Students’ Copy

Tampines Meridian Junior College

2024 JC1 H2 Chemistry 9729
Atomic Structure
Lecture Outline
A. Structure and Particles
A.1 Atoms
A.2 Atomic Number, Mass Number and Isotopes
A.3 Deducing the Number of Protons, Neutrons and Electrons in an Atom/Ion

B. Electronic Structure of an Atom

B.1 The Quantum Mechanical Atomic Model
B.2 Relative Energy Levels of Orbitals
B.3 Electronic Configuration of Atoms and Ions

C. Ionisation Energies
C.1 Factors Affecting Ionisation Energies of Elements
C.2 Ionisation Energy Trends in the Periodic Table
C.3 Successive Ionisation Energy Data
C.4 Predicting Group Number of Element from Ionisation Energy Data of Consecutive
Elements

Learning Outcomes (from 9729 syllabus; sections 1,5 and 13)

Candidates 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 the 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) (From Section 5 of syllabus)

describe and explain qualitatively the general trends and variations in first ionisation energy
(1) across a Period in terms of shielding and nuclear charge;

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(2) down a Group in terms of increasing number of electronic shells, shielding and nuclear
charge

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

(l) interpret successive ionisation energy data of an element in terms of the position of that
element within the Periodic Table.

Related Concepts

Understand and be able to define the following terms :

mass number nuclear charge electronic configuration

atomic number screening effect isoelectronic
ionisation energy effective nuclear charge degenerate
(general and specifically,
1st / 2nd)

References

1. Chemistry for Advanced Level, Peter Cann, Peter Hughes

2. A–Level Chemistry (4th Ed), E.N. Ramsden
3. Basic Inorganic Chemistry (3rd Ed), F.A. Cotton, G. Wilkinson, P.L. Gaus
4. Understanding Advanced Physical Inorganic Chemistry, The Learner’s Approach, Jeanne Tan,
Kim Seng Chan
5. Understanding Chemistry for Advanced Level (3rd Ed), Ted Lister, Janet Renshaw

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A. Structure and Particles LO (a): identify and describe protons,

neutrons and electrons in terms of their
relative charges and relative masses
A.1 Atoms
LO (c): describe the distribution of
▪ Atoms are made up of protons, electrons and neutrons. mass and charges within an atom.

▪ Protons and neutrons are located in the nucleus of the atom.

▪ Electrons are found in orbitals around the nucleus.

Nucleus (protons, neutrons)

Electrons (distributed in region of space around nucleus)

Subatomic particles Proton Neutron Electron

Symbol p n e
Actual mass 1.673 x 10–27 kg 1.675 x 10–27 kg 9.109 x 10–31 kg
Relative mass 1
(relative to proton) 1 1
1840
Actual charge +1.602 x 10–19 C 0 –1.602 x 10–19 C
Relative charge
+1 0 –1
(relative to proton)
Location in orbital
in the nucleus in the nucleus
within atom around the nucleus
Deflection in towards towards
not deflected
electric field negative electrode positive electrode

*Values in bold are important values to remember!

Behaviour of sub-atomic particles in an Electric Field

LO (b): deduce the behaviour of
e beams of protons, neutrons and
Deflection of charged sub- + electrons in an electric field.
atomic particles begins only
at the start of the electric
field  Note:  > 
 n
_
- p

Direction of Deflection
• Protons (positively charged) are deflected towards the negative plate.
• Electrons (negatively charged) are deflected towards the positive plate.
• Neutrons (uncharged) are not deflected at all.
• The direction of deflection is dependent on the charge on the subatomic particles.

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Angle / Extent of Deflection

charge charge q
• Angle of deflection  ( is denoted as )
mass mass m

q 1 q -1
for proton = =1; for electron = = 1840
m 1 m 1
1840

Thus, the extent of deflection for electrons is much more than for protons (due to its much
smaller mass).

Example [GCE A]
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,
1
H and 4He nuclei are deflected as follows:
1 +
1H nucleus (ie. H )
A
4He nucleus (ie. 4He2+)
4.0
2.0

source Information about nucleus (plural: nuclei)

B Example
4He → 4He2+ + 2e-
(atom) ( He nucleus) (all e- removed)
4

Giving reasons for your answer, suggest Refer to §A.2 on nuclide notation (to infer
number of protons, electrons, neutrons
(a) the polarity (+ or −) of plate A and §A.1 for relative mass)

(b) why 1H nucleus (1H+) is deflected twice as much as 4He nucleus (4He2+)
(c) the angles of deflection of
2
(i) H nucleus (2H+)
3
(ii) He nucleus (3He2+)

Solution:

(a) the polarity (+ or −) of plate A

▪ Plate A is __________________charged.

▪ ________________ charged 1H and 4He nuclei are attracted to it.

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(b) why 1H nucleus (1H+) is deflected twice as much as 4He nucleus (4He2+)

q
Concept : Extent of deflection 
m

q q
ratio for 1H nucleus (1H+) = __________ ratio for 4He nucleus (4He2+) = _________
m m
Hence 1H nucleus (1H+) is deflected twice as much as 4He nucleus (4He2+).

(c) the angles of deflection of

2
(i) H nucleus (2H+)

q
ratio for 2H nucleus (2H+) = _______________
m
q q
As ratio for 2H nucleus (2H+) = ratio for _____________ nucleus (4He2+)
m m
 angle of deflection of 2H nucleus (2H+) = ____________

3
(ii) He nucleus (3He2+)

q q
ratio for 3He nuclei =___________ ratio for 1H nuclei = ___________
m m

Hence angle of deflection of 3He nuclei = _______________

A.2 Atomic Number, Mass Number and Isotopes

▪ Mass number is the total number of protons and neutrons in the atoms.
▪ Atomic number is the number of protons in an atom (unique for each element).
▪ Nucleon number refer to the number of protons and neutrons in an atom.
▪ Nuclides are any species of given mass number and atomic number.

Nuclides are written as:

Mass number a

X
=p+n
symbol of the element

Atomic number
= p (= e for atoms) b

9
Example: 4 Be
Number of proton = ___ Number of neutrons = ___

Number of electrons = ___

Nucleon number = ____________

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

▪ Isotopes are atoms of the same element which contain the same number of protons but
different number of neutrons.

▪ Isotopes of the same element have similar chemical properties but different physical
properties.

Example:

12 13 14
Isotopes 6 C 6 C 6 C
mass number
p
n
e

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

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

A.3 Deducing the Number of Protons, Neutrons and Electrons in an Atom/Ion

The composition of a particular atom or ion can easily be deduced from the proton number, mass
number and charge on the ion.

A A
Consider an atom, Z X , a positive ion, Z Xn+ , or a negative ion AZ Xn- .

Number of Number of Number of

Symbol
protons neutrons electrons
A
Atom Z X Z A–Z Z
A
Positive ion Z Xn+ Z A–Z Z–n
A
Negative ion Z Xn- Z A–Z Z+n

Practice Example :

Species No. of protons (Z) No. of neutrons (A – Z) No. of electrons

37
17 Cl
207
82 Pb2+
31
15 P3-

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Quick Check 1

14 14
1 Which of the following statements concerning the two atoms 6 C and 7 N are correct?

1 The carbon atom has a higher proton number than the nitrogen isotope.
2 Both isotopes contain 14 nucleons per atom.
3 The carbon isotope has more neutrons per atom than the nitrogen isotope.

A 1, 2 and 3 B 1 and 2 C 2 and 3 D 1

Answer:
14 14
6 C 7 N

Number of proton = Number of proton =

Number of electrons = Number of electrons =
Number of neutrons = Number of neutrons =
Nucleon number = Nucleon number =

2 Which of the following ions has more electrons than protons and more protons than neutrons?
16
[H = 11H ; D = 21H ; O = 8 O ]

A D– B D3O+ C OD– D OH–

Answer:

Species Total no. of protons Total no. of electrons Total no. of neutrons
D–
D3O+
OD–
OH–

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B. Electronic Structure of an Atom

‘O’ Levels ‘A’ Levels

nucleus

1st shell = 2 electrons

2nd shell = 8 electrons

3rd shell = 18 electrons

Protons and neutrons are located in the nucleus.

Electrons are held in fixed circular orbits/shells Electrons are found in a region of space around
around the nucleus. the nucleus known as the atomic orbital.

Electron shells/orbits differ in their energy Electron shells/orbits differ in their energy
levels. levels, shape and orientation in space.
For chloride 17Cl –- For chloride 17Cl –
Electronic configuration : 2.8.8 Electronic configuration : 1s2 2s2 2p6 3s2 3p6

Dot and cross diagram: Dot and cross diagram:

*The above diagram used in O-level is not used *Only outermost electrons need to be shown.
in A-level.

The electronic configuration refers to the arrangement of electrons in the various orbitals around
the nucleus.

The energy level of an electron is determined by 4 characteristics:

• shell (represented by n)
• subshell
• orbital
• spin

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LO (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.

B.1 The Quantum Mechanical Atomic Model

1 Electron Shells
• An electron shell, also known as quantum shell, is a group of subshells that are about
equal distance from the nucleus.
• Each electron shell is assigned a principal quantum number, n, where n = 1, 2, 3 ...
• The first shell (n=1) is closest to the nucleus and has the lowest energy.
• As n increases, the distance of the orbital to the nucleus and hence size of the orbital
increases.

n=1 n=2 n=3

▪ The larger the value of n,

 the further the electron is to the nucleus.
 the less strongly the electron is bound to the nucleus.
 the higher the energy level of the electron.

2 Subshells

▪ A subshell is a group of orbitals with the same energy level (degenerate) but different
orientation in space.

▪ Subshells are labelled as s, p, d or f.

Relationship between Subshells and Orbitals

Each subshell contains a fixed number of orbitals in which the electrons are found.

Subshell No. of Orbitals Type of Orbitals

s 1 s
p 3 px, py, pz
d 5 dxy, dyz, dxz, dx2– y2, dz2
f 7

▪ Generally, the order of energy levels for the subshells within each quantum shell is:
s<p<d<f.

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3 Atomic Orbitals LO (g): describe the shapes of s, p and d orbitals

▪ Atomic orbitals can be defined as a region of space round the nucleus where there is a
high probability of finding an electron at any moment.

▪ Each orbital can hold a maximum of 2

electrons.

▪ Electrons occupy four types of atomic orbitals.

▪ They are the s orbitals, p orbitals, d orbitals

and f orbitals. They differ in shape and spatial
distribution.

A. Shapes and Sizes of Atomic Orbitals

Learn how to describe and draw the shapes
and orientations of s, p and d orbitals.
s orbitals

• The s orbital is spherical in shape and non-directional.

(Non–directional means the probability of finding an electron at a particular distance from the
nucleus is same in all directions.)

• The size of the s orbitals increases with principal quantum number.

e.g. size of 1s orbital < 2s orbital < 3s orbital

1s 2s 3s

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p orbitals (3 types: px, py and pz)

• There are three different types of p orbitals (px, py, pz).

• The p orbitals are “dumb–bell” shaped and directional as they are directed towards x, y and z
axes.
• The three p orbitals have different orientation in space.
• The size of the p orbitals increases with principal quantum number.
e.g. size of 2p orbital < 3p orbital

px orbital lies along py orbital lies along pz orbital lies along

the x axis the y axis the z axis

A p subshell consisting of
three p orbitals.
x
z

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d orbitals (5 types: dxy, dyz, dxz, dx2– y2, dz2)

• There are five different types of d orbitals (dxy, dyz, dxz, dx2– y2, dz2 ).
• d orbitals have two fundamental shapes.
o Four of the five d orbitals (dxy, dyz, dxz, dx2– y2) have four lobes (“butterfly shape”).
o The fifth d orbital (dz2) has two lobes along the z axis and a “doughnut” centred in the
xy plane.

• The five d orbitals are directional and have different orientation in space.

• The size of the d orbitals increases with principal quantum number.

e.g. size of 3d orbital < 4d orbital.

dxy orbital lies in the x-y plane dyz orbital lies in the y-z dxz orbital lies in the x-z plane
with the lobes directed plane with the lobes directed with the lobes directed
between the axes between the axes between the axes

dx2– y2 orbital lies in the x-y dz2 orbital has a dumbbell

plane with the lobes shape with collar
directed along the axes surrounding this dumbbell

A d subshell consisting of
five d orbitals.

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4 Spin Quantum Number, ms

1 1
▪ ms = + or –
2 2

▪ Indicates the direction of spin of electrons i.e. clockwise ( ) and anti–clockwise ( )

▪ Two electrons in the same orbital must have opposite spins.

▪ This is so that magnetic attraction which results from their opposite
spins can counterbalance the electrical repulsion which results
from their identical charges.

Relationship between quantum number, subshells, orbitals and electrons

Example
For quantum shell n = 3, there are 3 subshells :
• 3s subshell (contains one 3s orbital),
• 3p subshell (contains three 3p orbitals :3px, 3py, 3pz) and
• 3d subshell (contains five 3d orbitals : 3dxy, 3dyz, 3dxz, 3dx2– y2, 3dz2)

3s 3p 3d

quantum shell, n = 3 3p subshell 3d orbital

Electron shell Electron subshell Atomic orbital electrons

Principal No. of
Type of Maximum number of
quantum subshells No. of orbitals Type of orbitals
subshell electrons
number, n (=n)
1 1 1s 1 1s 2
2s 1 2s 2
2 2
2p 3 2px, 2py and 2pz 6
3s 1 3s 2
3p 3 3px, 3py and 3pz 6
3 3
3dxy, 3dyz, 3dxz,
3d 5 10
3dx2– y2, 3dz2
4s 1 4s 2
4p 3 4px, 4py and 4pz 6
4 4 4dxy, 4dyz, 4dxz,
4d 5 10
4dx2– y2, 4dz2
4f 7 not required 14

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LO (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.

B.2 Relative Energy Levels of Orbitals

• In an atom, the orbitals have different energy levels, with the orbital nearest to the
nucleus having the lowest energy level.
• As n increases, the energy levels come closer to each other.
• As a result, overlapping of subshells occur. The first overlap occurs between the 3d
and the 4s subshells. Hence, the 4s orbitals are filled up before 3d orbitals.

The relative energy levels of the quantum shells and subshells in an atom:

Energy

4f
n=4
4d 4d xy 4d yz 4d xz 4d x 2 − y 2 4d z2

4p 4px 4py 4pz

3d 3d xy 3d yz 3d xz 3d x 2 − y 2 3d z2

n=3 4s 4s

3p 3px 3py 3pz

3s 3s

2p 2px 2py 2pz

n=2
2s 2s

n=1 1s 1s

Shells subshells orbitals

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The following is a simplified energy level diagram of an atom:

Energy

4f

4d

4p

3d

4s
Important note: 4s subshell has a lower energy
level than 3d subshell (when it is not occupied
3p by electrons).

Once the 4s subshell is occupied by electrons,

3s
4s subshell will have a higher energy level than
3d subshell due to repulsion and close energy
gap between of 4s and 3d subshells.

2p

2s

1s

Quick-Check 2 [GCE A]

Which of the following statements about the s, p and d orbitals of principal quantum numbers 1, 2
and 3 are true?

1 Each s orbital can contain a maximum of two electrons.

2 An empty 3d orbital has a higher energy than an empty 4s orbital.
3 In principal quantum number n = 3, there are 3 subshells containing a total of
9 orbitals.

A 1, 2 and 3 B 1 and 2 C 1 and 3 D 1

Answer:

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B.3 Electronic Configuration of Atoms and Ions

LO (h): state the electronic configuration of atoms
B.3.1 Definition and ions given the proton number (and charge)

• The electronic configuration of an atom or ion refers to the arrangement of electrons in its
shells, subshells and orbitals.

Notation for writing electronic configuration:

principal quantum 1 number of electrons in

number 2p subshell

subshell

B.3.2 Rules for arrangement of electrons in atoms

Rule 1: The Aufbau Principle

▪ Electrons occupy the lowest energy orbital first before occupying the higher energy orbitals.

Order of filling orbitals:

IMPORTANT NOTE
▪ 4s has lower energy level than 3d when empty.

▪ When adding electrons, fill up 4s before 3d.

▪ 4s has higher energy level than 3d when filled.

▪ When removing electrons, remove from 4s before 3d.

Rule 2: Pauli's Exclusion Principle

▪ Each orbital can hold a maximum of 2 electrons. The two electrons must be in opposite spins.

NOT

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Rule 3: Hund's Rule

▪ Orbitals of a subshell must be occupied singly by electrons with parallel spins before pairing
occurs. This is to ensure electrons are as far apart as possible to minimise electron repulsion.

NOT NOT

Note:
▪ When an orbital contains only one electron, the electron is said to be unpaired.

B.3.3 Writing Electronic Configurations

Atoms

Atomic Writing the Ground State

Element Ground State Electronic Configuration
Number Electronic Configuration

Ne 10 ___ ___ ___ ___ ___ 1s2 2s2 2p6

1s 2s 2p

Cl 17 ___ ___ ___ ___ ___ ___ ___ ___ ___ 1s2 2s2 2p6 3s2 3p5
1s 2s 2p 3s 3p

___ ___ ___ ___ ___ ____ ___ ___ ___ ___
Ca 20
1s 2s 2p 3s 3p 4s

___ ___ ___ ___ ___ ____ ___ ___ ___ 1s2 2s2 2p6 3s2 3p6 3d3 4s2
1s 2s 2p 3s 3p ▪ When adding electrons, fill up 4s
V 23 before 3d.
___ ___ ___ ___ ___ ___ ▪ 4s has higher energy level than 3d
when filled.
3d 4s

___ ___ ___ ___ ___ ____ ____ ___ ___

 Cr 1s 2s 2p 3s 3p
24 1s2 2s2 2p6 3s2 3p6 3d5 4s1
___ ___ ___ ___ ___ ___
3d 4s

___ ___ ___ ___ ___ ____ ____ ___ ___

 Cu 1s 2s 2p 3s 3p
29 1s2 2s2 2p6 3s2 3p6 3d10 4s1
___ ___ ___ ___ ___ ___
3d 4s

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 Explanation:

▪ In 3d–block elements, the 3d and 4s orbitals are close in energy, with the 4s orbital being lower
in energy. Hence, the 4s orbitals are filled first, followed by the 3d orbitals.
▪ Exceptions:
▪ Cr atom gains extra stability with half–filled 3d subshell.
The configuration 1s2 2s2 2p6 3s2 3p6 3d5 4s1 is more stable than 1s2 2s2 2p6 3s2 3p6 3d4 4s2.
▪ Cu atom gains extra stability with a fully–filled 3d subshell.
The configuration 1s2 2s2 2p6 3s2 3p6 3d10 4s1 is more stable than 1s2 2s2 2p6 3s2 3p6 3d9 4s2.

These configuration are preferred as they result in a more symmetrical 3d electron cloud that
shield the nucleus more effectively.

Ions

Ground State Electronic Writing the Ground State Electronic

Particle Symbol Configuration Configuration

Atom F ___ ___ ___ ___ ___ 1s2 2s2 2p5

1s 2s 2p

Ion F– ___ ___ ___ ___ ___

1s 2s 2p

Atom Mg ___ ___ ___ ___ ___ ___ 1s2 2s2 2p6 3s2
1s 2s 2p 3s

Ion Mg2+ ___ ___ ___ ___ ___

1s 2s 2p

Ground State and Excited States

▪ A species (atom or ion) is in the ground state when its electron occupy the lowest energy levels.
▪ When the electron receives energy and is promoted to a higher energy level, the species
becomes unstable and is said to be in an excited state.
Consider an 8O atom:
Ground state electronic configuration is 1s22s22p4
An example of excited state electronic configuration of 8O atom: 1s22s22p33s1

Quick-Check 3 [GCE A]
A species Z has the following electronic configuration.

1s 2s 2p 3s 3p

What could Z be? 1. Cl+ ion:

1 Cl+ ion 2. S atom:

2 S atom 3. Ar2– ion:
3 Ar2– ion

A 1, 2 and 3 B 1 and 2 only C 1 and 3 only D 1 only

Answer:

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Example: On how to draw energy level diagram

Draw the energy level diagram and write the electronic configuration of each of the following
particles.

(a) Be (b) O2–

energy energy

2p

2s 2s

1s 1s

Electronic configuration of Be: Electronic configuration of O2– :

(c) Fe2+ (d) Cu2+

energy energy

4s 4s

3d 3d
3p 3p
3s 3s

2p 2p
2s 2s

1s 1s

Electronic configuration of Fe : Electronic configuration of Cu :

Electronic configuration of Fe2+ : Electronic configuration of Cu2+:

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Atoms / ions with the:

▪ same number of electrons (i.e. same electronic configuration) are said to be isoelectronic.
▪ same number of protons are isotopic.
▪ same number of neutrons are isotonic.

Isoelectronic species Electronic configuration Note

Ne Electronic configuration can
O2– 1s2 2s2 2p6 also be represented using a
Na+ noble gas ‘core’
Ar e.g. electronic configuration of
P3– 1s2 2s2 2p6 3s2 3p6 O2– represented as [Ne] and
Ca2+ that of Ca2+ as [Ar]

An alternative method to present electronic configuration is to replace the inner electronic

configuration with a noble gas symbol.

Example: Consider 26Fe

The full electronic configuration of Fe is 1s2 2s2 2p6 3s2 3p6 3d6 4s2.
The noble gas electronic configuration of Fe is [Ar] 3d6 4s2.

Note:
• When asked to state the electronic configuration, always give the full electronic configuration.
• You can only give the noble gas configuration when you want to support explanations for ionisation
energies questions.

Quick-Check 4 [N2016 P1 Q4 modified]

37 - 36 2-
What do the ions Cl and S have in common?

1 Both ions contain the same number of nucleons in their nuclei.

2 Both ions have more electrons than neutrons.
3 Both ions are isoelectronic with an outer electronic configuration of 3s2 3p6.

A Only 2 is correct
B Only 3 is correct
C Only 2 and 3 are correct
D 1, 2 and 3 are correct

Answer:
37 - 36 2-
17Cl 16S

Number of proton = Number of proton =

Number of electrons = Number of electrons =
Electronic configuration: Electronic configuration:
Number of neutrons = Number of neutrons =
Number of nucleons = Number of nucleons =

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B.3.4 Relationship between Electronic Configuration and Group Number

▪ Elements in the same (main) groups have the same outermost electronic configuration in their
atoms.

Group 1 2 13 14 15 16 17 18

Outermost
ns1 ns2 ns2 np1 ns2 np2 ns2 np3 ns2 np4 ns2 np5 ns2 np6
electronic
configuration except He

s–block d–block p–block

s-block

s-block p-block

d-block

f-block

▪ Another illustration:

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C. Ionisation Energies
Ionisation involves the removal of electrons, forming a cation. As the negatively charged electrons
are attracted to the positively charged nucleus, their removal requires the absorption of energy.

Definition of First Ionisation Energy:

First ionisation energy is the energy required to remove one mole of electrons from
one mole of gaseous atoms of the element to form one mole of singly positively charged
gaseous ions.
X (g) ⎯→ X+ (g) + e–

*state symbols are necessary for ionisation energy equations.

Example

First I.E. of magnesium: Mg (g) ⎯→ Mg+ (g) + e– 1st I.E. = +736 kJ mol–1

Definition of Second Ionisation Energy:

Second ionisation energy is the energy required to remove one mole of electrons from
one mole of singly positively charged gaseous ions to form one mole of doubly positively
charged gaseous ions.

X+ (g) ⎯→ X2+ (g) + e–

Example

Second I.E. of magnesium: Mg+ (g) ⎯→ Mg2+ (g) + e– 2nd I.E. = +1450 kJ mol–1

Note:
▪ The higher the ionisation energy of an element, the more difficult it is to remove an electron.
▪ For an element, its 2nd I.E. > 1st I.E. because more energy is required to remove an electron
from a positively charged ion compared to a neutral atom due to stronger net electrostatic
attraction.
▪ COMMON MISTAKE:
Mg(g) ⎯→ Mg2+(g) + 2e– does not represent 2nd ionisation energy.
The above equation represents the SUM of 1st I.E. and 2nd I.E.

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LO (i): explain the factors influencing the ionisation energies of elements
C.1 Factors Affecting Ionisation Energies of Elements

(a) Nuclear Charge (attraction towards nucleus)

▪ Nuclear charge is the attractive force of protons in the nucleus for electrons.

▪ The higher the number of protons in the nucleus, the stronger the nuclear charge.

(b) Screening (or shielding) Effect (repulsion away from nucleus)

▪ Screening effect is the shielding of the valence electrons from the electrostatic
attraction of the positively charged nucleus mainly by the inner shell electrons.

▪ Inner shell electrons shield the valence electrons much more effectively than
the electrons in the same valence shell.

▪ As shielding effect increases, the attraction of the nucleus for the valence electron
decreases, and less energy is required to remove an electron, i.e. ionisation energy
decreases.

nucleus

inner shell electrons

valence electrons

The Effective Nuclear Charge acting on an electron is the net electrostatic attraction
between the positively charged nucleus (due to the protons present) and the valence
electron that is to be removed.

It is the combined effect of nuclear charge and screening effect, and can be approximated
by:
Effective nuclear charge ≈ nuclear charge – shielding effect

The stronger the effective nuclear charge:

 the stronger the electrostatic forces of attraction between the nucleus and the valence
electron.
 the higher the ionisation energy.

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LO (j): describe and explain qualitatively the general trends and variations in first ionisation energy
(1) across a Period in terms of shielding and nuclear charge

C.2 Ionisation Energy Trends in the Periodic Table

C.2.1 Variation of lonisation Energies Across a Period

The following figure shows the variation of ionisation energies across Periods 2 and 3.

Trend: Ionisation energy generally increases across the period.

Explanation
Across a period,
▪ the number of protons increases, hence nuclear charge increases.
▪ Shielding effect remains relatively constant since the inner quantum shells of electrons
remain the same.
▪ Effective nuclear charge increases, resulting in stronger electrostatic attraction between the
nucleus and the valence electrons.
▪ Hence, more energy is required to remove the valence electron, and first ionisation energy
generally increases across the period.

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Deviations from General Trend

np electron has higher

energy than ns electron Inter-electronic repulsion between
paired electrons in np orbital

For Period 3 Elements

1. 1st I.E of Group 13 element < 1st I.E of Group 2 element

Example: 1st I.E. of Al < 1st I.E. of Mg

Al: Al (g) ⎯→ Al+ (g) + e–

2 2 6 2 1
1s 2s 2p 3s 3p 1s2 2s2 2p6 3s2

Mg: Mg (g) ⎯→ Mg+ (g) + e–

1s2 2s2 2p6 3s2 1s2 2s2 2p6 3s1

• The 3p valence electron to be removed from Al has higher energy than the 3s valence
electron in Mg.

• Hence, less energy is required to remove the 3p electron in Al than the 3s electron in Mg,
and first ionisation energy of Al is lower than that of Mg.

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

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2. 1st I.E of Group 16 element < 1st I.E of Group 15 element

Example: 1st I.E. of S < 1st I.E. of P

S: S (g) ⎯→ S+ (g) + e–
1s2 2s2 2p6 3s2 3p4 1s2 2s2 2p6 3s2 3p3

P: P (g) ⎯→ P+ (g) + e–
1s2 2s2 2p6 3s2 3p3 1s2 2s2 2p6 3s2 3p2

• Inter–electron repulsion is present between the paired electrons in 3p orbital of S atom.

• Hence less energy is required to remove the valence electron from S, and first ionisation energy
of S is lower than that of P.

LO (j): describe and explain qualitatively the general trends and variations in first ionisation energy
(2) down a Group in terms of increasing number of electronic shells, shielding and nuclear charge

C.2.2 Variation of Ionisation Energies Down a Group

The following figures show the variation of ionisation energies down Group 1 and 2.

Group 1 elements Group 2 elements

600 1000
1st Ionisation energy/ kJ mol-1

1st Ionisation energy/ kJ mol-1

500 800
400
600
300
400
200
100 200

0 0
Li Na K Rb Cs Be Mg Ca Sr Ba
Elements Elements

Trend: Ionisation energy decreases down the group.

Explanation
Down the group,
▪ the number of protons increases, hence nuclear charge increases.
▪ However, the number of electron shells and shielding effect also increases.
▪ Hence, the valence electrons experience weaker electrostatic forces of attraction to the
nucleus.
▪ Less energy is required to remove the valence electron, and first ionisation energy decreases
down the group.

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C.2.3 Comparison of lonisation Energies between Periods

The first ionisation energy between Group 18 element of a Period (Noble gas) and the
succeeding Group 1 element of the next Period decreases significantly.

1st I.E. of Na < 1st I.E. of Ne

11Na: 1s2 2s2 2p6 3s1 10Ne: 1s2 2s2 2p6

• Na has a higher nuclear charge than Ne.

• However, the valence 3s electron in Na experiences stronger shielding effect due
to additional inner shell of electrons compared to the 2p electron in Ne.
• Hence the valence 3s electron in Na experiences weaker electrostatic attraction
to the nucleus.
• Less energy is required to remove the 3s electron in Na than the 2p electron in Ne,
and first ionisation energy of Na is lower than that of Ne.

Note: explanation used here is similar to “Down the Group” explanation (see C2.2).

Quick Check 5 [GCE A]

Why is the first ionisation of neon higher than that of fluorine?

A Fluorine is more electronegative than neon.

B Neon has a complete octet, but fluorine does not.
C The atomic radius of fluorine is less than that of neon.
D The nuclear charge in neon is greater than that in fluorine.

Answer:
(1st I.E. of Ne is higher since ______________________________________ but shielding effect is
relatively constant since the electron is added to the same outermost shell.)

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LO (k): deduce the electronic configurations of elements from successive ionisation energy data.

C.3 Successive Ionisation Energy Data

Successive ionisation energy refer to the energy required to remove each of the electrons
from an atom, one after another.

Trend: Successive ionisation energy always increases for the same atom, i.e.
1st I.E. < 2nd I.E. < 3rd I.E.

Example:
O (g) ⎯→ O+(g) + e– 1st I.E. of oxygen = +1310 kJ mol–1
O+(g) ⎯→ O2+(g) + e– 2nd I.E. of oxygen = +3390 kJ mol–1
O2+(g) ⎯→ O3+(g) + e– 3rd I.E. of oxygen = +5320 kJ mol–1

Explanation
• After removal of the first electron, there are less electrons than protons.
• The remaining electrons are more strongly attracted to the constant positive nuclear charge
(number of protons remain the same).
• Hence, the electrostatic attraction between the nucleus and remaining electrons
increases.
• More energy is required to remove an electron.

Use of Successive Ionisation Data

The following information can be obtained from plotting successive ionisation energies against the
order of removal of electrons:
1. number of electrons in an atom
2. number of quantum shells (and number of subshells) occupied
3. group number of an element

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LO (l): Interpret successive ionisation energy data of an element in terms of the position of that element
within the Periodic Table

Example 1: Given successive IE information in graphical form

The element M has the following successive ionisation energies when all its electrons are
successively removed.

log10 I.E.

Outermost 1 2 3 4 5 6 7 8 9 10 11 12 Inner
electrons electrons
Order of electrons removed

a) Deduce the group which element M belongs to.

Method: 1. Find the largest difference / sharp increase in I.E. values.

2. Determine the number of valence electrons, and hence group number.

Concept: Sharp increase in I.E.  change in principal quantum shell

• There is a _______________________ between the 2nd and 3rd ionisation energy.

 _______ electron is removed from an _________________quantum shell which
is closer to the nucleus.
 Much stronger electrostatic attraction between the ______ electron and the
nucleus compared to the first 2 electrons. Hence, a lot more energy is required to
remove it.

• ________________ electrons are removed from the outermost / valence shell.

 There are only ______ valence electrons in the outermost/ valence shell.
 Element M is in Group ______.

Note:
The smaller jump in ionisation energies (e.g. from 8th to 9th I.E.) is due to a change
in subshell. The 8th electron is removed from the 2p subshell while the 9th electron is
removed from the 2s subshell. Since 2s electron has lower energy compared to the 2p
electron, more energy is required to remove the 2s electron.

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b) Deduce the number of occupied quantum shells in element M.

• There are ___________sharp increases in ionisation energies, i.e. between the 2nd and
3rd ionisation energies, and between the ______________________ ionisation energies.
• This indicates the presence of _____ occupied quantum shells.

c) Write the electronic configuration of element M.

Electronic configuration: __________________

Example 2: Given successive IE information in table form

Use the following data to predict, with reasoning, the group which this element belongs to.
Hence, write its general valence electronic configuration.

1st 2nd 3rd 4th 5th 6th 7th

I.E. / kJ mol–1 760 1600 3200 4400 16100 19800 23800

Method: 1. Find the largest difference / sharp increase in I.E. values.

2. Determine the number of valence electrons, and hence group number.

Explanation
• The largest increase is between __________________________ ionisation energy.
 ___ electron is removed from an ________ quantum shell which is closer to the
nucleus.
 There is much stronger electrostatic attraction between the _______ electron and
the nucleus compared to the first _______ electrons. Hence, a lot more energy is
required to remove it.
• ___________ electrons are removed from the outermost / valence shell.
 There are only _____ valence electrons in the outermost / valence shell.
 The element is in Group 14.
 The valence electronic configuration of the element is ____________

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C.4 Predicting Group Number of Element from Ionisation Energy Data of

Consecutive Elements

Example
The following graph shows the plot of the third ionisation energies of consecutive elements A – G
with atomic numbers less than 20.

3rd IE / kJ mol-1

6000

4000

2000 Elements
A B C D E F G

Suggest, with reasoning, the group number for element D.

Answer:

Element D is in Group _______.

Reason: Element A has the ____________ 3rd I.E.

 removal of ________ electron is from an inner quantum shell, which experiences
much stronger electrostatic attraction to the nucleus.
 element A has _____ valence electrons.
 element A is in Group ______.

Since element A – G are consecutive elements, element D is in Group ______.

Trends:
Group 1 elements have high 2nd I.E.
Group 2 elements have high 3rd I.E.
Group 13 elements have high 4th I.E.
Group 14 elements have high 5th I.E.
Group 15 elements have high 6th I.E.
Group 16 elements have high 7th I.E.
Group 17 elements have high 8th I.E.

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Annex: Atomic Theory (for self-reading)

The atomic model has changed over time with the surfacing of new evidence relating to the structure
of an atom. The development of atomic theory has come a long way since John Dalton’s work, and
our understanding of the nature of matter and the structure of atoms has deepened with the work of
scientists such as J. J. Thompson, Ernest Rutherford, Niels Bohr, Louis de Broglie, Erwin
Schrödinger and Werner Heisenberg, just to name a few.

Today, the atom is still a basic unit of matter and the current quantum mechanical model of an atom
features a dense central nucleus comprising protons and neutrons, surrounded by a cloud of
electrons, and we also know that although the electron is a true fundamental particle, the proton and
neutron are themselves made up of more elementary particles known as quarks.

Visit these websites to explore more about the evolution of the atomic model over the centuries.

http://ed.ted.com/lessons/
the-2-400-year-search-
for-the-atom-theresa- How do we know what matter is made of? The
The 2,400-year doud quest for the atom has been a long one, beginning
1 search for the 2,400 years ago with the work of a Greek
atom philosopher and later continued by a Quaker and a
few Nobel Prize-winning scientists.

Chemistry & https://www.youtube.com The model of the atom has undergone steady
Physics: History /watch?v=-4Us5PTb4J8 changes to reflect experimental results, starting
of the Atom with John Dalton's model (1803), to JJ Thomson's
2 (Dalton, model (1897), to Ernest Rutherford's model (1911),
Thomson, to Niels Bohr's model (1913). Our current atomic
Rutherford, and model, the "quantum mechanical model," will be
Bohr Models) discussed in a separate video.
https://www.youtube.com
/watch?v=DiOBvVkLHrA
The History of This short podcast provides a summary of the
Atomic Theory | A works of the four most important scientists in the
3
Podcast for AS evolution of Atomic Theory: John Dalton, J.J.
Level Chemistry Thomson, Ernest Rutherford, and Henry Moseley.

https://www.youtube.com
/watch?v=thnDxFdkzZs
This is from the Crash Course Chemistry series
The History of providing a quick snippet of the history behind the
4
Atomic Chemistry development of the understanding of atomic
chemistry.

Food for thought

1. Why are there multiple models of an atom? Why is there a need to review the earlier atomic
models?
2. Propose reasons on why electron is discovered first and neutron is discovered last.
3. Given the historical development of the atomic model, describe how scientific knowledge is
constructed.

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