CHEMISTRY Theory Notes on Chemical Bonding-III BULLS EYE

Polarisation (Change of ionic character into covalent character):

When two oppositely charged ions of unequal size approach each other closely, the ion smaller in size
attracts outermost electrons of the other ion and repel its nuclear charge. The net result is distortion or
polarisation of the bigger ion. The distortion is usually done by the cation as its size is smaller than the anion
but vice-versa is also true.
The cloud of anion no longer remains symmetrical but is elongated towards the cation.
The ability of cation to polarise the nearby anion is called its polarising power and the tendency of an anion
to get distorted or deformed or polarised by the cation is called its polarisability.
Due to polarisation, sharing of electrons occur between two ions to some extent and the bond shows some
covalent character.
So higher will be the polarisation, higher will be the covalent character.
The magnitude of polarisation depends upon a number of factors which are known as FAJAN’S RULE 
(1) Charge on cation: (Assuming other factors to be same ) higher the positive charge, more will be the
polarisation, more is the covalent character.
AlCl  MgCl  NaCl across the period size remaning same
  
3  2  
covalant charc. increases B.Pt. decreases
Fe2+ < Fe3+ FeCl2 < FeCl3 PbCl4 > PbCl2
(2) Size of the cation: Smaller the size of cation, more is the polarisation of anion & hence more is the
BeCl  MgCl  CaCl  SrCl  BaCl
covalant character.   2 2    2   2  2
covalant charc. increases B.Pt. decreases
Polarising power: Li+ > Na+ > K+ > Rb+ > Cs+ & F < Cl < Br < I
Covalant character: LiCl > NACl > KCl > RbCl > CsCl & LiF < LiCl < LiBr < LiI
Greater charge on anion, more it will be polarisable. (N3 > O2– > F–)
(3) Size of anion :
Larger will be the size of anion, larger it will be polarised so greater will be the covalent character.
AlF3  AlCl 3  AlBr3  AlI 3
covalent charac. increases
(4) Configuration of cation : The cations with 18 es in other most shell bring greater polarisation of the
anion than those with inert gas config. even if both the cations have same size & same charge. (ns2np6nd10)
Pseudo inert configuration
Cu+ Na +
Configuration 2,8,8 2,8
size 0.96 Å 0.95 Å
M.Pt. CuCl 442oC NaCl 800oC
So CuCl is more covalent than NaCl.
Due to poor shielding of d-orbitals.
(ns2np6nd10) > (ns2np6)
Application of Fazan’s rule (Ionic potential f )
“The polarizing power of cation can be expressed in terms of ionic potential f ”
(a) ionic potential can be defined as ratio of charge on cation to the size of cation.
charge on cation
(b) f =
size of cation
(c) f  polarising power  covalent character..
(d) In a period f increases from left to right.
(g) Reactivity of metal halides increases as the value of f decreases.
(h) Tendency to form complex compounds increases as the value of f increases.
(i) Thermal stability of carbonates increases as the value of f decreases.
Points to Remember
(i) On moving down a group, the polarising power of the cations goes on decreasing.
(ii) Polarising power of the cations increase in moving left in a period.
(iii) The polarisability of the anions by a given cation decreases in moving down a group.
(iv) The polarisability of the anions by a given cation increases moving down a group.
(v) Increase of polarisation brings more of covalent character in an ionic compound. The increased cova-
lent character is indicated by the decrease in melting point of the ionic compound. Examples:
Polarisation increases  ; Covalent character increases  ; Melting point decreases 
(a) NaF < NaCl < NaBr < NaI
(size of anion increases)
m.pt. (oC) 988 801 755 651
(b) CaF2 < CaCl2 < CaBr2 < CaI2
(size of anion increases)
o
m.Pt. ( C) 1392 772 730 575
(c) BaCl2 <SrCl2 < CaCl2 <BeCl2
(size of cation decreases)
m.pt. (oC) 960 872 772 712 405
(d) NaCl < MgCl2 < AlCl3
(charge on the cation increases)