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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.
Definition:
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:
Smaller the size of an atom, greater will be the attraction for the bonding electron
and larger will be the value of electronegativity.
Polar character of covalent bond : It can be explained with the help of three
combinations.
This type of bond could be considered of as a "pure" covalent bond - where the
electrons are shared evenly between the two atoms.
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 ( +).
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 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.
Note: Values in the bracket are on Mulliken scale while others are on
Pauling scale
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.
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.
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
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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