CHAPTER 1: ATOMIC STRUCTURE

1.4 Ionisation
energy………………………………………………………………………………………………………………..…

1. Define and use the term first ionisation energy, IE.

● 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 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.

2. Construct equations to represent first, second and subsequent ionisation energies.

➔ E.g. the first ionisation energy of gaseous calcium:

Ca(g) → Ca+ (g) + e– IE1 = +590 kJ mol-1

3. Identify and explain the trends in ionisation energies across a period and down a
group of the Periodic Table.

● Ionisation energies show periodicity – a trend across a period of the Periodic Table.

● As could be expected from their electron configuration, the group 1 metals have a
relatively low ionisation energy, whereas the noble gases have very high ionisation
energies.
● First ionisation energy increases across a period and decreases down a group.

Ionisation energy across a period

● The ionisation energy across a period generally 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.

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 are adding 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.

From one period to the next

● There is a large decrease in ionisation energy between the last element in one

period, and the first element in the next period.

● This is 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.

4. Identify and explain the variation in successive ionisation energies of an element

● The successive ionisation energies of an element increase.

● 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:

● 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.

5. Understand that ionisation energies are due to the attraction between the nucleus and
the outer electron.

● 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.

6. Explain the factors influencing the ionisation energies of elements in terms of nuclear
charge, atomic/ionic radius, shielding by inner shells and sub-shells and spin-pair
repulsion.

● 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 ionization energy is always the lowest).

● So, the first ionisation energy increases across a period and decreases down a group.

7. Deduce the electronic configurations of elements using successive ionisation energy

data.

● Successive ionisation data can be used to:

a. Predict or confirm the simple electronic configuration of elements.

b. Confirm the number of electrons in the outer shell of an element.

c. Deduce the Group an element belongs to in the Periodic Table.

● By analyzing where the large jumps appear and the number of electrons removed

when these large jumps occur, the electron configuration of an atom can be

determined.

● Na, Mg and Al will be used as examples to deduce the electronic configuration and

positions of elements in the Periodic Table using their successive ionisation energies.
8. Deduce the position of an element in the Periodic Table using successive ionisation
energy data.

Successive ionisation energies table.

Sodium

● For sodium, there is a huge jump from the first to the second ionisation energy,
indicating that it is much easier to remove the first electron than the second.
● Therefore, the first electron to be removed must be the last electron in the valence
shell thus Na belongs to group I.
● The large jump corresponds to moving from the 3s to the full 2p subshell
Na : 1s2 2s2 2p6 3s1

Magnesium

● There is a huge increase from the second to the third ionisation energy, indicating
that it is far easier to remove the first two electrons than the third.
 ● Therefore the valence shell must contain only two electrons indicating that
magnesium belongs to group II.
● The large jump corresponds to moving from the 3s to the full 2p subshell
Mg : 1s2 2s2 2p6 3s2

Aluminium

● There is a huge increase from the third to the fourth ionisation energy, indicating
that it is far easier to remove the first three electrons than the fourth.
● The 3p electron and 3s electrons are relatively easy to remove compared with the
2p electrons which are located closer to the nucleus and experience greater
nuclear charge.
● This is due to weakened shielding effects through the loss of three electrons.
● The large jump corresponds to moving from the third shell to the second shell
Al : 1s2 2s2 2p6 3s2 3p1