Periodic Properties and their variation

1. Atomic radii

An atom is considered to be spherical. Hence, the size of an atom is expressed

in terms of atomic radius. It is the distance between the centre of the nucleus
and the outermost shell having electrons. However, it is difficult to determine
the radius of an atom directly and precisely due to following reasons;
i. It is difficult to isolate an atom to measure its radius.
ii. In view of probability concept-position of electron can’t be defined
precisely- atoms do not have fixed boundary.
iii. The size of an atom is also affected by the type of neighboring atoms and
nature of bonding.
Hence, atomic size is measured indirectly in the given bonding condition as:
a. Covalent radius: Atoms of nonmetals are
bonded by covalent bond, hence, their size is
expressed in terms of covalent radius. It is
defined as the distance between centre of
the nucleus of an atom and the mean
position of the shared pair of electrons
between the bonded atoms. It is half of the distance between the two
nuclei in a homonuclear diatomic molecule bonded by a sigma bond.
b. Metallic radius: In metals, the atoms are held together by a metallic bond
and their size is expressed in terms of metallic radius. It is half of the
distance between nuclei of two adjacent metal atoms
held by metallic bond(in a close-packed metallic lattice).
c. Van der Waals radius: Non polar molecules (eg. Propane) are held together
by Van der waal's force of attaction and their atomic size is expressed in
terms of Van der waal's radius. It is half of the distance between two non-
bonded nuclei of atoms held by van der Waals force of attraction.
The strength of various bonds is in the order:
Covalent bond > metallic bond >> van der Waals force of attraction
Covalent bond is strong, hence, bonded atoms are pulled closely, therefore,
measured distance is small. van der Waals force of attraction is a very weak
force of attraction, hence, atoms are not pulled so closely and the distance
between two atoms held by such force of attraction is large.
Therefore,
Covalent radius < metallic radius << van der Waals radius.
 Variation of atomic radius in a period
On moving from left to right in a period, nuclear charge increases by one unit
and an electron is added to the same shell. The progressive increase in
nunclear charge is not neutralized by extra valence electrons. Former effect
overweights the latter one. Therefore, electrons are attracted more strongly
by the nucleus due to which size of atom decreases.

Variation of atomic radius in a group

On moving from top to bottom in a group, nuclear charge increases due to
which size is expected to decrease but number of shells in the atom of the
element increase due to which size of atom should increase. The latter effect
overweighs the former effect. Hence, net result is increase in size of atom.

2. Ionic radii
Ionic radius may be defined as the distance between the centre of the nucleus
of the ion and a point up to which the nucleus has its influence on its electron.
It is also measured indirectly by measuring distance between the two nuclei of
bonding ions. By the study of ionic radius, following conclusions are made;
1. A cation is smaller than the parent atom.
A cation is formed by the loss of electron(s) in the valence shell and therefore,
effective nuclear charge per electron increases. Thus, outermost electrons of
the cation are more tightly held by the nucleus resulting decrease in size.

2. An anion is larger than the parent atom.

Anion is formed by the addition of electron in the valance shell and therefore,
effective nuclear charge per electron is reduced. This, outermost electrons are
less tightly held by the nucleus.So the anions have larger size than the
corresponding atom
3. Size of cation decreases with increase in positive charge.
4. In isoelectronic ions, ionic radius decreases with increase in nuclear charge.

3. Ionization energy (I.E.): Ionization potential

The minimum amount of energy required to remove the most loosely held
electron from an isolated gaseous atom in its ground state is called ionization
energy of that element. For example,

M(g) + IE →M+(g) + e-

Li (g) + 520 kJ → Li+(g) + e-

Successive ionization energy

It is possible to remove more than one electron from an atom successively.

The minimum amount of energy required to remove subsequent electron
from an isolated gaseous atom in its ground state is called successive
ionization energy of that element. It is the first, second, third,.. Ionization
energy which refers to the removal of first, second, third,..electron
respectively.
M(g) + IE1 → M+(g) + e-
The minimum amount of energy required to remove the most loosely held
electron from an isolated gaseous monopositive cation in its ground state is
called the second ionization energy (IE2) of that element.
M+(g) + IE2 →M++(g) + e-

Similarly, the minimum amount of energy required to remove the most

loosely held electron from an isolated gaseous dipositive cation in its ground
state is called the third ionization energy (IE3) of that element and so on.
M++(g) + IE3 →M+++(g) + e-
Examples,
Al(g) + IE1→ Al+(g) + e- IE1= 577 kJ
Al+(g) +IE2 →Al++(g) + e- IE2 = 1816 kJ
Al++ (g) + IE3 →Al+++(g) + e- IE3 = 2744 kJ
For an element, IE1 < IE2 < IE3 < IE4 , and so on.
This trend in variation of ionization energies of an element is due to increase
in effective nuclear charge with increase in charge of cation

This is due to the following reasons:

1.Size of M+ is small since it is formed by removal of a valence shell.
2.Effective nuclear charge increases.
3. M+ has extra stability due to its noble gas configuration. This is the most
important factor.

Factors affecting ionization energy

Ionization energy of an element depends upon the following factors;
a. Size of atom or ion: As the size of atom or ion decreases, valence
electrons are more strongly attracted by the nucleus and more energy is
required to remove the electron. Therefore, ionization energy increases
with decrease in size of atom or ion.
b. Nuclear charge: As the nuclear charge of atom or ion increases, valence
electrons are more strongly attracted by the nucleus and more energy is
 required to remove the electron. Therefore, ionization energy increases
with increase in nuclear charge of atom or ion.
c. Electronic configuration: Half filled and completely filled orbitals are
more stable than other configurations. More energy is required to
remove electron from more stable orbitals. Therefore, ionization energy
is high to remove electron from half filled and completely filled orbitals.
d. Screening effect or shielding effect: The process by which valence
elctrons are shielded from nucleus by inner electrons is called screening
effect or shielding effect. Greater the number of electrons, higher the
shielding effect. As the screening effect increases, electrons are less
strongly attracted by the nucleus and less energy is required to remove
the electron. Therefore, ionization energy decreases with increase in
screening effect.
e. Penetration effect of electrons: The probability of finding the electrons
near the nucleus in a given shell is in the order :
s electrons > p electrons > d electrons > f electrons.
In other words, s electron penetrates more towards nucleus than
corresponding p electrons and so on. This means in a given shell, s
electrons are more strongly attracted by the nucleus than the
corresponding p electrons and so on. Therefore, more energy is required
to remove electron from s orbital than the corresponding p orbital and
so on. The screening effect of the orbitals also follows the order: s-
orbitals > p-orbital > d-orbital > f-orbital.

Nuclear charge and effective nuclear charge

There exist electrostatic force of attraction between positively
charged nucleus and negatively charged electron which is called
nuclear charge. As each electron is located differently in an atom,
the nuclear charge felt by each electron is different. However, if
some other electrons intervene between the particular electron and
nucleus, the actual nuclear attraction felt by the electron is a bit
different as it is assumed to be. In multi-electron atoms, in addition
to attraction between the nucleus and the electron, there is
repulsion between the electrons so that the valence electron
experiences less nuclear attraction. This effect of inner electrons is
called screening effect or shielding effect (σ). Greater the number of
electrons, greater the shielding effect. The nuclear attraction felt by
valence electron is called effective nuclear charge.
 Effective nuclear charge (Zeff) = Nuclear charge ( Z) - shielding
constant (σ)

The nuclear attraction felt by valence electron is called effective nuclear

charge.
Variation of ionization energy in a period

On moving from left to right in a period, nuclear charge increases and

size of atom decreases due to which electrons are more strongly
attracted by the nucleus and more energy is required to remove the
electron. Hence, ionization energy increases.

Variation of Ionization Energy in a group

On moving from top to bottom, the nuclear charge increases. However,

its effect is negligible with compared to the effect of increased screening
effect and size of atom. Therefore, electron experiences less attraction
force and consequently ionization energy decreases.

Note: Electro positivity(Metallic character) is inversely proportional to

IE.

4. Electron Affinity (EA)

Electron of an element is defined as the amount of energy released when an electron is added to
an isolated gaseous atom to convert it into anion.
X (g) + e -→ X - (g) + energy released (EA)
Eg. Cl (g) + e -→ Cl - (g) + E.A
Thus electron affinity is also a measure of tendency of an atom to form anion.
Factor affecting the magnitude of Electron Affinity
1. Size of the atom:
With the increase in size of an atom, there will be decrease in tendency of an atom to attract
the additional electron hence the value of electron affinity decrease.
2. Nuclear charge:
With the increase in nuclear charge, there will be greater force of attraction between nucleus
and incoming electron. Hence electron affinity value increases.
3. Screening effect:
With the increase in screening effect, there is decrease in the value of electron affinity. This is
due to the reason that force of attraction between the nucleus and the incoming electron
decreases.
4. Electronic configuration:
Half-filled and completely filled electronic configurations are highly stable and hence more the
stable electronic configuration of an atom, less will be the tendency to attract additional
electron, consequently electron affinity value decreases.
Variation of EA in the periodic table.
In period:
Electron affinity value increases while moving from left to right in a period. This is because on
moving from left to right, there is decrease in atomic size and increase in nuclear charge, both
these factors result in the greater attraction for the incoming electron and hence electron affinity
value increases.
In group:
Electron affinity value decreases while moving down the group. This is because on moving down
the group, there is increase in atomic size, nuclear charge and screening effect. The increase in
nuclear charge is balanced by increase in atomic size and screening effect. This results decrease in
force of attraction for incoming electron. Hence electron affinity value decreases.
Explain why?
1. Electron affinity of halogen is very high.
2. Electron affinity of F is less than that of Cl.
Ans: Due to small size and high electron density addition of an extra electron results in strong
electron-electron repulsion, as a result addition of an extra electron is unfavourable. Hence
electron affinity of F is less than that of Cl.
3. Electron affinity of noble gases is zero.
4. Second electron affinity is positive.
Ans: When an electron is added to the gaseous atom it forms a uninegative ion and energy is
released during the process. Now if another electron is added to the uninegative ion, it
experiences a repulsive force from anion. As a result the energy has to be supplied to overcome
the repulsive force. Thus in order to add the second electron, the energy is required rather
than released. Therefore the value of second electron affinity is positive.
Eg: O (g) + e → O (g) + (energy released)
- -

O (g) + e + energy → O
- - 2-

5. The electron affinity value of O → O has positive sign. Explain.

2-

5.Electronegativity
Electronegativity of an element is defined as the measure of tendency of and atom in a molecule
to attract the shared pair of electron towards itself. Thus the value of electronegativity of an
element describes the ability of an atom to attract the shared pair of electrons with another atom
to which it is bonded.
Factors affecting electronegativity
1. Size of atom:
Smaller the size of atom, greater will be the tendency of an atom to attract the electrons and
hence value of electronegativity increases.
2. Number of inner shell (Screening effect):
Larger the number shells, greater will be the value of screening effect, as a result there is
decrease in force of attraction and consequently the electronegativity decreases.
3. Size of the ion:
Cation has smaller size than the parent atom. So, it has high tendency to attract the electron.
Hence cation has higher value of electronegativity. On the other hand, anion being larger than
the parent atom has less tendency to attract the electron and hence it has lower value of
electronegativity.
4. Ionization energy and electron affinity:
High ionization of an atom means that it is difficult to remove an electron from an isolated
gaseous atom which also leads to higher value of electron affinity. Hence the atoms of the
element having higher value of ionization energy and electron affinity also have higher value of
electronegativity.
5. Types of hybridization:
 The magnitude of electronegativity also depends upon the s-character present in the hybrid
orbitals.
Compound: CH 4 CH2 4 CH 2 2

Types of hybridization: sp 3 sp 2 sp
% of s-character: 25% 33.33% 50%
Higher the % of s-character higher will be the electronegativity value. Hence the
electronegativity value takes an order; CH < C H < C H
4 2 4 2 2

Variation of electronegativity (EN) in the periodic table

In period:
On moving from left to right in a period, EN increases. This is because;
1. On moving from left to right, there is decrease in atomic size and smaller atoms have greater
tendency to attract the electrons. Hence the EN increases.
2. While moving from left to right, there is increase in IE and EA which results in increase in the
value of EN.
In group:
While moving down in a group, EN decreases. This can be explained as;
1. On moving down the group, there is increase in atomic size due to the successive addition of
new shell in each step which results in less tendency of an atom to attract the electrons.
Hence EN decreases.
2. On moving down the group, ionization energy and electron affinity decrease and hence the
value of EN also decreases.