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
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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 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)
Ionisation Energy & the Periodic Table
So, the first ionisation energy increases across a period and decreases down a group
Graph of first ionisation energies from H to Na
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Your notes
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 Your notes
2s2 2px1 2py1 2pz1
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: 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
Distance from the outer electron to the Distance from the outer electron to the
nucleus decreases nucleus increases
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
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The successive ionisation energies of an element increase
This is because once you have removed the outer electron from an atom, you have Your notes
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 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 an element
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The ionisation energy increases as you remove more electrons from an element
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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
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
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
Atomic/ionic radius
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The larger the radius, the greater the distance between the nucleus and the outer
shell electron(s)
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Increasing distance weakens the strength of the attractive forces
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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