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ELECTRONEGATIVITY

What is electronegativity and how does it vary around the Periodic Table? What
is the reason of its variation? It will also tell that differences in electronegativity
affect bond type and also explain what are polar bonds and polar molecules.

To understand all this in details, please go through the page.

Definition:

Electronegativity is a measure of the tendency of an atom to attract a bonding


pair of electrons.

It can also be defined as the power of ability of an atom to attract the shared pair
of electrons towards itself in a molecule. Shared pair means bonding pair of
electrons.

Two scales of electronegativity are used commonly: the Pauling scale (proposed
in1932) and the Mulliken scale (proposed in 1934). Another proposed scale is the
Allred-Rochow scale.

The Pauling scale is the most commonly used to measure electronegativity and
it is based on bond energy data. Fluorine is the most electronegative element
having value of 4.0, but caesium and francium are the least electronegative
having value 0.7.

Pauling pointed out that the difference in electronegativities lхA – хBl = 0.102√∆

The Mulliken scale is related to the values of electron gain enthalpy and
ionization enthalpy of the concerned atoms. This scale explains that an atom with
high value of ionization enthalpy and low electron gain enthalpy will have greater
tendency of attracting the electrons and thus will have high value of
electronegativity. It is represented as:

Electronegativity depends on the atomic size:

Smaller the size of an atom, greater will be the attraction for the bonding electron
and larger will be the value of electronegativity.

Example: Atomic radius of oxygen is less than that of nitrogen. Therefore


electronegativity of oxygen (3.5) is more than that of nitrogen (3)

Polar character of covalent bond : It can be explained with the help of three
combinations.

1) Combination of atoms having equal electronegativity:

Consider a bond between two atoms, A and B. having same electronegativity.


If the atoms are of equal electronegativity, then both have the same tendency to
attract the bonding pair of electrons, and then this bond pair will be found on
average mid way between the two atoms .For example, bond formation between
H2 and Cl2 molecules.

This type of bond could be considered of as a "pure" covalent bond - where the
electrons are shared evenly between the two atoms.

2) Combination of atoms having different electronegativity:

Again consider two atoms A & B. B is more electronegative than A. So B will


attract the electron pair more strongly than A.

B end of the bond will have large share of electron density as compared to that of
A. So it becomes slightly negative ( -). At the same time, the A end will become
slightly positive ( +) due to the shortage of electrons.
3) Combination of atoms, in which one atom has very large
electronegativity than the other:

Consider two atoms A&B forming a bond between them. B atom has very large
electronegativity as compared to A. Then B atom has complete control on both
the electrons and drags these electrons towards it. With this two ions are formed.

Polar Bond - It is the covalent bond, which develops a partial ionic character
as a result of the difference of electronegativities of the atoms forming the bond.
Formation of polar covalent bond occurs due to the unequal distribution of
electron charge density. The more electronegative atom acquires a partial
negative charge ( -) where as the less electronegative atom will acquire a partial
positive charge ( +).

Examples: The hydrogen-chlorine bond in HCl or the hydrogen-oxygen bonds in


water are typical examples of polar covalent bond
In a pure covalent bond, the shared pair of electrons lies midway between the
nuclei of two atoms. But in a polar bond, the shared pair of electrons has been
dragged slightly towards one end, which is more electronegative.

Let’s take the example of Lithium iodide, which is ionic with some covalent
character. In this case, the shared pair of electron hasn't moved entirely over to
the iodine end of the bond. Unlike other ionic compounds Lithium iodide is
soluble in non-polar solvents like ethanol.

The above three combinations can be summarized as:

• No electronegativity difference between two atoms formation of pure non-


polar covalent bond.

• A small electronegativity difference forms polar covalent bond.

• A large electronegativity difference forms an ionic bond.

Some complicated examples of polar bond:

In CCl4, each bond is polar but not the molecule.


The molecule as a whole isn't polar because it doesn't have an end or a side,
which is slightly either negative or positive. All external ends of the molecule are
negative, but there is no overall separation of charge from top to bottom or from
left to right in a molecule.

In contrast to above, CHCl3 is polar molecule.

The hydrogen at the top of the molecule is less electronegative meaning thereby
it is slightly positive as compared to carbon. Carbon has slightly negative charge.
This shows that the molecule is slightly positive at "top" and slightly negative at
"bottom", and therefore it is a polar molecule.

A polar molecule will need to be "asymmetrical" in some way.

Periodic Trends of Electronegativity:

The most electronegative element in periodic table is fluorine and as we know


that electronegativity is a periodic function of atomic number of elements. It
should always increase towards fluorine in the Periodic Table.
Trends in electronegativity across a period:

As we move across a particular period till the elements of group 17 the


electronegativity of the elements increases because size of the atom decreases
and force of attraction for the bonding electrons increases.

Consequently the value of electronegativity increases. In a periodic table the


electronegativity of group 17 elements is found to be the highest. The following
chart depicts electronegativities from sodium to chlorine, which is increasing.
Trends in electronegativity down a group:

As we move down in a group, electronegativity decreases because the size of


the atom increases due to the addition of new shell. As a result the force of
attraction for the electrons decreases. With this electronegativity also decreases.
(If it increases up to fluorine, it must decrease as you go down.) The graph below
depicts the patterns of electronegativity in Groups 1 and 7.
Values of electronegativities given by Pauling & Mulliken:

Note: Values in the bracket are on Mulliken scale while others are on
Pauling scale

As we observe from the table, values of electronegativity decrease down a


particular group and increase across a particular period.

Increase in electronegativities can be explained by taking an example of


sodium chloride (across a period).

Taking sodium the first element of period 3 and chlorine the last (except noble
gas - argon), assuming that sodium chloride was covalently bonded.
Both sodium and chlorine have their bonding electrons in the 3rd level. The
electron pair is shielded from both the nuclei by the 1s, 2s and 2p electrons, but
the force of attraction of chlorine nucleus is more due to the presence of 6
protons in it. So electron pair gets dragged towards the chlorine and ions are
formed.

Increase in the number of charges on the nucleus increases the electronegativity


that attracts the bonding pair of electrons more strongly.

Decrease in electronegativities down a group can be explained with the


help of an example of hydrogen fluoride and hydrogen chloride.

The bonding pair of electrons is shielded from the fluorine's nucleus by the 1s2 (2
electrons). But In case of chlorine the bonded pair is shielded by 1s22s22p6 (10
electrons).
There is a net force of attraction from the centre of the fluorine or chlorine of +7
electrons in both the cases. But fluorine has the bonding pair in the 2nd level
whereas chlorine has 3rd level. If the bonded pair is closer to the nucleus then it
will have greater attraction.

Electronegativity decreases down a group because the bonding pair of electrons


is at a large distance from the nucleus and is not experiencing force of attraction.

Covalent character in ionic bond:

As we have discussed covalent bond develops ionic character due to the


difference of electronegativities of bonded atoms. Similarly the ionic bond also
develops covalent character.

When two oppositely charged ions come close the positive ion tends to distort
the electron cloud of negative ion towards itself. As a result the electron cloud of
negative ions gets polarized and electron density is pulled in between the nuclei
of the 2 atoms. It means the ionic bond dies not remain 100% ionic but develops
some covalent character

The polarisability

It is the ability of anion to undergo distortion.

Polarising power

The power of the cation to cause distortion in the electron cloud of negative ion is
called polarizing power.

Fajan rules

The extent of covalent character in ionic bond depends on the polarizing power
of cation and polarisability of anion which are decided on the set of rules. These
are called Fajan Rules.
1) Smaller the size of cation, larger will be the polarizing power. For example:
Li+< K+ ions. Therefore LiCl is more covalent than KCl.

2) For 2 cations of similar size the one with pseudo nobel gas configuration
ns2np6nd10 has larger polarizing power than with actual noble gas
configuration. For example – CuCl is more covalent in nature than NaCl
because polarizing power of Cu+ is greater than Na+.

3) Larger the size of an anion, higher will be the polarizability e.g. LiI is more
covalent than LiF. Similarly AlF3 is more ionic but AlCl3 is covalent.
Aluminium fluoride is ionic because the aluminium ion can't polarize the
small fluoride ion sufficiently to form a covalent bond.

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