CHEMICAL BONDING

INERT PAIR EFFECT

 In p-block elements the stability of the lower oxidation state increases on descending the group.

Because increased effective nuclear charge holds ns electrons tightly due to poor shielding
effect of inner d & f orbitals and thereby, restrict their (ns electrons) participation in bonding
only np electrons take part in bond formation. As a result of this, +1 oxidation state of Tl is
more stable than it's +3 oxidation state. Pb shows +2 stable oxidation state and Bi shows +3
stable oxidation state.

 For example:

Group 13 Group 14
B (+3) C (+4)
Al (+3) Si (+4)
Ga (+3), (+1) Ge (+4), (+2)
In (+3), (+1) Sn (+4), (+2)
Tl (+3), (+1) Pb (+4), (+2)
Order of stability : Tl+1 > In+1 > Ga+1 (due to inert pair effect)
Pb+2 > Sn+2 > Ge+2 (due to inert pair effect)

Ex. PbCl4 is stable at room temperature whereas PbI4 doesn't exist.

Sol. Due to inert pair effect Pb(+4) is less stable than Pb(+2). Hence it is very good oxidant.
Pb(IV) + 2e–  Pb(II)
Reducing abilities of halides follows the sequence
I– > Br– > Cl–

 Inert pair effect : order of stability

Due to inert pair effect :
 (a)Tl+1> Tl+3 (b) Bi+3> Bi+5 (c) Pb+2> Pb+4 (d) Hg > Hg+2

 (a) Pb4  2e Pb+2 (b) Tl3  2e Tl+ (c) Bi 5  2e  Bi+3
(Oxidizing agent) (Oxidizing agent) (Oxidizing agent)

Note : PbO2, Pb2O3 (PbO + PbO2), Pb(ClO4) are oxidizing agents because Pb+2 is more stable
than Pb+4
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 CHEMICAL BONDING
 Reducing power order I– > Br– > Cl– > F–

PbI4  PbI2 + I2

Spontaneous
(a)
PbI4 does not exist because Pb+4 act as oxidizing agent and I– act as reducing agent.

Pb+4 + I– 
 Pb+2 + I2
PbBr4   PbBr2 + Br2
On
(b) Warming

PbCl4 
 PbCl2 + Cl2
Heating
(c)
CuI2 

FeI3 
   does not exist
BiI5 
 
TlI3[with I ]
Note : Only pentahalide of Bi is BiF5 is possible. [F is weak reducing agent]
2  3 
  (a) Cu  I 
Cu2I2  I2  Fe2  I2
(b) Fe  I 
(O.A.) (R.A.) (O.A.) (R.A.)

5 
 Bi3  I2
(c) Bi  I 
3 
Tl  I2
(d) Tl  3I 
(O.A.) (R.A.) (O.A.) (R.A.)

But TI3 [with I3] exists, TI3 T+ I3

Note : [CuI4]2– complex does not exists, [CuI4]3– exists.

Stability of higher oxidation state  down the group
CX4> SiX4> GeX4> SnX4> PbX4 (Where X is F, Cl, Br, I)
Stability of lower oxidation state  down the group.
CX2< SiX2< GeX2< SnX2< PbX2 (Where X is F, Cl, Br, I)

 Application of Fajan’s Rule:

 Thermal stability:
Anionic part polyatomic
Ionic
Anionic part monoatomic

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 CHEMICAL BONDING
 Thermal stability of Ionic compound having polyatomic anion:
Order of Thermal stability:
(a) Li2CO3< Na2CO3< K2CO3< Rb2CO3< Cs2CO3

(b) BeCO3< MgCO3< CaCO3< SrCO3< BaCO3

(c) Li2SO4< Na2SO4< K2SO4< Rb2SO4< Cs2SO4

(d) BeSO4< MgSO4< CaSO4< SrSO4< BaSO4

(e) LiNO3< NaNO3< KNO3< RbNO3< CsNO3

(f) Be(NO3)2< Mg(NO3)2<Ca(NO3)2<Sr(NO3)2< Ba(NO3)2

(g) NaHCO3< KHCO3< RbHCO3< CsHCO3

(h) Be(HCO3)2< Mg(HCO3)2<Ca(HCO3)2<Sr(HCO3)2< Ba(HCO3)2

Note: Na, K ,Rb, Cs carbonate do not decompose on heating, they melt at high temperature.
 Heating effect of carbonate:

(a) CaCO3   CaO + CO2

(b) PbCO3   PbO + CO2

(c) FeCO3   FeO + CO2

(d) ZnCO3   ZnO + CO2

(e) Li2CO3   Li2O + CO2

 Oxides of native metal (Ag, Hg, Au, Pt) are less stable and further decompose on heating


 
Ag 2CO3   Ag 2O  CO2  Ag 2Ois obtained
(yellowish  white
or white) 

 1
Ag 2O   2Ag  O2
2

 1 
HgCO3   Hg  O2  CO2  HgO is not obtained
2 

Note: CuO 
high temp.
 Cu 2O
Black Red

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 CHEMICAL BONDING
 Thermal stability of ionic compound having monoatomic anion :
MX  M+ + X– [Thermal Stability decided by Lattice Energy]
L.E = Kq1q2/r2(rc + ra)
1
  L.E.  charge L.E. 
size
  Charge , L.E.   size, L.E. 
Thermal stability Lattice energy

Ex : (a) LiCl > NaCl > KCl > RbCl > CsCl (b) LiBr > NaBr > KBr > RbBr > CsBr
(c) Li2O > Na2O > K2O > Rb2O > Cs2O (d) Li3N > K3N > Rb3N
(e) KF > KCl > KBr > KI

 Important :

 O2–2 , O2–1, —
OH (They are diatomic anion)
Peroxide Superoxide
T.S. acts as polyatomic

acts as monoatomic
Solubility
(a) LiOH<NaOH< KOH <RbOH<CsOH
(b) Na2O2< K2O2< Rb2O2< CS2O2
(c) KO2< RbO2< CsO2

 Colour of Ionic compound :

Higher the polarization of ionic compound greater will be the colour intensity of ionic
compound.
AgF AgCl AgBr AgI
Ex.:
white pale yellow yellow

Que. Predict the colour of CuCl and CuBr if colour of CuI is white :
Ans. White
** Ionic Mobility :
, Hydrate size , Ionic mobility 
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 CHEMICAL BONDING
    
Ex. (i) Hydrate Size Li(aq) > Na (aq) > K (aq) > Rb(aq) > Cs(aq)
    
Ionic Mobility Li(aq) < Na (aq) < K (aq) < Rb(aq) < Cs(aq)
2 2 2 2 2
(ii) Hydrate Size Be(aq.) > Mg(aq.) > Ca (aq.) > Sr(aq.) > Ba (aq.)
2 2 2 2 2
Ionic Mobility Be(aq.) < Mg(aq.) < Ca (aq.) < Sr(aq.) < Ba (aq.)
– – – –
(iii) Hydrate Size F(aq.) > Cl(aq.) > Br(aq.) > I(aq.)
– – – –
Ionic Mobility F(aq.) < Cl(aq.) < Br(aq.) < I(aq.)
Exception Case
(iv) Note :  of : Be+2 > Al+3
6.4 6
2 3
Hydrate Size Ba (aq.) > Al(aq.)
2 3
Ionic Mobility Be(aq.) < Al(aq.)

 Solubility
Case-I:Down the group, H.E.  , L.E  , solubility 
(a) LiF < NaF < KF < RbF < CsF (b) BeO < MgO < CaO < SrO < BaO
(c) BeS < MgS < CaS < SrS < BaS (d) LiOH < NaOH < KOH < RbOH < CsOH
Case-II: Down the group, solubility 
(a) LiClO3 > NaClO3 > KClO3 > RbClO3 > CsClO3 (chlorate)
(b) LiClO4 > NaClO4 > KClO4 > RbClO4 > CsClO4 (perchlorate)
(c) BeSO3 > MgSO3 > CaSO3 > SrSO3 > BaSO3 (sulphite)
(d) BeSO4 > MgSO4 > CaSO4 > SrSO4 > BaSO4 (sulphate)
(e) BeS2O3 > MgS2O3 > CaS2O3 > SrS2O3 > BaS2O3 (thiosulphate)
(f) BeCrO4 > MgCrO4 > CaCrO4 > SrCrO4 > BaCrO4 (chromate)
(g) BeCO3 > MgCO3 > CaCO3 > SrCO3 > BaCO3 (carbonate)
Note : Br–/I– : They follow trend of polyatomic
(a) LiBr > NaBr > KBr > RbBr > CsBr (b) NaI > LiI > KI > RbI > CsI
Case –III: If number of cations> number of anions, then solubility  down the group.
(a) Li2O < Na2O < K2O < Rb2O < Cs2O
(b) Li2CO3 < Na2CO3 < K2CO3 < Rb2CO3 < Cs2CO3
(c) NaHCO3< KHCO3< RbHCO3< CsHCO3
(Sparingly soluble)
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