Hydration

Energy
 Hydration Energy

Hydrated Radius (H.R.)

It is the distance from the centre of ion to the last layer of water which is
bonded with ion.

q
Hydrated Radius ∝ Hydration energy ∝
r
 Example

Radii order
Li(g) Na(g) K(g) Rb(g) Cs(g)

Solution

Ans. Li(g) < Na(g) < K(g) < Rb(g) < Cs(g)
 Example

Radii order
Li+(g) Na+(g) K+(g) Rb+(g) Cs+(g)

Solution

Ans. Li+(g) < Na+(g) < K+(g) < Rb+(g) < Cs+(g)
Example

Radii order
Li+(aq) Na+(aq) K+(aq) Rb+(aq) Cs+(aq)

Solution

Ans. Li+(aq) > Na+(aq) > K+(aq) > Rb+(aq) > Cs+(aq)
 Hydration Energy

Ionic Mobility (I.M) in water

1
Ionic mobility ∝
Hydrated Radius
 Example

Ionic mobility order

Li+(aq) Na+(aq) K+(aq) Rb+(aq) Cs+(aq)

Solution

Ans. Li+(aq) < Na+(aq) < K+(aq) < Rb+(aq) < Cs+(aq)
 Example

Ionic mobility order

F –(aq) Cl– (aq) Br– (aq) I– (aq)

Solution

Ans. F –(aq) < Cl–(aq) < Br–(aq) < I–(aq)

 Hydration Energy
Condition for solubility of ionic compound in water

∆Hsol
NaCl (s) Na+ (aq) + Cl– (aq)

∆Hhyd (Na+) +H2O +H2O ∆Hhyd (Cl–)

L.E.
Na+ (g) + Cl- (g)
∆Hsol = L.E. + ∆Hhyd

𝐍𝐨𝐭𝐞

When hydration energy is dominant over lattice energy then, that particular
ionic compound is soluble in water.
𝐍𝐨𝐭𝐞

Some Important Solubility order

1. LiF < NaF < KF < RbF < CsF

2. LiOH < NaOH < KOH < RbOH < CsOH

3. Be(OH)2 < Mg(OH)2 < Ca(OH)2 < Sr(OH)2 < Ba(OH)2

4. MgF2 < CaF2 < SrF2 < BaF2 < BeF2

 𝐍𝐨𝐭𝐞

1. BeSO4 > MgSO4 > CaSO4 > SrSO4 > BaSO4

2. BeCO3 > MgCO3 > CaCO3 > SrCO3 > BaSO3

3. Li2CO3 < Na2CO3 < K2CO3 Rb2CO3 < Cs2CO3

4. NaHCO3 < KHCO3 < RbHCO3 < CsHCO3

 𝐍𝐨𝐭𝐞

1. AgF > AgCl > AgBr > AgI

2. PbF2 > PbCl2 > PbBr2 > PbI2

Fajan’s
Rule
 Fajan’s Rule
Fajan’s Rule

No bond is 100 % covalent bond due to Vander Waal forces or weak forces
or London dispersion forces as well as no bond is 100% ionic bond due to
polarization which is explained by Fajan’s rule.
 Fajan’s Rule
Polarisation

Deformation of electron cloud of anion by cation is known as polarization.

 Fajan’s Rule
Polarising Power

It is the power of cation with which it can deform electron cloud of anion.
Example

Polarising power order

Li+ Na+ K+ Rb+ Cs+

Solution

Ans. Li+ > Na+ > K+ > Rb+ > Cs+

Example

Polarising power order

Na+ Mg2+ Al3+

Solution

Ans. Al3+ > Mg2+ > Na+

 Fajan’s Rule
Polarisability

It is the easiness of anion with which it can get deform.

Example

Polarisibility order
F– Cl– Br– I–

Solution

Ans. F – < Cl– < Br– < I–

Example

Polarisibility order
F- O2- N3-

Solution

Ans. F – < O2– < N3–

 Fajan’s Rule
Factors affecting Polarisation

1
1. Polarisation ∝ Size of cation

2. Polarisation ∝ charge on cation

3. Polarisation potential (𝜑) = charge density of cation

Charge on cation
φ=
Size of cation

Polarisation potential (𝜑) increases, polarisation also increases.

 Fajan’s Rule
4. Polarisation ∝ size of anion (rA)

5. Polarisation ∝ charge on anion

6. If all above factors are same then cation having pseudo inert gas electronic
configuration causes more polarization due to the poor shielding of d-
electron.
 Fajan’s Rule
Inert (Noble) gas configuration

ns2np6

Example

Ne, Na+, Mg2+, F-,Ca2, O2-, N3- etc.

 Fajan’s Rule
Pseudo Inert (Noble) gas configuration

ns2p6d10

Example

Zn2+, Cd2+, Hg2+, Cu+, Ag+, Au+, etc.

 Fajan’s Rule
Non inert gas configuration (18+2 e–)

(n-1)s2p6d10ns2

Example

Tl+, Hg, Pb2+, Bi3+ etc.

Properties Affected
by
Polarisation
 Fajan’s Rule
Properties which are affected by polarisation

Solubility in polar
Covalent character increases solvent decreases

Solubility in non-polar
Ionic character decreases
solvent increases
High
Melting point decreases polarisation
means Electrical conductivity decreases

Thermal stability decreases

Acidic nature of oxide increases

Intensity of colour increases

Example

Covalent character order.

LiCl NaCl KCl RbCl CsCl

Solution

Ans. LiCl > NaCl > KCl > RbCl > CsCl
Example

Covalent character order.

NaF NaCl NaBr NaI

Solution

Ans. NaF < NaCl < NaBr < NaI

Example

Covalent character order.

NaF MgF2 AlF3

Solution

Ans. NaF < MgF2 < AlF3

Example

Covalent character order.

SnCl2 SnCl4

Solution

Ans. SnCl2 < SnCl4

Example

Covalent character order.

NaCl CuCl

Solution

Ans. CuCl > NaCl

Example

Covalent character order.

ZnCl2 CdCl2 HgCl2

Solution

Ans. ZnCl2 < CdCl2 < HgCl2

Example

Electrical conductivity order.

KF KCl KBr KI

Solution

Ans. KF > KCl > KBr >KI

Example

Electrical conductivity order.

BeO MgO CaO SrO BaO

Solution

Ans. BeO < MgO < CaO < SrO < BaO
 Fajan’s Rule

Colour of compound

Polarisation increases, intensity of colour increases

AgCl AgI
White yellow

PbCl2 PbI2
White Dark yellow

Hg2Cl2 Hg2I2
White Green
 Fajan’s Rule
𝐍𝐨𝐭𝐞

1. It is not necessary that all metal iodide should be coloured

𝐄𝐱𝐚𝐦𝐩𝐥𝐞

1. All alkali metal iodide are colourless or white in colour

2. If metal iodide is colourless then it is necessary that bromide, chloride and

fluoride of that particular metal must be colourless but vice versa not true.
 Fajan’s Rule
Nature of Oxide
Example

Acid character order-

Li2O BeO B2O3 CO2 N2O5

Solution

Ans. Li2O < BeO < B2O3 < CO2 < N2O5
Example

Acid character order -

Na2O MgO Al2O3 SiO2 P4O10

Solution
Example

Acid character order-

CO CO2

Solution

Ans. CO < CO2

Example

Acid character order-

HClO4 HBrO4 HIO4

Solution

Ans. HClO4 < HBrO4 < HIO4

Example

Acid character order-

SO3 SO2

Solution

Ans. SO3 > SO2

 Example

Compare bond order (BO), bond length (BL) and bond strength in O2 , O2+, O2–,
O22+, O22– ?

Solution
Example

Compare bond order, bond length , bond energy and in NO and NO+ ?

Solution
Example

The common features among CN- , CO , NO+ and N2 are ?

(A) Isoelectronic , paramagnetic , Bond order = 3
(B) Isoelectronic , diamagnetic , Bond order = 3
(C) Isoelectronic , paramagnetic , Bond order = 2
(D) Isoelectronic , diamagnetic , Bond order = 2

Solution

Ans. (B)
Example

If Hund’s rule is violated then B2 molecule have :

(A) Bond order = 2 ,paramagnetic (B) Bond order = 2 ,diamagnetic
(C) Bond order = 1 ,paramagnetic (D) Bond order = 1 ,diamagnetic

Solution

Ans. (D)
 Example

Compare bond order (BO), bond length (BL) and bond strength in N2 , N2+, N2–,
N22+, N22– ?

Solution
Example

If sp intermixing is not operative, then which of the following will be

paramagnetic ?
(A) B2 (B) C2 (C) N2 (D) O2

Solution

Ans. B, D
Example

Consider the following oxidation/reduction process,

+e- –e-
(A) N2 N2- (B) N2 N2+
–e- +2e-
(C) O2 O2+ (D) O2+ O2-

Solution

Ans. (C)
Extra Questions For
practice

Example

Which contains strongest H-bond ?

(A) O-H…S (B) S-H…O
(C) F-H…F (D) O–H…O

Solution

Ans. (C)
Extra Questions For
practice

Example

Comment on polarity order of given molecules

CH3 CH3 CH3
NO2

NO2
NO2

Solution
Extra Questions For
practice

Example

Comment on polarity order of given molecules

Cl Cl Cl
NO2

NO2
NO2

Solution
Extra Questions For
practice

Example

Give the decreasing order of solubility in H2O

CH4 NF3 NH3 H2O

Solution

Ans. H2O > NH3 > NF3 > CH4

Extra Questions For
practice

Example

Which bond angle ‘θ’ would result in the maximum dipole moment for the
triatomic molecule YXY

(a) θ = 90° (b) θ = 120° (c) θ = 150° (d) θ = 180°

Solution

Ans. (A)
Extra Questions For
practice

Example

The dipole moment is zero for the molecule

(A) Ammonia (B) Boron trifluoride
(C) Sulphur dioxide (D) Water

Solution

Ans. (B)
Extra Questions For
practice

Example

PClxF5-x shows non-polar behaviour when x is;

(A) 0,5 (B) 0 (C) 2,1,4 (D) 0,4,1

Solution

Ans. (A)
Extra Questions For
practice

Example

Hydrogen bond strength order in H2O and H2O2.

Solution