IONISATION ENERGY

Ionisation is the complete removal of an electron from an atom

or ion in the gaseous state.
Ionisation is an endothermic process as energy must be supplied
to the electron in order to overcome the electrostatic force
between the electron and the nucleus.
The energy required is called the standard ionisation energy.
The first ionisation energy is the heat enthalpy required to
remove the most loosely held electron from every atom in one
mole of free gaseous atoms under standard conditions.
The second ionisation energy is the energy required to remove
the most loosely held electron from every unipositive ions in
one mole of free gaseous unipositive ions under standard
conditions.

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Higher ionisation energies are defined in the same way. For
example, the third ionisation energy refers to:

However, the following is not the third ionisation energy:

The energy H is the sum of the first, second and third
ionisation energy.
For any one element, the ionisation energies increase. As
each electron is removed from an atom, the remaining ion
becomes more positively charged. Moving the next electrons
away from the increased positive charge is more difficult and
the next ionisation energy is even larger.

IONISATION ENERGY
Factors Influencing Ionisation Energies
Generally, the bigger the size of an atom, the lower is the
ionisation energy.
The three strongest influences on ionisation energies of
elements are the following:
1) The Size of the Positive Nuclear Charge
This charge affects all the electrons in an atom. The
increase in nuclear charge with atomic number will tend to
cause an increase in ionisation energies.

IONISATION ENERGY
2) The distance of the electron from the nucleus
It has been found that, if F is the force of attraction between
two objects and d is the distance between them, then F is
1
proportional to 2 .

This distance effect means that all forces of attraction

decrease rapidly as the distance between the attracted bodies
increases. Thus the attraction between a nucleus and electrons
decrease as the quantum numbers of the shells increase.
The further the shell is from the nucleus, the lower are the
ionisation energies for electrons in that shell.

IONISATION ENERGY
3) The shielding effect by electrons in filled inner shells
All electrons are negatively charged and repel each
other.
Electrons in the filled inner shells repel electrons in the
outer shell and reduce the effect of the positive nuclear
charge.
This is called the shielding effect. The greater the
shielding effect upon an electron, the lower is the energy
required to remove it and thus the lower the ionisation
energy.

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Hydrogen has an electronic structure of 1s1. It is a very small

atom, and the single electron is close to the nucleus and
therefore strongly attracted. There are no electrons screening it
from the nucleus and so the ionisation energy is high (1310 kJ
mol-1).
Helium has a structure 1s2. The electron is being removed from
the same orbital as in hydrogen's case. It is close to the nucleus
and unscreened. The value of the ionisation energy (2370 kJ
mol-1) is much higher than hydrogen, because the nucleus now
has 2 protons attracting the electrons instead of 1.
Lithium is 1s22s1. Its outer electron is in the second energy
level, much more distant from the nucleus. You might argue that
that would be offset by the additional proton in the nucleus, but
the electron doesn't feel the full pull of the nucleus - it is
screened by the 1s2 electrons. Lithium's first ionisation energy
drops to 519 kJ mol-1

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The first ionisation energies of the first 36 elements in the

Periodic Table are plotted against their atomic number and
presented in the following graph:

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First Ionisation Energy Across a Period
From the graph, we see a general trend of increasing
ionisation energies across a Period. However, the trend is
uneven.
For example, at element 3 (lithium 1s22s1), 4 (beryllium
1s22s2) and 5 (boron 1s22s22p1). We might have predicted
boron would have the highest ionisation energy of the three;
in fact, it is beryllium.

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Our modern theories for electronic structure show that the p

orbitals are higher energy level than the s orbital for a given
quantum number.
Hence we predict that an electron is more easily removed
from the p orbital than the s orbital. Thus, the 2p electron in
boron is easier to remove than one of the 2s electrons.
Therefore, though the nuclear charge in boron is larger than
in beryllium, boron has the lower first ionisation energy.

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Lets look at another example of elements in Period 2:

In the general trend across the Period, we might expect the

ionisation energy of oxygen to be higher than that of nitrogen.
In fact, the ionisation energy of nitrogen is the higher of the
two.
Nitrogen has three electrons in the p orbitals, each of them
unpaired; Oxygen has four electrons, with two of them paired.
The repulsion between the electrons in the pair increases the
energy and makes it easier to remove one of them and to ionise
an atom of oxygen, even though the nuclear charge is larger
than in an atom of nitrogen.

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First Ionisation Energies in Groups
Elements are placed in Groups in the Periodic Table, as they
show many similar physical and chemical properties.
The first ionisation energies generally decrease down a
vertical Group, with increasing atomic number.
With increasing proton number, in any Group:
The positive nuclear charge increases;
The atomic radius increases so the distance of the outer
electrons from the nucleus also increases with each new
shell;
The shielding effect of the filled inner electron shells
increases as the number of inner shells grows.
The distance and shielding effects together reduce the effect
of the increasing nuclear charges from element to element
down any Group.

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