on a valence electron is
actually less than the number of protons in the nucleus. This net attractive force is termed effective
nuclear charge which is a measure of the actual attraction on the outer electrons by the nucleus by
taking into account the nuclear charge and the shielding effect.

Therefore, 13Al has a higher effective nuclear charge than 11Na since it has a higher nuclear charge
but approximately the same shielding effect as 11Na.

EXAMPLE 4

Comment and explain the difference in the first ionisation energy of sodium with that of aluminium and
potassium.

Na Al K
st −1
1 I.E. / kJ mol 494 577 418

Comparing Na and Al:

11Na: 1s22s22p63s1
2 2 6 2 1
13Al: 1s 2s 2p 3s 3p

The 1st ionisation energy of Na is lower (or less endothermic) than that of Al.

Na has a lower nuclear charge than Al but they have approximately the same shielding effect as
both have 2 inner quantum shells. Consequently, the effective nuclear charge of Na is lower than
that of Al. Therefore, lesser amount of energy is required to remove the electron in Na than in Al.

(This explains why the ionisation energy of the elements in the same Period increases across the
Period)

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Comparing Na and K:

11Na: 1s22s22p63s1
2 2 6 2 6 1
19K: 1s 2s 2p 3s 3p 4s

The 1st ionisation energy of Na is higher (or more endothermic) than that of K.

Although K has a higher nuclear charge than Na, it also has a higher shielding effect, due to having
1 more inner quantum shell.
The higher shielding effect of K outweighs its higher nuclear charge compared to Na.
Consequently, the effective nuclear charge of K is lower than that of Na. Therefore, a lower amount
of energy is required to remove the electron in K than in Na.

(This explains why the ionisation energy of the elements in the same Group decreases down the
Group.)

2. The orbital where the electron comes from

The orbital where the electron to be removed comes from also affects the ionisation energy.

For example, the first ionisation energy of boron (+799 kJ mol−1) is lower than that of beryllium (+900
kJ mol−1) despite boron having a higher effective nuclear charge than beryllium.

4Be 1s2 2s2

↿⇂ ↿⇂
1s 2s 2px 2py 2pz

5B 1s2 2s2 2p1

↿⇂ ↿⇂ ↿
1s 2s 2px 2py 2pz

The outermost electron in beryllium is in the 2s subshell, while the outermost electron in boron is in the
2p subshell. As the 2p subshell is at a higher energy level than the 2s subshell, As the average
distance from the nucleus of a 2p orbital is slightly larger than that of a 2s orbital, less energy
is required to remove the 2p electron in boron.

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3. Inter-electronic repulsion between electrons in the same orbital

Ionisation energy can be lowered if the electron is being removed from an orbital is paired as compared
to the case where the orbital contains a singly unpaired electron.

For example, the first ionisation energy of oxygen (+1310 kJ mol−1) is lower than that of nitrogen (+1400
kJ mol−1) even though oxygen has a higher effective nuclear charge than nitrogen.

7N 1s2 2s2 2p3

↿⇂ ↿⇂ ↿ ↿ ↿
1s 2s 2px 2py 2pz

8O 1s2 2s2 2p4

↿⇂ ↿⇂ ↿⇂ ↿ ↿
1s 2s 2px 2py 2pz

The electron to be removed in nitrogen is one of three 2p electrons and it is unpaired and the mutual
repulsion between these electrons is minimised.
However, in oxygen, the electron to be removed in the 2px-orbital is paired and since these two
electrons experience inter-electronic repulsion, it is easier to remove one of them than the p electron
in nitrogen. Hence less energy is required to remove it.

4. The charge of the cation

As the charge of the cation increases, a greater amount of energy is required to remove the subsequent
electron due to an increase in attraction by the same number of protons on a fewer number of electrons,
which results in an increase in the effective nuclear charge.

For example,

Mg(g)  Mg+(g) + e− 1st I.E. = +736 kJ mol−1

Mg+(g)  Mg2+(g) + e− 2nd I.E. = +1450 kJ mol−1

The 1st ionisation energy of magnesium (736 kJ mol−1) is lower than its 2nd ionisation energy (1450 kJ
mol−1). In 12Mg(g) there are 12 protons attracting 12 electrons, while in 12Mg+(g) the 12 protons are
attracting only 11 electrons. Consequently, the effective nuclear charge of 12Mg+(g) is higher than that
of 12Mg(g) and more energy is required to remove the next electron from 12Mg+(g).

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5.3 Successive Ionisation Energies

Learning outcome
(i) deduce the electronic configurations of elements from successive ionisation energy data
(j) interpret successive ionisation energy data of an element in terms of the position of that element within the
Periodic Table

Successive ionisation energies of the same element are always greater in magnitude than the
preceding ones. For instance,

1st I.E. < 2nd I.E. < 3rd I.E. etc

This shows that electrons are being removed with increasing difficulty.
log IE

1st shell: 1s2

“big jump”

2nd shell: 2s2 2p6

‘small jump”

“big jump”

3rd shell: 3s1

1 2 3 4 5 6 7 8 9 10 11 electrons removed

The following 3 questions will explain the above graph in greater detail.

(i) Why is there an increase in the successive ionisation energies?

The general increase in the successive ionisation energies is due to the increasing positive
charge on the cation. As successive electrons are being removed, the same number of
protons is attracting fewer electrons. Consequently, there is an increase in effective
nuclear charge (since nuclear charge remains constant; but shielding effect decreases) of the
cation and requiring more energy to remove the next electron. Also, there is a decrease in the
distance between the electron to be removed and the nucleus.

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(ii) What causes the large increase (ie. big jump) in the ionisation energies?

The large increase (“big jump”) in the ionisation energies indicates the electrons removed
come from a different quantum shells and hence there is a significant decrease in the
shielding effect on the outermost electron (due to decrease in number of inner electrons) while
nuclear charge remains constant. Consequently, there is an increase in effective nuclear
charge and hence more energy is required to remove the electrons in the inner principal
quantum shell.

For example, the 1st ionisation energy of 11Na is much lower than its 2nd ionisation energy.
Both the first electron and second electron that are removed are attracted by eleven protons
however the 1st electron has ten inner electrons (from shells 1 & 2) shielding it while the
second electron is only shielded by two inner electrons (from shell 1).

(iii) What causes the gradual increase (ie. small jump) in the ionisation energies?

The gradual increase (“small jump”) in the ionisation energy indicated that the electrons
removed come from two different sub-shells within the same principal quantum shell. This
gradual increase is due to the electrons removed are in sub-shells of different energy level.

For example, the 7th ionisation energy of 11Na is slightly lower than its 8th ionisation energy. The
7th electron removed is in the 2p subshell, while the 8th is in the 2s subshell. As the 2p subshell
is at a higher energy level than the 2s subshell , As the average distance from the nucleus
of a 2p orbital is slightly larger than that of a 2s orbital, the 7th electron experiences less
attraction to the nucleus than the 8th electron and hence less energy is required to remove it.

CHECKPOINT 7

The following graph shows the ionisation energy for the successive removal of the first 9 electrons in
an atom. Deduce which Group in the Periodic Table the element belongs to and hence deduce its
identity if the element is in Period 2.

log IE

1 2 3 4 5 6 7 8 9
electron removal
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…………………………………………………………………………………………………………………….

…………………………………………………………………………………………………………………….

…………………………………………………………………………………………………………………….

…………………………………………………………………………………………………………………….

…………………………………………………………………………………………………………………….

CHECKPOINT 8

The first eight ionisation energies of an element E are as follows:

790 1600 3200 4400 16100 19800 23800 kJ mol1

State, giving reasons, the Group in the Periodic Table to which E is likely to belong to, and write the
electronic configuration for the outermost shell.

790 1600 3200 4400 16100 19800 23800 kJ mol1

……………………………………………………………………………………………………………………..

……………………………………………………………………………………………………………………..

……………………………………………………………………………………………………………………..

In summary:
 Given the electronic configuration or atomic number of an atom, we can predict the relative
magnitude of the successive ionisation energies of this atom.

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 Given the successive ionisation energies of an unknown element or atom (in the form of
numerical data or a graph), we can identify the number of valence electrons present and
hence the group number of this element, or even its identity.

6 APPLICATIONS IN THE REAL WORLD CONTEXT

Fireworks

Fireworks contain the metal powders and are often coated in gunpowder to aid in ignition. The heat
given off during combustion cause electrons of the metal atoms to be excited to higher energy levels.
These excited states are unstable, so the electron quickly returns to its original energy (or ground
state), emitting excess energy as light. Different metals will have a different energy gap between their
ground and excited states, leading to the emission of different colours.

Sodium-vapour Street Lamps

The lamp contains neon gas and a small amount of sodium solid.
When a current is passed through the lamp tube, neon gas will heat up rapidly and ionise, causing the
lamp to appear red.

When the temperature starts to increase, solid sodium atoms will then vapourise. The vapourised
sodium atoms absorb energy and the electrons are able to move from ground state to excited state.
The electrons will relax back to a lower energy state by emitting photons of bright yellow light, causing
the lamp to appear yellow.

Televisions
Modern plasma television screens emit light when mixtures of noble gases, such as neon and xenon,
are ionised.

CHEM~IS~TRY

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