Periodic Properties

Part 3
Atomic and ionic sizes and Electronegativity
Atomic size

The size of an atom is generally expressed in terms of its radius called atomic radius.

Atomic radius is taken as the distance from the center of the nucleus to the outermost
shell of the electrons.

The electron density in an atom is greatly influenced by the presence of other atoms
around the given atom and by its mode of bonding with the neighboring atoms. This
results in terms such as Metallic radius, Covalent radius, Vander Waal’s radius etc.

(i) Metallic radius

It is defined as one half of the distance between the centers of the nuclei of the two
adjacent atoms in a metallic crystal.
Atomic size (Contd.)

Example:
The distance between two adjacent atoms of sodium in a crystal of sodium is found to
be 3.72Å (through X-ray diffraction). Therefore, the crystal radius of sodium in a crystal
of sodium is 3.72Å /2 = 1.86Å

(ii) Covalent radius

It is defined as the one half of the distance between the centers of nuclei of two
similar atoms bonded together by a single covalent bond.

Example:
The distance between the nuclei of oxygen atoms in a molecule of O2 is found to be
1.32Å/2 = 0.66Å
Atomic size (Contd.)

• For H2, 0.74 Å (internuclear distance)

Thus, Covalent radius= 0.74 Å/2=0.37Å

• For Cl2 1.98 Å (internuclear distance)

Thus, Covalent radius= 1.98 Å/2 =0.99Å

(iii) Vander Waal’s radius

It is defined as one half of the distance between the nuclei of two non-bonded
isolated atoms.
OR
Two adjacent atoms belonging to two neighboring molecules of an element in the
solid state.
Atomic size (Contd.)

Example:

• The internuclear distance between two adjacent hydrogen atoms of two

neighboring hydrogen molecules in the solid state is found to be at 2.4 Å.

Thus, the van der waal’s radius for hydrogen would be 2.4/2 = 1.2 Å.

• The internuclear distance between two adjacent Chlorine atoms of two

neighboring molecules in the solid state is found to be at 3.6 Å.

Thus, the van der waal’s radius for Chlorine would be 3.6/2 = 1.8 Å.
Atomic size (Contd.)

Closest approach of two atoms and Van der Waals’ radius

Covalent radii and Van der Waals’ radii of Chlorine

Atomic size (Contd.)

Factors affecting atomic radius

(i) Principal quantum number
Atomic size increases with the increase in number of shells. Thus, atomic radius is
directly proportional to the number of electronic shells.

(i) Nuclear charge

As the nuclear charge increases, the atomic radius decreases due to the increase in
the attractive force on the outermost electrons.

(iii) Screening/Shielding effect

Inner shells or electrons shield the outermost electrons from the nucleus. Thus, the
valence electrons don’t experience the full charge of the nucleus. As a result, atomic
radius increases.
Hence, atomic radius increases with the increase in shielding effect.
Atomic size (Contd.)

Comparison of covalent radius and Van der Waals’ radius

• Van der Waals’ radii are always larger than covalent radii because
Van der Waals’ forces of attraction are weak, thus the internuclear distance in case of
atoms held by Van der Waals’ forces are much larger than the covalently bonded
atoms.

Overlapping of atomic orbitals to form a covalent bond

• Covalent radii are always smaller than the Van der Waals’ radii because
Covalent bond is formed by overlap of two half-filled orbitals, a part of electron cloud
becomes common. Thus, covalent radii are always smaller than the Van der
waals’radii.
Atomic size (Contd.)

Periodic trends in atomic radii

Along a period
On moving from left to right in a period, atomic radii (Covalent or Van der Waals’)
decreases. It is because

In a period, nuclear charge increases by one unit in each succeeding element while
the number of shells remains the same.

Because of increase in nuclear charge, the electrons of the shells feel more attraction
by the nucleus and thus pulled closer to the nucleus.

Thus, atomic radius decreases along a period.

Atomic size (Contd.)

In a period, atomic radius decreases so it should be minimum for noble gases.

Thus, alkali metals have largest atomic radius, decreases along the period and its
minimum for halogens while Inert gases have maximum radius in the period as for
them van der Waals’ radius is considered.
Atomic size (Contd.)

Variation of atomic radii in second period

Atomic size (Contd.)

Down the group

On moving down the group, atomic size increases. It is because

On moving down a group, the nuclear charge increases with atomic number but at the
same time the number of shells also increases (new energy shell is added at each
succeeding element).

As the number of shells increases in a group, the outermost electrons move farther
and farther away from the nucleus.

Thus, effective nuclear charge felt by the valence shell electrons decreases which
results in increase of atomic size.
Atomic size (Contd.)

Variation of atomic radii in Group 1

Ionic radii

Ionic radii means the radii of ions in ionic crystals.

The ionic radius of an ion is defined as the distance from its nucleus to the point up to
which the nucleus has influence in the ionic bond.

This distance is taken as the sum of the radii of the two ions involved. If the ionic
radius of one ion is known, that of the other ion can be calculated.

Ionic radii of a cation and an anion

Ionic radii (Contd.)

Radii of cations
Cations are positively charged ions

During their formation one or more valence electrons are removed from the neutral
atom but the positive charge on the nucleus remains the same.

A cation possess the same nuclear charge but less number of electrons as compared
to the present atom.

Thus, effective nuclear charge on the remaining electrons increases. As a result the
size of cation decreases.

Thus, the radius of a cation is always smaller than the radius of the atom from which it
is formed.
Ionic radii (Contd.)

Example:

Atomic radius of Na = 1.54 Å Atomic radius of K = 1.96 Å

Ionic radius of Na+ = 0.95 Å Ionic radius of K+ = 1.33 Å
Ionic radii (Contd.)

Radii of anions

Anions are negatively charged ions and are formed with addition of one or more
electrons to the valence shell of a neutral atom.

Anion contains the same nuclear charge but more electrons as compared to its parent
atom.

Thus, the same nuclear charge acts on large number of electrons than are present in
the neutral atom or effective nuclear charge on the valence electrons decreases.

Hence, the radius of an anion is always larger than that of the parent atom.
Ionic radii (Contd.)

Example:

Cl= 0.99 Å Cl-= 1.81 Å

Br= 1.14 Å Br-= 1.81 Å

Anion> Atom> Cation

Ionic radii (Contd.)

Trends in ionic radii in the periodic table

Along a period
Ionic radius decreases for metals forming cations as the metals lose their outer
electron orbitals.
The ionic radius increases for nonmetals as the effective nuclear charge decreases due
to the number of electrons exceeding the number of protons.

Down the group

Ionic radii increases down the group as the atomic radii due to a regular increase in
the number of shells.
Ionic radii (Contd.)

Variation of ionic radii in isoelectronic species

Isoelectronic species
Species which possess same number of electrons are called as isoelectronic species.

Example
(i) Na+ Mg2+ Al3+
3s1 3s2 3s23p1
Atomic radii (Å) 0.95 0.65 0.50

10e- 10e- 10e- → Isoelectronic species

11p+ 12p+ 13p+

In an isoelectronic series, there is an increase in nuclear charge and thus the attraction
for the same number of electrons increases. Thus, electrons are pulled more and more
strongly and ionic radius decreases.
Ionic radii (Contd.)

(ii) P3- S2- Cl- K+ Ca2+

Atomic radii (Å) 2.12 1.84 1.81 1.33 0.99

18e- 18e- 18e- 18e- 18e- → Isoelectronic

species
15p+ 16p+ 17p+ 19p+ 20p+
Ionic radii (Contd.)

(iii)
Electronegativity

Formation of a covalent bond involves the sharing of valence electrons between the
combining atoms.

Covalent bond between two similar atom is 100% covalent and there is no polarity in the
molecule.

For two dissimilar atoms, the covalent bond is found to be partially ionic and the
constituent atom appear to have partial positive and partial negative charges

A:A A:B

δ+ δ-

A-A A_____B

100% Covalent (partially ionic, polar molecule)

Electronegativity (Contd.)

Linus Pauling suggested

In a covalent molecule of dissimilar atoms, the shared pair of electrons does not
remain exactly in the middle but gets shifted to one side or the other.

Introduced a term “Electronegativity” to describe the shifting of shared pair of

electrons from its equilibrium position

Shared pair of electron shifts towards the atom which exerts a greater pull on it.

Such an atom is said to be more electronegative compared to the other atom.

Electronegativity is defined as the property of an atom to pull the shared pair of

electrons towards itself in a covalent bond.
Electronegativity (Contd.)

Factors affecting Electronegativity

(I) Effective Nuclear Charge

Higher the effective nuclear charge of an atom, greater is its tendency to pull the
shared pair of electron and greater is its electronegativity.

(ii) Size of the atom

Electronegativity decreases with the increase in the size.

Atoms with small size have higher value of electronegativities as small atoms have
higher nuclear charge and thus the shared pair of electrons are pulled more strongly
by the nucleus and the electronegativity is high.
Electronegativity (Contd.)

With increase in size → Zeff decreases → ElectronegaLvity decreases

With decrease in size → Zeff increases → ElectronegaLvity increases

Higher the Zeff , more will be the tendency of the atom to pull the electron and more
the electronegativity.

(iii) Oxidation State

Higher the oxidation state of an atom, higher will be its electronegativity

Eg. Fe3+ (Oxidation state = +3) is more electronegative than Fe2+ (Oxidation state = +2)
Electronegativity (Contd.)

Fe < Fe2+ < Fe3+

Electronegativities 1.8 1.84 1.95

Higher the positive oxidation state, greater the tendency to attract the electrons,
greater the electronegativity

(Electronegativity α +ve charge on cation)

For anions, electronegativity decreases with increasing negative charge of the ion. This
is due to the fact that a more negatively charge ion will attract electrons less in
comparison to a less negatively charged (or neutral) ion.
Electronegativity (Contd.)

4. Type of Hybridization

Electronegativity increases with the increasing s-character of the hybrid orbital.

s-orbitals are nearer to the nucleus than p, d and f-orbitals because of their higher
penetrating power.

Thus, s-orbital have greater electron attracting power or electronegativity.

Electronegativity increases with the increasing s-character of the hybrid orbital

Electronegativity (Contd.)

Hydrocarbon Type of s-character Electronegativity

Hybridization
Methane CH4 sp3 25% 2.48
Ethylene C2H4 sp2 33% 2.75
Acetylene C2H2 sp 50% 3.29

Electronegativities of C in different hybridization states

Electronegativity (Contd.)

5. Nature of the substituent attached to the atom

Electronegativity of an atom is not the property of isolated atom

It depends on the number and nature of the atoms to which the atom (whose
electronegativity is to be considered) is bonded.

Therefore the electronegativity of the atom varies as the substituents attached to it

are changed.

For example, the electronegativities of chlorine in ClF and hydrogen chloride is

different.

Electro-negativity value of P atom in PCl3 molecule is different from that in PF5

molecule.
Electronegativity (Contd.)

Trends in Electronegativity in a period

Along a period
In general, electronegativity increases on moving from left to right in a period.

On moving along a period

• Atomic size decreases

• Nuclear charge increases

Thus, effective nuclear charge (Zeff) increases in a period and as a result

electronegativity increases.
Electronegativity (Contd.)

Li Be B C N O F
1.0 1.6 2.0 2.6 3.0 3.4 4

The elements of group 1 (alkali metals) have least electronegativities and have no
tendency to pull the shared electrons rather they loose electrons and form ionic
compounds.

While the elements of group 17 (halogens) have the highest value of

electronegativities in their respective periods. Thus, they are most electronegative and
have a strong tendency to attract electrons.
Electronegativity (Contd.)

Down the group

Electronegativity decreases on moving down in a group.

On moving down the group

• Atomic size increases because of increase in number of shells

• Nuclear charge increases

But in a group, the atomic size coupled with screening effect dominates over the
effects of nuclear charge.

Thus, in a group effective nuclear charge (Zeff) decreases and hence, electronegativity
decreases down the group.
Electronegativity (Contd.)

Group 1
Li Electronegativity decreases
Na
K ↓
Rb
Cs
Fr

Among halogens, F has the highest electronegativity and it is the most electronegative
elements in the group.
Electronegativity (Contd.)

Applications of electronegativity

• Nomenclature of binary compounds

H – Cl P – Cl3
2.1 3 2.1 3
Hydrogen chloride Phosphorus trichloride

More electronegative atom is put at the last with ‘ide’ suffix

 Electronegativity (Contd.)

• Percentage of ionic character in a covalent bond

Pauling suggested that in a heteronuclear covalent bond A–B, the ionic character may be
related to electronegativity difference between the two atoms.

1. When electronegativity difference (XA-XB) is = 1.7, the amount of ionic character is 50%
and that of covalent character is also 50%. Thus A-B bond is 50% ionic and 50% covalent.

2. When (XA-XB) < 1.7, the bond is predominantly covalent

3. When (XA-XB) > 1.7, the bond is predominantly ionic

Electronegativity (Contd.)

Also, ionic character can be measured quantitatively as mentioned below

% ionic character = 16 (xA-xB) + 3.5 (xA-xB)2 where xA and xB are the

electronegativities of the two atoms

In HCl xH =2.20 and xCl = 3.16 gives

% ionic character= 16(3.16-2.20) + 3.5 (3.16-2.20)2 = 18.58%

Thus, percent ionic character of the H-Cl bond = 18.6%

Electronegativity (Contd.)

• Determination of bond strength

Bond strength is directly proportional to electronegativity difference

H-F H - Cl H - Br H-I
2.1 4 2.1 3 2.1 2.8 2.1 2.5

H-F > H - Cl > H - Br > H-I

Strongest Weakest
bond bond

Acidic H-I > H - Br > H - Cl > H–F

character