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CIE A Level Chemistry Your notes

1.4 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 atoms of an element to form one mole of 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 (IE) of an element is the amount of energy required to remove one mole
of electrons from one mole of gaseous ions of an element to form one mole of gaseous 2+ ions
E.g. the second ionisation energy of gaseous calcium:

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Ca+ (g) → Ca2+ (g) + e- IE2 = +1145.4 kJ mol-1

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Exam Tip
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 trend across a period of the Periodic Table
As could be expected from their electronic configuration, the group I metals have a relatively low
ionisation energy, whereas the noble gases have very high ionisation energies
The size of the first ionisation energy is affected by four factors:
Size of the nuclear charge
The nuclear charge increases with increasing atomic number, which means that there are
greater attractive forces between the nucleus and electrons, so more energy is required to
overcome these attractive forces when removing an electron
Distance of outer electrons from the nucleus
Electrons in shells that are further away from the nucleus are less attracted to the nucleus - the
nuclear attraction is weaker - so the further the outer electron shell is from the nucleus, the
lower the ionisation energy
Shielding effect of inner electrons
The shielding effect is when the electrons in full inner shells repel electrons in outer shells,
preventing them from feeling the full nuclear charge, so the more shells an atom has, the
greater the shielding effect, and the lower the ionisation energy
Spin-pair repulsion
Electrons in the same atomic orbital in a subshell repel each other more than electrons in
different atomic orbitals which makes it easier to remove an electron (which is why the first
ionisation energy is always the lowest)

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Ionisation Energy & the Periodic Table

So, the first ionisation energy increases across a period and decreases down a group Your notes
Graph of first ionisation energies from H to Na

There are ionisation energy trends within periods and groups

Ionisation energy across a period
The ionisation energy over a period increases due to the following factors:
Across a period the nuclear charge increases
This causes the atomic radius of the atoms to decrease, as the outer shell is pulled closer to the
nucleus, so the distance between the nucleus and the outer electrons decreases
The shielding by inner shell electrons remain reasonably constant as electrons are being added to
the same shell
It becomes harder to remove an electron as you move across a period; more energy is needed
So, the ionisation energy increases
There is a rapid decrease in ionisation energy between the last element in one period, and the first
element in the next period because:
There is increased distance between the nucleus and the outer electrons as you have added a new
shell
There is increased shielding by inner electrons because of the added shell
These two factors outweigh the increased nuclear charge
There is a slight decrease in IE1 between beryllium and boron as the fifth electron in 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

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Boron has a first ionisation energy of 800 kJ mol-1 as its electron configuration is 1s2 2s2 2px1
Nitrogen has a first ionisation energy of 1400 kJ mol-1 as its electron configuration is 1s2 2s2 2px1 2py1
2pz1 Your notes
Oxygen has a first ionisation energy of 1310 kJ mol-1 as its electron configuration is 1s2 2s2 2px2 2py1
2pz1There is a slight decrease in IE1 between nitrogen and oxygen due to spin-pair repulsion in the 2px
orbital of oxygen

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: Down a group:

Ionisation energy increases Ionisation energy decreases

Increase in nuclear charge Increase in nuclear charge

The same number of shells Increased number of shells

Distance from the outer electron to the nucleus Distance from the outer electron to the nucleus
decreases increases

Shielding remains relatively constant Shielding increases

Decreased atomic / ionic radius Increased atomic / ionic radius

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

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Successive Ionisation Energies of an Element

The successive ionisation energies of an element increase Your notes
This is because once you have removed the outer electron from an atom, you have formed a positive
ion
Removing an electron from a positive ion is more difficult than from a neutral atom
As more electrons are removed, the attractive forces increase due to decreasing shielding and an
increase in the proton to electron ratio
The increase in ionisation energy, however, is not constant and is dependent on the atom's electronic
configuration
Taking calcium as an example:
Table Showing the Successive Ionisation Energies of Calcium Table
Electronic 1s2 2s2 2p6 3s2 3p6
1s2 2s2 2p6 3s2 3p6 1s2 2s2 2p6 3s2 3p5 1s2 2s2 2p6 3s2 3p4
Configuration 4s1

IE First Second Third Fourth

IE (kJ mol-1) 590 1150 4940 6480

Successive ionisation energies of an element

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Your notes

The ionisation energy increases as you remove more electrons from an element

The first electron removed has a low IE1 as it is easily removed from the atom due to the spin-pair
repulsion of the electrons in the 4s orbital
The second electron is more difficult to remove than the first electron as there is no spin-pair repulsion
The third electron is much more difficult to remove than the second one corresponding to the fact that
the third electron is in a principal quantum shell which is closer to the nucleus (3p)
Removal of the fourth electron is more difficult as the orbital is no longer full, and there is less spin-pair
repulsion

Exam Tip
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
Energy is required to remove an outer shell electron as this involves breaking the attractive forces
between the electron and the positively charged nucleus
There are several factors which affect the magnitude of the ionisation energy:
Nuclear charge
Positive nuclear charge increases with increasing number of protons
The greater the positive charge, the greater the attractive forces between the outer electron(s)
and the nucleus
More energy is required to overcome these forces so ionisation energy increases with increasing
nuclear charge
Shielding
Electrons repel each other and electrons occupying the inner shells repel electrons located in
shells further outside the nucleus and prevent them from feeling the full effect of the nuclear
charge
The greater the shielding effect is, the weaker the attractive forces between the positive nucleus
and the negatively charged electrons
Less energy is required to overcome the weakened attractive forces so ionisation energy
decreases with increasing shielding effects
Diagram demonstrating nuclear attraction and shielding

Shielding makes it easier to remove the outermost electrons

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Atomic/ionic radius
The larger the radius, the greater the distance between the nucleus and the outer shell electron(s)
Increasing distance weakens the strength of the attractive forces Your notes
Larger atoms/ions also result in greater shielding due to the presence of more inner electrons
Less energy is required to remove the outer shell electron(s) so ionisation energy decreases with
increasing atomic/ionic radius
Spin-pair repulsion
Spin pair repulsion occurs when the electron being removed is spin paired with another electron in
the same orbital
The proximity of the like charges of electrons in the orbital results in repulsion
Less energy is required to remove one of the electrons so ionisation energy decreases when there
is spin-pair repulsion
Summary of factors affecting ionisation energies of atoms

Nuclear charge and shielding link to the atomic / ionic radius

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