VARIATION IN ATOMIC RADIUS AND
IONISATION ENERGY
Variation in atomic radius
i) Across the period
On moving across e.g Period 3 from left to right, the nuclear charge increases,
but the shell number is constant and the shielding stays the same.
The attraction of the outer electrons to the nucleus thus increases and the
outer electrons are pulled in closer.
The size of the atoms just decreases on crossing a period – i.e. sodium is the
largest atom in Period 3 and neon is the smallest.
ii) Down the group
- On moving down a group, e.g group 2, the shell number as the atomic
number increases
- The shielding effect increases
- The attraction of the outer electrons to the nucleus decreases and so
the atomic radius increases
Variation in ionic radius
i) Across the period
- Cationic radius decreases across the period with increase in proton
number greater attraction on the remaining electrons
- The outer shell is lost and ionic size is smaller than atomic size
- Anionic radius also decreases with increase in proton number and
attraction of outer electrons increase
- However the anions are bigger than the atoms gaining of electrons in
the outer shell increases the repulsions between the electrons
- Cation are smaller the anions because cations would have lost a shell
ii) down a group
- Increases down the group with increase in shell number and increase in
shielding effect
IONISATION ENERGY, IE
- Energy is supplied to knock an electron
- Energy is required to overcome the forces of attraction between the
positively nucleus and the outer electron
- Measurements are under standard conditions
- Units are kilojoules per mole (kJ mol-1)
- Symbol is ΔHi
First ionisation energy of an element is the energy needed to remove one
electron from an atom per mole of atoms in the gaseous state ( to form one
mole of gaseous +1 ions)
- Eg Mg(g) → Mg+( g) + e- ΔHi1 = 736 kJ mol-
1
Second ionisation energy
- Energy requird to remove an electron from a mole of gaseous +1 ion to
form gaseous +2 ion
- Mg+(g) → Mg2+( g) + e- ΔHi2 1450 kJ mol-1
Successive ionisation energies
- Successive ionisation energies are when we continue to remove
electrons from an atom until only the nucleus is left
- For each element successive ionisation energies increase as the charge
on the ion increases
- There is a greater attractive force between the nucleus and the
remaining electrons therefore more energy is required to overcome
these forces of attraction
-
-
Deducing electronic configurations of elements and position of an element in
the periodic table from successive ionisation energies
Factors that affect ionisation energies
1. Nuclear charge
Ionisation energy increases as the proton number increases
As atomic number increases the nuclear charge increases and attractive
forces between the nucleus and the electrons become greater
More energy is required to overcome forces of attraction and remove an
electron
2. Atomic/ionic radius
Ionisation energy decreases with increase in atomic /ionic radius/ shell
number
The distance of the outer electrons from the nucleus increases and the
attractive forces between the nucleus and the outer electron decreases
Less energy is required to remove an electron
3. Shielding effect of inner shell electrons
Ionisation energy decreases with increase in number of inner shells and
increase in shielding effect
Inner electrons prevents the full nuclear charge to be felt by the outer
electron
The greater the shielding of outer electron by the inner elctrons, the
lower the attractive forces between the nucleus and the outer electrons
Less energy is required to remove an electron
4. Spin pair repulsions
Electrons which are spin paired in the same orbital have greater
repulsions between themselves than those occupying orbitals singly
Spin pair repulsions lowers the energy required to remove an electron
Trends in ionisation energy across the period
Explanation of this trend
General increase across the period
Going across Period 3:
o there are more protons in each nucleus so the nuclear charge in
each element increases …
o therefore the force of attraction between the nucleus and outer
electron is increased, and …
o there is a negligible increase in shielding because each successive
electron enters the same shell …
o so more energy is needed to remove the outer electron.
Magnesium to aluminium
Look at their electronic configurations:
o Magnesium: 1s2 2s2 2p6 3s2
o Aluminium: 1s2 2s2 2p6 3s2 3p1
The outer electron in magnesium is in an s sub-shell. However, the outer
electron in aluminium is in a p sub-shell, so it is higher in energy than the
outer electron in magnesium. This means that less energy is needed to
remove it.
Phosphorus to sulfur
Look at their electronic configurations:
o Phosphorus: 1s2 2s2 2p6 3s2 3p3
o Sulfur: 1s2 2s2 2p6 3s2 3p4
It's not immediately obvious what's going on until you look at the
arrangements of the electrons:
The 3p electrons in phosphorus are all unpaired. In sulphur, two of the
3p electrons are paired. There is some repulsion between paired
electrons in the same sub-shell, so the force of their attraction to the
nucleus is reduced. This means that less energy is needed to remove
one of these paired electrons than is needed to remove an unpaired
electron from phosphorus.
It may help your understanding when you look at the diagrams below.
Trend in ionisation energy down a group
