S-13 : Ionization Energy, Electron Affinity and
Electronegativity
S-14: Polarizability, Explanation based on Fajan’s rule
and Oxidation State of Ions
Ionization Energy
The quantity of energy required to remove an electron from an atom is called as the
ionization energy.
Ionization energy is usually expressed in terms of electron volt (eV) per atom or
kJ/mole.
1 eV/atom = 96.48 kJ/mol
Low IE: Easy to remove an electron from the atom
High IE: Hard to remove an electron from the atom
Factors affecting the ionization energy
❖ Effective nuclear charge:
Higher the effective nuclear charge, higher the force of attraction between the
nucleus and the electron and hence higher the ionization energy.
❖ Size of the atom:
With the increase in the size of the atom, the electrons remain farther from the
nucleus. As a result, the force of attraction between the nucleus and the outermost
electron decreases and the ionization energy decreases with an increase in the
Trends in Ionization Energy
What happens down a group?
• The ionization energy decreases down the group.
As the size of atom increases down the group, the attraction becomes
weaker between the outer shell electrons and the nucleus. Hence less
energy is required to remove an electron from the outermost shell.
What happens across a period?
▪ The ionization energy increases along a period.
Across a period, as the size of atom decreases from left to right, the force of
attraction between the nucleus and electrons increases. Hence higher
energy is required to remove the electron from the outermost shell.
Electron Affinity
The amount of energy released when an electron is added to a neutral
atom in gaseous state is called as its electron affinity.
X (g) + e- X- (g)
Factors affecting the electron affinity
❖ Effective nuclear charge
• Higher the effective nuclear charge of the atom, higher the force of attraction between the
nucleus and the additional electron and hence higher the electron affinity
❖ Size of the atom
• Smaller the size of the atom, smaller will be the distance between the nucleus and the
additional electron. As a result, the force of attraction between the nucleus and the
outermost electron increases and the electron affinity increases with the smaller size of
the atom.
❖ Electronic configuration
• Atoms having stable electronic configuration (half-filled or full-filled outer orbitals) do not
show much tendency for an extra electron. Hence they have either zero or very low
electron affinity.
Trend in Electron Affinity
What happens down a group?
▪ The electron affinity decreases down the group.
As the size of atom increases down the group, the attraction becomes weaker
between the nucleus of atom and the additional electron. Hence the atom possess
less electron affinity.
What happens across a period?
▪ The electron affinity increases on moving from left to right along a
period.
Across a period, as the size of atom decreases from left to right, the force of
attraction between the nucleus and electrons increases. Hence the electron
affinity increases along the period from left to right.
Electronegativity
The ability of an atom to attract the shared electrons towards itself is
called as electronegativity.
Note: Electronegativity is not a property of an atom alone, but rather a
property of an atom in a molecule.
❖ The term "electronegativity" was introduced by Jöns Jacob Berzelius in 1811.
❖ An accurate scale of electronegativity was not developed until 1932, when Linus
Pauling proposed an electronegativity scale.
❖ Electronegativity cannot be directly measured and must be calculated from other
atomic or molecular properties.
Pauling Electronegativity:
The difference in electronegativity between atoms A and B is given by
|χA- χB| = (eV)-1/2 [Ed (AB) – (Ed (AA) + Ed (BB))/2]1/2
where Ed represents the bond dissociation energy in eV
Mulliken Electronegativity:
Robert S. Mulliken proposed that the arithmetic mean of the
first ionization energy (Ei) and the electron affinity (Eea) should be a
measure of the tendency of an atom to attract electrons.
χ = (Ei + Eea)/2
Trend in Electronegativity
In general, electronegativity increases on passing from left to right along
a period and decreases on descending a group.
Hence, Fluorine is the most electronegative of the elements, whereas
Francium is the least electronegative.
Polarizability
The unevenly distribution of charge over an anion and distortion of
electron density in the presence of a cation is referred to as
polarization.
Factors affecting the polarization of anion
(i) Polarizing Power of Cation
The polarizing power of cation depends on its size
and charge
❖ Smaller the size of cation, higher is the
polarizing power of cation
❖ Higher the charge on cation, greater is the
polarizing power of cation
Covalent nature α polarizing power
(ii) Polarizability of Anion
The ease with which an anion undergoes polarization
The polarization of anion depends on its size and charge
❖ Larger the size of anion, higher is the polarizability of anion
❖ Higher the charge on anion, higher is the polarizability of anion
❖ Size polarizability covalent nature
❖ Charge polarizability covalent nature
Fajan’s Rules
Rule-1: Smaller the cation or larger the anion, greater is the covalent
nature
Ex: Covalent character of Metal halides
Cation size: Li+ < Na+ < K+ < Rb+ < Cs+
Covalent nature: LiX> NaX> KX > RbX > CsX
Anion size: F- < Cl- < Br- < I-
Covalent nature: MF < MCl < MBr < MI
Fajan’s Rules
Rule-2: Greater the charge on either cation or anion, greater is the
covalent nature.
Charge on the cation:
Na+ < Mg2+ < Al3+ < Si4+
Covalent nature:
NaCl < MgCl2 < AlCl3 < SiCl4
Charge : Al3+ > Mg2+ > Na+
Al3+ > Mg2+ > Na+
Polarizing power : Al3+ > Mg2+ > Na+
Fajan’s Rules
Rule-3:
Cation with octet-configuration: Less covalent or greater ionic
nature
✔ ns2 np6: Effective nuclear charge is properly shielded by inner s
and p-electrons. Thus, less polarizing power and hence
compounds are less covalent.
Cation with pseudo-octet configuration: Greater covalent nature
✔ (n-1)d10 ns2: Effective nuclear charge is not properly shielded by
inner d-electrons. Hence more polarizing power and compounds
are more covalent.
Fajans’ rules – A summary
Ionic Covalent
Low charge on ions High charge on ions
Large cation Small cation
Small anion Large anion
Valence shell electron
Noble gas
configuration with
configuration
incomplete d/f subshell
