Electronegativity

Electronegativity
 Electronegativity (EN) is defined as the tendency of an atom to attract shared
pair of electrons towards itself in a covalently bonded molecules. It is
represented as 𝝌 pronounced as (chi).
It may be noted that both I.E and ∆egH relates to the gaseous isolated state
where as EN is a property of an atom in the bonded state. Unlike IE and ∆egH,
EN is not a measurable quantity i.e. dimensionless. The EN of any element is
not constant i.e. it varies with the element to which it is bonded. F is the most
electronegative element in periodic table

 Electropositivity (EP) is a measure of an element's ability to donate electrons

and form positive ions and thus it is opposite to electronegativity. Mainly, this
is a property of metals i.e. greater the metallic character of an element, the
greater the electropositivity. Therefore, the alkali metals are most
electropositive of all.
 Factor Affecting Electronegativity
Following are the factors which affect the electronegativity:-
 Atomic radius:-
As atomic radius of the element increases the EN value decreases.

𝟏
EN∝ 𝐀𝐭𝐨𝐦𝐢𝐜 𝐑𝐚𝐝𝐢𝐮𝐬

 Effective nuclear charge (Zeff):-

The EN value increases as the Zeff on the atomic nucleus increases.

EN∝ Zeff
 Number of inner shells:-
The atoms with greater number of inner shells has less value of En than the atom
with lower number of inner shells
𝟏
EN∝
𝐧𝐮𝐦𝐛𝐞𝐫 𝐨𝐟 𝐢𝐧𝐧𝐞𝐫 𝐬𝐡𝐞𝐥𝐥𝐬
 Charge on the ion or oxidation state of the atom:-
The EN increases as the oxidation state (OS), i.e. the number of positive charge of the atom
increases while the EN decreases as the negative charge of the atom increases. This is
because as +ve charge increases size decreases while as -ve charge increases size increases.

EN∝ +ve charge

𝟏
EN∝
−𝐯𝐞 𝐜𝐡𝐚𝐫𝐠𝐞

 Nature and number of atoms (i.e. substituent attached to the atom):-

EN of an atom depends on the number and nature of the atoms to which it is bonded. For
this reason EN value of an atom is not constant.
e.g. out of bromomethane and triflouromethane, the
carbon atom of triflouromethane is more electro-
negative as it contains higher magnitude of +ve
charge due to more electronegative F atom
 State of hybridization:-
The magnitude of EN increases as the s-character in the hybrid orbitals
increases because s-electrons are comparatively near to the nucleus, and
are more attracted or penetrated into the nucleus.

Increasing order of electronegativity

 Scales of Electronegativity
A number of scales have been developed to measure electronegativity of the atoms. These
scales are arbitrary and are based on various types of experimental data such as bond
energy, IE, EA, dipole moment, Zeff etc. following are the scales of electronegativity


 Pauling’s Scale of Electronegativity
Linus Pauling was the first to propose a scale of electronegativity on the basis of bond energy.
According to Pauling, in a purely covalent bond, the bond energy of a molecule A-B, E A-B is the
geometric mean of the bond energies of atoms A and B i.e. EA-A and EB-B is

EA-B =[EA-A × EB-B]1/2

Because of the partial ionic character, A-B bond is stronger than would be expected for bond.
This extra bond energy is given by ∆E

∆E= (Actual bond energy) - (energy for 100% covalent bond)

=EA-B-[EA-A × EB-B]1/2

By calculating ∆E for different bonds, Pauling suggested the following empirical expression to
correlate ∆E with the electronegativity of two atoms 𝝌A and 𝝌B
𝝌A − 𝝌B =0.18 (∆E)1/2 where ∆E is in kcalmol-1.
𝝌A − 𝝌B =0.208 (∆E)1/2 where ∆E is in eVmolecule-1
𝝌A − 𝝌B =0.088 (∆E)1/2 where ∆E is in kJmol-1
 Mulliken’s Electronegativity Scale
Mulliken proposal is based upon the ionisation energy and electron affinity of an
atom. According to Mulliken, the tendency of an atom to compete for the shared
pair of electrons in a bond is the average of the ionization energy (IE) and electron
affinity (EA). It can be mathematically expressed as

Ionisation energy + Electron affinity

𝛘= 𝟐

Mulliken’s values of EN are about 2.8 times more than the Pauling’s values.
Therefore

𝐈𝐏+𝐄𝐀
𝛘pauling = 𝟐 ×𝟐.𝟖

𝛘𝐦𝐮𝐥𝐥𝐢𝐤𝐞𝐧
𝛘pauling = 𝟐.𝟖
 Allred Rochow’s Electronegativity Scale
Allred and Rochow proposed a new scale of electronegativity based upon the
electrostatic force of attraction between an electron and the nucleus. According to
Allred and Rochow, electronegativity of the atom is defined as the force of attraction
exerted by the nucleus on its valence electrons

𝒁∗ × 𝒆𝟐
Force of attraction = 𝒓𝟐
where Z*= effective nuclear charge,
e = charge on the electron
r = covalent radius of the atom

Thus the following empirical relationship for measuring electronegativity is given by

𝒁∗
𝛘 = 0.359 𝒓𝟐
+ 0.744
 Sanderson Electronegativity Scale
Sanderson suggested that electronegativity of an atom is stability ratio (S.R.)
which may be defined as the ratio of the average electron density of an atom to
that of a hypothetical inert atom, i.e.
𝐃
S.R = 𝐃
𝐢

where D = average electron density of an atom

Di = density of a hypothetical inert atom
The value of D is calculated by the following relation:

𝐀𝐭𝐨𝐦𝐢𝐜 𝐍𝐮𝐦𝐛𝐞𝐫 𝐙 𝟑𝐙 𝟑𝐙
D= 𝐀𝐭𝐨𝐦𝐢𝐜 𝐕𝐨𝐥𝐮𝐦𝐞
=𝟒 = 𝟒𝛑𝐫𝟑 = 𝟒.𝟏𝟗𝐫𝟑
𝟑
𝛑𝐫 𝟑

The Sanderson (S.R) and Pauling values (𝛘) are related by the expression.

𝛘 = 0.21S.R +2.77
 Jaffe’s Electronegativity Scale
According to Jaffe, electronegativity may be defined as follows-
𝐝𝐄
𝛘 =𝐝𝐪
where E = the total energy of the atom
q =partial ionic change.
The E and q are related by the following quadratic equation :
E = 𝛂q + 𝛃q2
Thus,

𝐝𝐄
𝐝𝐪
= 𝛂 + 2𝛃q

𝛘 = a + bq
where a = electronegativity of neutral atom, i.e., when q = 0
b = coefficient of electronegativity and is equal to the rate of change of 𝛘
with the ionic charge q on the atom.
Trends of Electronegativity in Periodic Table
I. Size of atom decreases
II. Shell No. remains constant
III.Zeff increases
IV. 𝛘 increases

I. Size of atom increases

II. Shell No. increases
III.Zeff constant
IV. 𝛘 decreases