Cambridge (CIE) AS Your notes

Chemistry
Ionisation Energy
Contents
Defining Ionisation Energy
Ionisation Energy Trends
Ionisation Energy & Electronic Configuration

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 Defining Ionisation Energy
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Ionisation Energy Definition & Equations

Ionisation is the process by which an electron is removed from an atom or a molecule

Process of ionisation

In the first ionisation of sodium, the single outer electron is lost

The ionisation energy (IE) of an element is the amount of energy required to remove one
mole of electrons from one mole of gaseous atoms of an element to form one mole of
gaseous ions
Ionisation energies are measured under standard conditions which are 298 K and 101
kPa
The units of IE are kilojoules per mole (kJ mol-1)
The values for ionisation energies are always positive as this is an endothermic process
This is because energy is required to break the force of attraction between the
electron and the central positive nucleus

First ionisation energy

The first ionisation energy (IE1) is the energy required to remove one mole of electrons
from one mole of gaseous atoms of an element to form one mole of gaseous 1+ ions
E.g. the first ionisation energy of gaseous calcium:
Ca (g) → Ca+ (g) + e- IE1 = +590 kJ mol-1

Second ionisation energy

The second ionisation energy (IE2) of an element is the amount of energy required to
remove one mole of electrons from one mole of gaseous 1+ ions of an element to form
one mole of gaseous 2+ ions

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 E.g. the second ionisation energy of gaseous calcium:
Ca+ (g) → Ca2+ (g) + e- IE2 = +1145.4 kJ mol-1 Your notes

Examiner Tips and Tricks

It is a common mistake to write ionisation energies in more than one step
For example; Ca (g) → Ca2+ (g) + 2e-
Ionisation energies should take place one step at a time
Students often miss out the gaseous state symbol in the equation and also in the
definition, so make sure you include this

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 Ionisation Energy Trends
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Trends in Ionisation Energy

Ionisation energies show periodicity, a recurring trend across each period of the
Periodic Table
As you move left to right across a period, first ionisation energy generally
increases
This trend is linked to the electronic configuration of elements:
Group 1 metals (e.g. Na) have low first ionisation energies because they have a
single outer electron that is easy to remove
Noble gases (e.g. Ne, Ar) have very high ionisation energies due to their full
outer shells and strong nuclear attraction
There are four factors that affect ionisation energy
Nuclear charge
Distance from the nucleus
Electron shielding
Spin-pair repulsion

Nuclear charge (number of protons)

As atomic number increases, so does the positive charge of the nucleus
A higher nuclear charge creates a stronger electrostatic attraction between the
nucleus and outer electrons
Therefore more energy is required to remove the electron means a higher ionisation
energy

Distance from the nucleus (atomic radius)

Outer electrons that are further from the nucleus experience weaker attraction
The greater the distance, the easier it is to remove the electron
Ionisation energy decreases with increased distance from the nucleus

Electron shielding (inner shell repulsion)

Electrons in inner shells repel electrons in outer shells and partially block the attraction
of the nucleus
This is known as the shielding effect
More inner electron shells means greater shielding and therefore a lower ionisation
energy

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Spin-pair repulsion (electron–electron repulsion)
In orbitals that contain two electrons, the electrons experience repulsion due to their Your notes
like charges
This repulsion slightly reduces the energy needed to remove one of the electrons
This explains small drops in ionisation energy across a period, such as:
Oxygen vs nitrogen (O’s paired 2p electrons are easier to remove)
Aluminium vs magnesium (Al’s 3p¹ electron is higher in energy than Mg’s 3s²)

Ionisation Energy & the Periodic Table

Across a period:
first ionisation energy increases due to higher nuclear charge and same shielding
Down a group:
first ionisation energy decreases due to greater atomic radius and more shielding

Graph of first ionisation energies from H to Na

There are ionisation energy trends within periods and groups

Ionisation energy across a period

Across a period, ionisation energy increases because:
Nuclear charge increases, pulling electrons closer
Atomic radius decreases, reducing the distance to outer electrons
Shielding stays roughly constant, since electrons are added to the same shell
Outer electrons are held more tightly, so more energy is needed to remove them

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Dips in the trend
There is a slight decrease in IE1 between beryllium and boron as the fifth electron in Your notes
boron is in the 2p subshell, which is further away from the nucleus than the 2s subshell of
beryllium
Beryllium has a first ionisation energy of 900 kJ mol-1 as its electron configuration
is 1s2 2s2
Boron has a first ionisation energy of 800 kJ mol-1 as its electron configuration
is 1s2 2s2 2px1
There is a slight decrease in IE1 between nitrogen and oxygen due to spin-pair
repulsion in the 2px orbital of oxygen
Nitrogen has a first ionisation energy of 1400 kJ mol-1 as its electron configuration is
1s2 2s2 2px1 2py1 2pz1
Oxygen has a first ionisation energy of 1310 kJ mol-1 as its electron configuration is
1s2 2s2 2px2 2py1 2pz1
In oxygen, there are 2 electrons in the 2px orbital, so the repulsion between those
electrons makes it slightly easier for one of those electrons to be removed

Ionisation energy down a group

The ionisation energy down a group decreases due to the following factors:
The number of protons in the atom is increased, so the nuclear charge increases
But, the atomic radius of the atoms increases as you add more shells of electrons,
making the atoms bigger
So, the distance between the nucleus and outer electron increases as you descend
the group
The shielding by inner shell electrons increases as there are more shells of electrons
These factors outweigh the increased nuclear charge, meaning it becomes easier
to remove the outer electron as you descend a group
So, the ionisation energy decreases

Table summarising ionisation energy trends across a period &

down a group
Across a period: Ionisation energy Down a group: Ionisation energy
increases decreases

Increase in nuclear charge Increase in nuclear charge

The same number of shells Increased number of shells

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 Distance from the outer electron to the Distance from the outer electron to the
nucleus decreases nucleus increases
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Shielding remains relatively constant Shielding increases

Decreased atomic / ionic radius Increased atomic / ionic radius

The attraction between the outer electron The attraction between the outer electron
and the nucleus gets stronger so the outer and the nucleus gets weaker so the outer
electron is harder to remove electron is easier to remove

Successive Ionisation Energies of an

Element
Successive ionisation energies of an element increase
This is because once the outer electron is removed, the atom becomes a positive ion,
making further electron removal more difficult
As more electrons are removed:
Shielding decreases
The proton-to-electron ratio increases
Attraction between nucleus and remaining electrons increases
The increase is not constant, it depends on the electronic configuration
Taking calcium as an example:

Table showing the successive ionisation energies of calcium

table
Electronic 1s2 2s2 2p6 3s2 1s2 2s2 2p6 3s2 1s2 2s2 2p6 1s2 2s2 2p6
Configuration 3p6 4s1 3p6 3s2 3p5 3s2 3p4

IE First Second Third Fourth

IE (kJ mol-1) 590 1150 4940 6480

Successive ionisation energies of calcium

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 Your notes

Graph to show the successive ionisation energies for the element calcium

The first ionisation energy is relatively low due to spin-pair repulsion in the 4s orbital
The second electron is harder to remove because this repulsion is no longer present
The third ionisation energy increases sharply as the electron is removed from the 3p
subshell, which is closer to the nucleus
The fourth electron is also more difficult to remove due to reduced spin-pair repulsion
within the 3p orbital
Successive ionisation energies always increase because electrons are being removed
from an increasingly positive ion
A large jump in ionisation energy indicates a change in shell, while smaller jumps reflect
changes within the same shell or subshell

Using successive ionisation data

Helps predict or confirm electronic configuration.
Identifies the number of outer-shell electrons.
Indicates the group number by locating the position of a significant jump in ionisation
energy.
Commonly applied to elements like sodium (Na), magnesium (Mg), and aluminium (Al)
to deduce their place in the Periodic Table.

Successive ionisation energies table

Element Atomic Number Ionisation Energy (kJ mol-1)

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 First Second Third Fourth
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Na 11 494 4560 6940 9540

Mg 12 736 1450 7740 10500

Al 13 577 1820 2740 11600

Sodium
A large increase between the first and second ionisation energies shows that the first
electron is much easier to remove than the second
This first electron is in the 3s subshell
This is the outermost shell
This electron experiences less nuclear attraction due to shielding and distance
from the nucleus
This suggests Na has one valence electron, so it belongs to Group 1
The jump corresponds to removing the next electron from the 2p subshell, which is
closer to the nucleus and more strongly held
Na: 1s2 2s2 2p6 3s1

Magnesium
A large increase between the second and third ionisation energies shows that the first
two electrons are easier to remove than the third
These two electrons are in the 3s subshell
This is the outermost shell
These two electrons experience less nuclear attraction due to shielding and
distance from the nucleus
This suggests Mg has two valence electrons, so it belongs to Group 2
The jump corresponds to removing the next electron from the 2p subshell, which is held
more tightly
Mg: 1s2 2s2 2p6 3s2

Aluminium
A large increase between the third and fourth ionisation energies shows that the first
three electrons are easier to remove
These three electrons are in the 3s and 3p subshells
These are part of the outermost shell

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 These three electrons experience less nuclear attraction due to shielding and
distance from the nucleus
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This suggests Al has three valence electrons, so it belongs to Group 13 (Group III)
The jump corresponds to removing the next electron from the 2p subshell, which is
closer to the nucleus and more strongly held
Al: 1s2 2s2 2p6 3s2 3p1

Examiner Tips and Tricks

It is easy to remove electrons from a full subshell as they undergo spin-pair
repulsion.
It gets more difficult to remove electrons from principal quantum shells that get
closer to the nucleus as there is less shielding and an increase in attractive forces
between the electrons and nuclear charge.

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 Ionisation Energy & Electronic Configuration
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Ionisation Energies: Electronic

Configuration
Using Successive Ionisation Energy Data
Each ionisation energy refers to the energy required to remove one one mole of
electrons from one mole of a specific species in the gaseous state
First ionisation energy is the energy required to remove one mole of electrons from
one mole of gaseous atoms
Successive ionisation energies are the energy required to remove one mole of
electrons from one mole of gaseous positive ions
As electrons are removed, the ion becomes more positively charged
This increases the electrostatic attraction between the nucleus and remaining
electrons
Therefore, ionisation energies increase progressively
A large jump in successive ionisation energies indicates that:
An electron is being removed from a new, inner shell closer to the nucleus
These electrons experience a stronger attraction to the nucleus and require more
energy to remove

How to deduce electronic configuration

Look for the largest increase between two successive ionisation energies
The number of electrons removed before this jump = number of outer-shell (valence)
electrons
This corresponds to the element’s group number in the Periodic Table (for s- and p-
block elements)

Worked Example
Deduce the electronic configuration of element Z, a Period 3 element, using
successive ionisation energy data.

IE 5th 6th 7th 8th

IE (kJ mol-1) 6542 9362 11,018 33,606

Answer

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You are told that the element is in Period 3
Period 3 elements have electrons up to the 3rd shell:
Your notes
3s and 3p subshells are included
There is a large jump between the 7th and 8th IE, so element Z must be in Group 17
So element Z is in Period 3 and Group 17:
This corresponds to chlorine, Cl
The electronic configuration of Cl is:
1s22s22p6 3s23p5

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