Ionisation Energy

Ionisation is a big theme in AS Chemistry but the questions are very predictable.

Firstly, you need to know a definition for ionisation energy:

The energy required to remove one mole of electrons from one mole of gaseous atoms to form one
mole of gaseous ions.

For example:
Na(g) Na+(g) + e-

Having an example is very useful. You can just say what you see to get the definition.

So, ionisation just means that you are forming a positive ion (the ion part should give you a big clue if
you forget) in the gas state. Need to break the electrostatic attraction between nucleus and electron.

One of the outer electrons is removed as these electrons are furthest from the nucleus and are not
held as strongly or attracted as much as the inner electrons.

Successive ionisation

You can then remove a 2nd or 3rd electron or as many as you want, but only one at a time. Below shows
the 2nd ionisation of sodium.

Na+(g) Na2+(g) + e-

The 2nd ionisation is always higher than the 1st, and the 3rd will be higher than the 2nd and so on.

This is because after the 1st ionisation, you are trying to remove an electron from a positive ion, which
will attract the outer electron more and make it more difficult to remove.

Three factors affecting Ionisation

atomic radius (size) shielding nuclear charge

When looking at these, you need to think what happens down a group or across a period.

If you can become good at writing out electronic structures i.e. 1s2 etc. or simply by shells, 2,8,1 etc., you
can work out a lot of the answers.
Down a group

Trend: the ionisation energy decreases down a group

The main reason for this is that the atomic radius (size) increases as you go down a group. The size
increases are more inner shells are added but there is still the same number of outer electrons.

The electronic structures of the first three elements of Group 1 are shown below.

Li 2,1

Na 2,8,1

K 2,8,8,1

As you go down Group 1, the outer electron becomes further from the nucleus. The outer electron feels
less attraction from the nucleus in going from Li to Na to K etc. and therefore becomes easier to remove.

This increase in the number of inner shells can also be viewed as shielding. The inner electrons shield
the outer electron from the full attractive force of the nucleus, which results in it being easier to remove.

Across a period:

Trend: the ionisation energy increases across a period (generally)

I have put the word generally in brackets as there are couple of dips in the trend where there are
decreases, which we will look at later.

Going across a period, the key phrase you need is increase in nuclear charge. Again, you need to look at
the electronic structure.

Looking at period 3, starting with Na and going across the period:

Na has 11 electrons and 11 protons

Mg has 12 electrons and 12 protons

 Al has 13 electrons and 13 protons

The key point is that a proton is added as going across the period and therefore increasing the positive
charge on the nucleus. This is what we mean by the increase in nuclear charge.

If we now look at the electronic structures:

Na 2,8,1

Mg 2,8,2

Al, 2,8,3

We can see that although we are adding extra electrons as we go across the period, they are being added
to the same shell, in contrast to going down a group.

This means that shielding is not an issue here and the elements actually become slightly smaller across a
period.

Because of the increase in nuclear charge, the outer electron feels a stronger attraction from the nucleus
as you go across the period, and it is therefore more difficult to remove this electron.

The dips

Examiners like to ask questions on the points that go against the general trend. These dips occur between
groups 2 and 3 and between groups 5 and 6. Again, the electronic structure is your friend.

Between groups 2 and 3

This trend is the same for any elements going across a period from group 2 to 3. We will look at
magnesium, group 2, and aluminium, group 3, as an example:

Mg 1s2 2s2 2p6 3s2

Al 1s2 2s2 2p6 3s2 3p1

All you are doing here is comparing the electronic structures and looking for differences. We can clearly
see that with aluminium there is an extra sub-shell, 3p.

This new sub shell means that the outer electron is further from the nucleus and is easier to remove than
for magnesium, a bit like when you go down a group.
Between groups 5 and 6

We will look at nitrogen in group 5 and oxygen in group 6 as the example here:

Nitrogen: 1s2 2s2 2p3

Oxygen: 1s2 2s2 2p4

It is best to draw these out:

So whats the difference between these two diagrams? Yes, one has blue writing I know, but other than
that.

There is an extra electron for oxygen in the 2p orbitals and it is paired up, whereas nitrogen has 3
unpaired electrons in the 2p orbitals.

This pairing up of electrons in oxygen causes a bit repulsion (two negative things put together), which
destabilises oxygen slightly, and enables one of those electrons to be removed easier than for nitrogen.

You can make this comparison for any of the elements in groups 5 and 6.

Successive ionisation energies

look for a big jump between two successive ionisation values

Questions on successive ionisation energies are an exam favourite. For example, you could have 11
different ionisation energies for sodium as it has 11 electrons to remove.

The key thing to look out for is a big jump in ionisation energy. Examiners tend to give this information
either in the form of a diagram or a table of values.

In the example above, the big jump is between the 3rd and 4th values. This means that the element is in
group 3. The first 3 electrons were easy to remove but the 4th electron is much more difficult i.e. requires
a lot more energy as a new shell is broken into.

Noble gases always have high 1st ionisation energies as they have a full shell. When you then go to
the next element in group 1 of the next period, there is a big drop in ionisation energy.