Introduction

Definition and Concept

Applications

➢ Bond parameters
➢ Lewis Acidic / Basic nature
➢ Hybridisation & Geometry
➢ Stability
 BACK BONDING

Introduction

Lone pair sometimes may be transferred from filled orbital of an atom to

unfilled (vacant) orbital of adjacent atom in a covalent molecule or ion.

This phenomena is known as back bonding.

 BACK BONDING

Introduction

It is a type of p dative bond.

Coordinate Bond / Dative Bond

s - Type p - Type

H 3N BF3 C === O

••

••
••
It may be partial or full depending upon the donating and the

accepting capacities of donor and acceptor atom.

 BACK BONDING

Introduction

It is a type of intramolecular (within the molecule) Lewis acid – Lewis

base interaction.

Lewis Acid Lewis Base

(Acceptor) (Donor)
 BACK BONDING

Introduction

In general, second period elements C, N, O and F having lone pair are

good donor atoms.

•• •• •• ••
C < N < O < F

••

••

••

••
•• •
•• •
 BACK BONDING

Conditions for Back Bonding

There should be a covalent bond between two atoms.

One of them atom must have lone pair.

Another atom must have vacant orbital.

At least one atom either donor or acceptor atom should be of

2nd period.
 BACK BONDING

Types of Back Bond

(1) pp – pp Back Bond (2) pp – dp Back Bond

Example BF3 Example PF3

Why dp – dp is not there ?

 BACK BONDING

Types of Back Bond

(1) pp – pp Back Bond (2) pp – dp Back Bond

Example BF3 Example PF3

Due to size of d orbital

 BACK BONDING

Back Bonding in BF3

Fact dB – F experimental < dB – F calculated

2p ↿ ↿ Vacant orbital
E
2s ↿

Boron
 BACK BONDING

Back Bonding in BF3

+
F +
F F F
− − −
F B F B F B F B +
F F F F

d+
F – d+
B F
d+
F

Resonance Hybrid
 BACK BONDING

Back Bonding in BF3

Both atoms belong to 2nd period.

Nature of back bonding is 2pp - 2pp.

Direction of back bonding is from ‘F’ → ‘B’.

 BACK BONDING

Effect of back bonding in BF3

B-F Bond order Increase (↑) d+

F – d+
dB–F Decrease (↓) B F
d+
F
∠FBF No change
Resonance Hybrid
Geometry or shape No change
Back Bonding in BF3
Compare dB–F (bond length) in BF3 and 𝐁𝐅𝟒– .
F
F
Solution
B F B–
F F
F F
Vacant orbital

Back Bonding

Partial double bond

character
Hybridisation sp2 sp3
% s character in bond
33.3 25
Ans. dB–F : BF3 < 𝐁𝐅𝟒−
 BACK BONDING

Driving force for Back Bonding

➢ Interelectronic repulsion in donor atom.

➢ Tendency to lower potential energy (P.E.).
PE ↑

0
𝐅𝐑 > 𝐅𝐀 𝐫𝟎 𝐅𝐀 > 𝐅𝐑 𝐫→

𝐅𝐀 ≈ 𝐅𝐑
In which of the following specie back bonding may takes place ?
(A) PH3 (B) PF3 (C) 𝐁𝐅𝟒– (D) CF4

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

Lone pair Vacant orbital Donor / acceptor

(Period)
PH3

PF3

𝐁𝐅𝟒–
CF4

Ans. B
 BACK BONDING

Back Bonding in PF3

••
••
–
P
•• + ••
••
F+ F••F••

••
••

••
FF +

••
••
••
••
••
F••
FF

••
••

••
••

••
••
•••
••
•
••
••
••

••
–
P
d+ d+
F F
d+
F
Nature of back bonding is 2pp – 3dp. Resonance Hybrid

Direction of back bonding is from F → P.

 BACK BONDING

Effect of back bonding in PF3

P-F Bond order Increase (↑) ••

–
P
dP–F Decrease (↓) d+ d+
F F
d+
∠ FPF Increase (↑) F
Resonance Hybrid

Geometry or shape No change

Compare extent of Back Bonding and Lewis acidic nature in the following:
BF3 BCl3 BBr3 BI3

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

2pp – 2pp 2pp – 3pp 2pp – 4pp 2pp – 5pp

B F B Cl B Br B I

Extent of Back bonding : BF3 > BCl3 > BBr3 > BI3

Lewis acidic nature : BF3 < BCl3 < BBr3 < BI3
BACK BONDING

Effect of Back Bonding

Bond order increases.

Bond length decreases.

Bond strength increases.

Bond angle may increases but it never decreases.

Lewis acidic and Lewis basic nature changes.

Hybridisation may or may not change.

Geometry of the molecule may change.

N (Me)3 is pyramidal with respect to NC3 unit, N(SiH3)3 is planar with
respect to NSi3 unit. Discuss why ?

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧 N(CH3)3 Trimethlylamine

N
H3C CH3
CH3
No Back Bonding
N (Me)3 is pyramidal with respect to NC3 unit, N(SiH3)3 is planar with
respect to NSi3 unit. Discuss why ?

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧 N(SiH3)3 Trisilylamine

–
SiH33
– +
H33Si N
–
H3Si SiH333
SiH
SiH
SiH3

d–
SiH3
d– +
H3Si N
d–
Resonance Hybrid SiH3
 BACK BONDING

Conclusions

d–
2pp - 3dp back bond is present. SiH3
d– +
H3Si N
dN–Si (bond length) decreases ↓ d–
SiH3
∠ SiNSi increases ↑

Lewis basic nature decreases ↓

Direction of back bonding from ‘N’ → ‘Si’.

NSi3 unit becomes planar.

Hybridisation of Nitrogen changes from ‘sp3’ to ‘sp2’.

BACK BONDING

𝐍 𝐒𝐢𝐇𝟑 𝟑 Trisilylamine
Which is more Lewis basic ?

(A) N(CH3)3 (B) N(SiH3)3

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

d–
SiH3
d– +
N H3Si N
d–
H3C CH3 SiH3
CH3
No Back Bonding 2pp - 3dp Back Bonding

Ans. A > B
CH3NCS is bent where as SiH3NCS is linear with respect to ‘N’ why ?

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧 CH3NCS

N == C == S
H 3C 142°

No Back Bonding.

Shape with respect to ‘N’ is ‘Bent’.

Hybridisation of ‘N’ is sp2.

CH3NCS is bent where as SiH3NCS is linear with respect to ‘N’ why ?

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧 SiH3NCS

180°

N ==C == S → H3Si — N == C == S

2pp – 3dp back bonding.

Direction of back bonding from ‘N’ → ‘Si’.
Hybridisation changes from sp2 to sp.
Shape with respect to ‘N’ changes from ‘Bent’ to ‘linear’
In which of the following species back bonding may take place ?

(A) CO (B) B3N3H6 (C) 𝐁𝟑𝐎𝟑−

𝟔 (D) P(SiH3)3
In which of the following species back bonding may take place ?
(A) CO

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

C == O

••

••
2p 2p

2p𝝅 - 2p𝝅 back bonding is present.

Direction of back bonding from ‘O’ → ‘C’.

In which of the following species back bonding may take place ?

(B) B3N3H6 (Inorganic Benzene/Borazine/Borazole)

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

H 2p𝝅 - 2p𝝅 back bonding is present.

H B H Direction of back bonding from ‘N’ → ‘B’.

N N
Hybridisation of ‘N’ and ‘B’ is sp2.

B B Molecule is planar and aromatic.

H N H
More reactive then organic benzene.
H
Resonance in B3N3H6

B-
-
H
HH H
+
N++
N
N N+
N

BB-- B--
BB
+
H
H N+
N H

H
H
H
Resonance in B3N3H6
In which of the following species back bonding may take place ?
(C) 𝐁𝟑𝐎𝟑−
𝟔

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

••
O−

••
••
2p𝝅 - 2p𝝅 back bonding is present.

B Direction of back bonding from ‘O’ → ‘B’.

O O

••

••
Hybridisation of ‘O’ and ‘B’ is sp2.

B B Molecule is planar and aromatic.

•• ••−
O − O
O

••
••

•• •• ••
Resonance in 𝐁𝟑𝐎𝟑−
𝟔
In which of the following species back bonding may take place ?
(D) P(SiH3)3

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

.. No back bonding since ‘P’ and ‘Si’ both

belongs to third period
P

H3Si SiH3

SiH3
In which of the following specie(s) back bonding may take place ?
(A) CO (B) B3N3H6 (C) 𝐁𝟑𝐎𝟑−
𝟔 (D) P(SiH3)3

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

Ans. A,B,C
Why bond angle in Cl2O is greater than H2O ? Discuss.

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

On the basis of electronegativity

O O

••
••

••
••
•• ••
H 𝛉𝟏 H Cl Cl

••

••
•• 𝛉𝟐 ••

Expected angle should be H2O > Cl2O

Why bond angle in Cl2O is greater than H2O ? Discuss.

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

Fact Experimental angle order is Cl2O > H2O

+
O

••
••
due to back bonding
d- Cl d-
Cl
Cl 111°

••
••
Cl

••
••
••
••
••
••
••
•• ••
••
Resonance hybrid
Nature of Back bonding = 2pp – 3dp

Bond angle increases due to following two reasons :

Steric crowding (more prominent).
Back bonding.
Subtopic 2
ADVANCED LEVEL ILLUSTRATIONS
AND
CONCEPTS
In (SiH3)3 N, ‘N’ forms bond in excited state. [ TRUE/FALSE ]

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

2p ↿ ↿ ↿
Ground
State
Excitation
2s ↿⇂
In Back Bonding

2p ↿ ↿ ↿⇂
Excited
State
2s ↿
Ans. True
sp2
For H3BO3 molecule, select the correct statement(s) regarding effect of
back bonding.

(A) Bond length changes.

(B) Bond angle changes.
(C) pp – pp back bonding is observed.
(D) Electronic arrangement around B changes.
For H3BO3 molecule, select the correct statement(s) regarding effect of
back bonding.

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧
(A) Bond length changes. [dB – O decreases]
(B) Bond angle changes. [∠OBO does not change but ∠BOH increases]
(C) pp – pp back bonding is observed. [2pp – 2pp back bonding is present]
(D) Electronic arrangement around B changes. [No change]
H H

O O

B B H
H q ~112°

O O O O

H H
For H3BO3 molecule, select the correct statement(s) regarding effect of
back bonding.

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧
(A) Bond length changes. [dB – O decreases]
(B) Bond angle changes. [∠OBO does not change but ∠BOH increases]
(C) pp – pp back bonding is observed. [2pp – 2pp back bonding is present]
(D) Electronic arrangement around B changes. [No change]
H H

O O

B B H
H q ~112°

O O O O
Ans. A,B,C

H H
Compare dB – O bond length in the following
(a) H3BO3 (b) Na[B(OH)4]

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧 H
O
OH–

B q ~112° H
B
O O
OH OH

H OH
Back Bonding takes place No Back Bonding

Ans. (a) < (b)

Discuss the reason of Lewis acidic nature order in the following ?

(i) BeF2 < BeCl2 < BeBr2 < BeI2

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

(i) BeF2 < BeCl2 < BeBr2 < BeI2

In ‘BeF2’ electron denticity on ‘Be’ due

to back bonding is more prominent.
Discuss the reason of Lewis acidic nature order in the following ?

(ii) SiF4 > SiCl4 > SiBr4 > SiI4

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

(ii) SiF4 > SiCl4 > SiBr4 > SiI4

In ‘SiF4’ partial positive charge

on ‘Si’ is more prominent
R3SiOH is more acidic than R3COH. Why ?

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

R3SiOH R3SiO– + H+ R3COH R3CO– + H+

Conjugate Conjugate
base base

O–
O–

Si
C

R R
R R
R R
Get stabilized due to back bonding No back bonding

R3SiOH > R3COH (Acidic nature)

Why CHCl3 is more acidic than CHF3 ? Discuss.

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

CHF3 𝐂𝐅𝟑– + 𝐇 + CHCl3 𝐂𝐂𝐥–𝟑 + 𝐇 +

Acid Conjugate Acid Conjugate
base base

•• •• d-
C– •• Cl

••
C–

••
•• ••
F | F due to |

••

••
•• •• back bonding
••
F
••
Cl | Cl C

••
••
••

••
••
•• d- d-
••
Cl Cl Cl

••
••

••
••
••
••
NO Back bonding •• •• ••

CHCl3 > CHF3 (Acidic nature)

Why CHCl3 is more acidic than CHF3 ? Discuss.

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

Hybridisation changes from sp3 to sp2.

CHCl3 𝐂𝐂𝐥–𝟑 + 𝐇 +
Acid Conjugate
base

Pyramidal changes to Planar.

•• d-
•• Cl

••
C–

••
Direction of Back bond C → Cl. •• ••
due to |
back bonding
Cl | Cl C

••
••
•• •• d- d-
Nature of Back bond 2pp – 3dp . Cl Cl Cl

••
••

••
••
••
••
•• •• ••
Discuss the stability order in the following species ?
CF2 CCl2 CH2

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

•• •• ••
C C C
•• •• •• ••
F F Cl Cl H H

••

••

••

••
•• •• •• ••
2pp – 2pp 2pp – 3pp No back bond

CF2 > CCL2 > CH2 (Stability order)

••

••

••
Compare Lewis basic strength in the following :
(a) (CH3)2O (Dimethyl ether) (b) (SiH3)2O (Disilyl ether)
𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

(CH3)2O (SiH3)2O

O O

H3C 110° CH3 H3Si 144° SiH3

No back bonding pπ-dπ back bonding

sp3 hybridisation sp2 hybridisation

V – shape V – shape

Stronger Lewis base Weaker Lewis base Ans. (a) > (b)
Maximum number of atoms in a plane in the molecule N(SiH3)3 ?

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

H
H
d–
H
Si
H + d–
H
N Si
H d–
Si H
H
H
H
Trisilylamine N(SiH3)3

Ans. 7
Match the column with respect to underlined atom :
I II
(A) O(SiH3)2 (P) pp-pp back bond
(B) N(SiH3)3 (Q) pp-dp back bond

(C) BF3 (R) L.P. is involved in back bonding

(D) H3BO3 (S) B.A. in molecule increases due to back bond
(T) B.A. is 120o
Match the column with respect to underlined atom :
I II
(A) O(SiH3)2 (P) pp-pp back bond
(Q) pp-dp back bond
(Q)

(R)
(R) L.P. is involved in back bonding
(S) B.A. in molecule increases due to back bond
(T) B.A. is 120o

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧
Match the column with respect to underlined atom :
I II
(B) N(SiH3)3 (P) pp-pp back bond
(Q) pp-dp back bond
(Q)

(R)
(R) L.P. is involved in back bonding
(S) B.A. in molecule increases due to back bond
(T) B.A. is 120o

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧
Match the column with respect to underlined atom :
I II
(C) BF3 (P) pp-pp back bond
(Q) pp-dp back bond

(R) L.P. is involved in back bonding

(S) B.A. in molecule increases due to back bond
(T) B.A. is 120o

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧
Match the column with respect to underlined atom :
I II
(D) H3BO3 (P) pp-pp back bond
(Q) pp-dp back bond

(R) L.P. is involved in back bonding

(S) B.A. in molecule increases due to back bond
(T) B.A. is 120o

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧
Match the column with respect to underlined atom :
I II
(A) O(SiH3)2 (P) pp-pp back bond
(B) N(SiH3)3 (Q) pp-dp back bond
(C) BF3 (R) L.P. is involved in back bonding
(D) H3BO3 (S) B.A. in molecule increases due to back bond
(T) B.A. is 120o

Ans. A→ Q ,R ,S B→ Q ,R ,S, T C→ P, T D→ P, R, S
Introduction
 Inert pair effect
Inert pair effect

This effect is caused due to inertness of outermost s-electrons (ns2)

of heavier p-block elements (6th period).

As we move down in 13, 14 and 15 group there is presence of d &

f-electrons in inner shells which have poor shielding effect hence Zeff
increases.

As a result the ns2 electron pair becomes more and more tightly held
by the nucleus and becomes reluctant to participate in bonding.
 Inert pair effect

13th Group/Boron Family :

5B – [He] 2s2 2p1 +3

13Al – [Ne] 3s2 3p1 +3

31Ga – [Ar] 3d10 4s2 4p1 + 3, + 1

49In – [Kr] 4d10 5s2 5p1 + 3, + 1

81Tl – [Xe] 4f14 5d10 6s2 6p1 + 3, + 1

No. of poor shielding e- ↑ Zeff ↑

B3+ > Al3+ > Ga3+ > In3+ > Tl3+ Stability of higher O.S. ↓

B+ < Al+ < Ga+ < In+ < Tl+ Stability of lower O.S. ↑
 Inert pair effect

Group-13 Group-14 Group-15

ns2np1 ns2np2 ns2np3

(Group oxidation state) +3 +4 +5
On the basis of number of
electrons which takes part in B +3 C +4 N +5
bond formation Al +3 Si P
+4 +5
Ga +3 > +1 Ge +4 > +2 As +5 > +3
ln +3 > +1 Sn +4 > +2 Sb +5 > +3
Tl +3 < +1 Pb +4 < +2 Bi +5 < +3

For the last element group oxidation state is highly oxidising in nature.
 Inert pair effect
Application of inert pair effect

Relative stabilities of oxidation state

1. Tl+ > Tl+3

2. Pb+2 > Pb+4

3. Sn+2 < Sn+4

4. Bi+3 > Bi+5

 Inert pair effect
Application of inert pair effect

Relative stabilities of oxidation state

1. Ga+ < In+ < Tl+

2. Ga+3 > In+3 > Tl+3

3. Ge+4 > Sn+4 > Pb+4

4. Ge+2 < Sn+2 < Pb+2

The stability of +1 oxidation state among Al, Ga, In and TI
increases in the sequence :
(A) TI < In < Ga < Al
(B) In < TI < Ga < Al
(C) Ga < In < Al < TI
(D) Al < Ga < In < TI

Solution

Ans. D
The stability of +5 oxidation state among P, As, Sb and Bi
increases in the sequence :
(A) P > As > Sb > Bi
(B) P < As < Sb < Bi
(C) As < P < Sb < Bi
(D) Sb > As > P > Bi

Solution

Ans. A
 Inert pair effect
Application of inert pair effect

Relative oxidizing and reducing action

➢ Compounds in which ‘Pb’ is present in +4 , ‘Tl’ in +3 and ‘Bi’ in +5

oxidation state act as good oxidizing agent.

Pb+4 + 2e- → Pb+2

Tl+3 + 2e- → Tl+
Bi+5 + 2e- → Bi+3

Example

NaBiO3
PbO2 Act as good oxidizing agent
TlCl3
 Inert pair effect
➢ Compounds in which ‘Sn’ is present in +2 oxidation state act as good
reducing agent.

Sn+2 → Sn+4 + 2e-

Act as good reducing agent

Example

SnCl2 + BiCl3 → SnCl4 + Bi

SnCl2 + HgCl2 → SnCl4 + Hg

SnCl2 + AuCl3 → SnCl4 + Au

Write the correct order of oxidizing strength :

GeO2 SnO2 PbO2

Solution

Ans. GeO2 < SnO2 < PbO2

Which of the following compound does not exist?
A) PbF4 B) PbCl4 C) PbO2 D) PbI4

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

– – – –
Order of Reducing Nature: F < Cl < Br < I
Gain of e–

Pb+4 + I– → Pb+2+
𝟏
I
𝟐 2
Loss of e–

(Pb+4 acts as an Oxidizing Agent & I– acts as a Reducing Agent )

Ans. D
BiF5 exists but BiCl5 does not exist . Why ?

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

Bi+5 + 5F– BiF5

(Oxidizing) (Less reducing) (Stable)

Bi+5 + 5Cl– Bi+3 + 3Cl- + Cl2

(Oxidizing) (Reducing)
PbCl2 is more stable than PbCl4. Why ?

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

Due to inert pair effect

Consider the following decomposition reactions
T1
PbCl4 PbCl2 + Cl2
T2
PbBr4 PbBr2 + Br2
T3
PbI4 PbI2 + I2
Correct order of temperature is:

(A) T1 > T2 > T3

(B) T1 < T2 < T3
(C) T1 = T2 = T3
(D) T1 > T3 > T2

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧
Ans. A
TlI3 exists as:

(A) Tl+3, I– (B) Tl+, I– (C) Tl+3, 𝐈𝟑– (D) Tl+, 𝐈𝟑–

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

Ans. D
GaCl2 exists as:

(A) Ga+1,Cl- (B) Ga+2,Cl-

(C) Ga+3,Cl- (D) Ga[GaCl4]

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

Ans. D
Definition and Concept

Applications

➢ Bond parameters
➢ Lewis Acidic nature
➢ Hybridisation & Geometry
➢ Stability
 Bridge Bonding
Bridge bond is any bond which bridges two molecules to form a dimer,
trimer, etc.

Conditions for formation of Bridge Bond

Central atom must have vacant orbital.

Back bond formation tendency must be low.

Monomer must not have unpaired e–.

 Driving Force for Bridge Bonding

To attain eight e– system.

To minimise ℓ𝒑 − ℓ𝒑 repulsion.
 Bridge Bonding

Type of Bridge Bond

1. 3c-2e– bridge bond / banana bond

If bridging atom do not have lone pair , like H, –CH3 etc. .
Be2H4 , B2H6 , (BeH2)n , Al2(CH3)6 , etc.

2. 3c-4e–bridge bond / bridge bond by coordinate bond

If bridging atom have lone pair, like F, Cl, Br, I, –OH etc. .
Be2Cl 4 , (BeCl2)n , Al2Cl6 , I2Cl6 , etc.

‘3c’ bond is always bridge bond

 3c–2e– Bond / Banana Bond / e– Deficient Bond

B2H6 (Diborane)
 Bridge Bonding

3c–2e– Bond / Banana Bond / e– Deficient Bond

B2H6 (Diborane)

2BH3 B2H6

Driving Force

To attain 8e- system temporarily.

 Bridge Bonding

3c–2e– Bond / Banana Bond / e– Deficient Bond

B2H6 (Diborane)

2BH3 B2H6

Ht Hb
H Ht
B B
B
Ht Ht
H H Hb

E sp2 E sp3
B(Excited State) B(Excited State)
 Bridge Bonding

B2H6 (Diborane)

Ht Hb
Ht

B B

Ht Ht
Hb

Hybridisation state of boron is sp3and it is a non planar molecule.

 Bridge Bonding

B2H6 (Diborane)

All four terminal Ht and two B atoms are present in same plane &
both bridging Hb atoms are present in perpendicular plane.
Compare the bond lengths ‘x’ and ‘y’ in B2H6 (Diborane).

Solution

Ht Hb
Ht
B B
Ht Ht
Hb

x y
Hb B > Ht 119pm
B
134pm Ans. x > y
 Bridge Bonding

Methylation of Diborane

In substitution reaction, maximum four terminal hydrogen atom

gets substituted.

B2H6 + 4 CH3Cl ⎯→ B2H2(CH3)4 + 4HCl

Hb
H3C CH3

B B

H3C CH3
Hb

➢ Bridge ‘Hb’ is attracted by two ‘B’ atoms, hence

difficult to replace.

➢ Bridge bond is stronger than terminal bond.

Which of the following cannot be prepared from B2H6 ?

(A) B2(CH3)2H4 (B) B2(CH3)5H

(C) B2(CH3)3H3 (D) B2(CH3)H5

Solution
Hb
H3C CH3

B B

H3C CH3
Hb

Ans. B
 Bridge Bonding

Reaction with Lewis base

B2H6 + 2:O: 2 H3B  O :

Lewis acid Lewis base

Tetrahydrofuran Adduct

B2H6 is an electron deficient molecule act as a Lewis Acid.

Which of the following statement is correct for B2H6 (Diborane).
(A) Two bridged hydrogen and four terminal hydrogen are present.
(B) Three bridged and three terminal hydrogen are present.
(C) Four bridged hydrogen atoms are not in the same plane.
(D) One bridged hydrogen and one terminal hydrogen are present.

Solution

Ans. A
How many 2c-2e– bonds and 3c-2e– bonds are present in B2H6 (Diborane) ?
(A) 2 and 4 (B) 2 and 2
(C) 4 and 2 (D) 4 and 4

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

Ans. C
Maximum number of atoms in a plane in B2H6 .

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

Ans. 6
Nature of overlapping in bridge bond of B2H6.
(A) sp2 – sp2 – sp2 (B) sp3 – sp3 – sp3
(C) sp3 – s – sp3 (D) p – s – p

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

s
sp3 sp3

sp3 sp3
s

Ans. C
Number of valence electrons in B2H6 .
(A) 6 (B) 12
(C) 8 (D) 4

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

Ans. B
 Bridge Bonding

3c–4e– Bond / Coordinate Bond

Al2Cl6 (Dimer of AlCl3)

Al2Cl6 is a dimer of AlCl3 in solid state as well as in solution of non-polar
solvents .
2AlCl3 Al2Cl6

Cl Cl

Al Al
Cl Cl Cl Cl
 Bridge Bonding

3c–4e– Bond / Coordinate Bond

Al2Cl6 (Dimer of AlCl3)

Al2Cl6 is a dimer of AlCl3 in solid state as well as in solution of non-polar
solvents .
2AlCl3 Al2Cl6

Cl Cl Cl
Al Al
Cl Cl Cl

Driving Force

To attain 8e- system

 Bridge Bonding

3c–4e– Bond / Coordinate Bond

Al2Cl6 (Dimer of AlCl3)

Al2Cl6 is a dimer of AlCl3 in solid state as well as in solution of non-polar
solvents .
2AlCl3 Al2Cl6

Clt Clb
Cl Clt
Al Al
Al
Clt Clt
Cl Cl Clb

E sp2 E sp3
Al(Excited State) Al(Excited State)
 Bridge Bonding

Al2Cl6 (Dimer of AlCl3)

 Bridge Bonding

Al2Cl6 (Dimer of AlCl3)

Order of bond angle : a < b

Clb
Clt
y Clt
x
Order of bond length : x > y b
Al Al
a
Hybridisation state of ‘Al’ is sp3. Clt Clt
Clb

Non-planar

Octet of ‘Al’ is complete.

Nature of Bridge Bonding : sp3 – sp3 – sp3

3c - 4e- Bond = 2 , 3c - 2e- Bond = 0, 2c - 2e- Bond = 4

 Bridge Bonding

Key Points

Type Nature of Bridge

Bond
If bridge atom is having lone pair. (e.g. Cl, Br etc.) 3c – 4e–

If bridge atom does not have lone pair (e.g. : H, CH3 etc.) 3c – 2e–
 Bridge Bonding

Note

(i) BCl3, BBr3 & BI3 do not form dimer due to smaller size of boron &
large size of halogen (due to more steric repulsion).

(ii) BF3 cannot form dimer due to presence of back bonding.

(iii) AlF3 cannot form dimer due to its ionic nature.

ADVANCED LEVEL ILLUSTRATIONS
AND
CONCEPTS
 Bridge Bonding

(Be2H4) (Dimer of BeH2)

(BeH2)2 is dimer of BeH2 in vapor state.

Hb
Ht Be Be Ht
Hb

Driving Force

To attain 6e- system

temporarily.
 Bridge Bonding

(Be2H4) (Dimer of BeH2)

(BeH2)2 is dimer of BeH2 in vapor state.

Hb
Ht Be Be Ht
Hb

Hybridisation state of Be is sp2.

Planar
Electron deficient molecule.
3c - 4e- Bond = 0 , 3c - 2e- Bond = 2, 2c - 2e- Bond = 2
 Bridge Bonding

(BeH2)n (Polymer of BeH2)

(BeH2)n is polymer of BeH2 in solid state.

H H H

Be Be Be Be
H H H

Driving Force

To attain 8e- system temporarily.

 Bridge Bonding

(BeH2)n (Polymer of BeH2)

(BeH2)n is polymer of BeH2 in solid state.

H H H

Be Be Be Be
H H H

Hybridisation state of Be is sp3.

Non-planar.

Electron deficient molecule.

What is the hybridisation of ‘Be’ in BeH2(s) ?
(A) sp (B) sp2 (C) sp3 (D) can’t say

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

H H H

Be Be Be Be
H H
H

Ans. C
 Bridge Bonding

(BeCl2)2 (Dimer of BeCl2)

(BeCl2)2 is dimer of BeCl2 in vapour state.

Clb
Clt Be Be Clt
Clb

Driving Force

To attain 6e- system.

 Bridge Bonding

(BeCl2)2 (Dimer of BeCl2)

(BeCl2)2 is dimer of BeCl2 in vapour state.

Clb
Clt Be Be Clt
Clb

Hybridisation state of Be is sp2.

Planar

Electron deficient molecule.

3c - 4e- Bond = 2 , 3c - 2e- Bond = 0, 2c - 2e- Bond = 2

 Bridge Bonding

(BeCl2)n (Polymer of BeCl2)

(BeCl2)n is polymer of BeCl2 in solid state.
Cl Cl Cl
Be Be Be Be
Cl Cl Cl

Driving Force

To attain 8e- system.

 Bridge Bonding

(BeCl2)n (Polymer of BeCl2)

(BeCl2)n is polymer of BeCl2 in solid state.

Cl Cl Cl
Be Be Be Be
Cl Cl Cl

Hybridisation state of ‘Be’ is sp3.

Non-planar
Octet of Be is complete so it is not e– deficient.
Why ICl3 forms dimer ?

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

Driving Force

To minimise lp-lp repulsion.

 Bridge Bonding

I2Cl6 (dimer of ICl3)

Cl Cl Cl

I I

Cl Cl
Cl

Hybridisation state of ‘I’ is sp3d2.

Molecule is planar.

e– rich molecule (12 e–).

In which of the following specie(s) bridge bonding is /are NOT present.
(A) Dimer of CH3 (B) Dimer of FeCl3
(C) Si2Cl6 (D) S2F10

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧
In which of the following specie(s) bridge bonding is /are NOT present.
(A) Dimer of CH3 (B) Dimer of FeCl3

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧
H
H
H
H
(A) 2 CH3 C2H 6 C C
H
H

Clt Clb
Clt
(B) 2 FeCl3 Fe2Cl6 Fe Fe
Clt Clt
Clb
In which of the following specie(s) bridge bonding is /are NOT present.

(C) Si2Cl6 (D) S2F10

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

Cl Cl
(C) Si2Cl6 Cl Si Si Cl
Cl Cl

F F F F
(D) S2F10 F S S F
F FF F
In which of the following specie(s) bridge bonding is /are NOT present.
(A) Dimer of CH3 (B) Dimer of FeCl3
(C) Si2Cl6 (D) S2F10

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

Ans. A,C,D
Which of the following compound exist in nature?

(A) B2H6 (B) B2F6

(C) B2Cl6 (D) B2I6

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

Ans. A
Which of the following compound does not exist in nature?
(A) BH3 (B) BF3
(C) BCl3 (D) Al2Cl6

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧

Ans. A
Find the number of 2c – 2e- bond in dimer of Be(OMe)2

𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧
H
H H
C
Me
H O H
H Me
C O Be Be O Me H
C
H O H
C
Me
H H
H
Ans. 18
Atomic and Physical Properties

Introduction Group-13 (Boron Family)  ns2np1

B Non-metal

Al

Ga

In Metal

Nihonium Tl
(Latest element)

Nh
Atomic and Physical Properties

Occurrence

‘B’ is rare element found in combined form.

(e.g. H3BO3, Na2B4O7. 10H2O etc.)

‘Al’ is most abundant metal in earth crust.

‘Al’ is mainly found in Bauxite Al2O3.2H2O and Cryolite Na3AlF6.

‘Ga’, ‘In’, & ‘Tl’ are Less abundant.

‘Nh’ (Nihonium) is synthetically prepared radioactive element.

Atomic and Physical Properties

Physical State

Boron exist as (B12) extremely hard, black coloured non-metallic solid and
poor conductor of electricity.
Atomic and Physical Properties

Physical State

Boron has very high melting point due to icosahedron

crystal structure which consist of 12 atoms.

In boron crystal each boron atom is bonded to five equidistant

another boron atoms to form 12 corners and 20 faces.

B
B B
B B
B
B
B B
B B
B
Atomic and Physical Properties

Physical State

Rest are soft metals with low melting

point and high electrical conductivity.

All elements are solid except Ga

(melting point- 302.9K).
Atomic and Physical Properties

Physical State

Boron exists in five allotropes, four of which are crystalline and one is
amorphous.

Crystalline Amorphous
Atomic and Physical Properties

Physical State

All crystalline forms are black and chemically inert but amorphous form is
brown and chemically active.

Crystalline Amorphous
There are two isotopic forms of boron 10B(19%) and 11B(81%).
Atomic and Physical Properties
Electronic Configuration

5B
– [He] 2s2 2p1

13Al – [Ne] 3s2 3p1

31Ga – [Ar] 3d10 4s2 4p1

49In – [Kr] 4d10 5s2 5p1

81Tl
– [Xe] 4f14 5d10 6s2 6p1

113Nh – [Rn] 5f14 6d10 7s2 7p1

Atomic and Physical Properties

Atomic Properties
Atomic and Physical Properties

Atomic Radius

B < Al < Ga < In < Tl Expected

B < Ga < Al < In < Tl Actual

88 pm 135 pm 143 pm 167 pm 170 pm

Atomic and Physical Properties

Atomic Radius

B < Ga < Al < In < Tl Actual

88 pm 135 pm 143 pm 167 pm 170 pm

Tl

In

Atomic Radius
Al
Ga

Atomic Number
Atomic and Physical Properties

Reason

13Al → [Ne], 3s2, 3p1

31Ga → [Ar], 4s2, 3d10, 4p1

Transition contraction (scandate contraction) due to poor shielding of 3d10

electrons of Ga.
Atomic and Physical Properties

Melting point

B > Al > Ga > In > Tl

2453K 933K 576K 430K 303K

Melting point
Al

Tl
In
Ga

Atomic Number
Atomic and Physical Properties

Density

B < Al < Ga < In < Tl

2.35 2.70 5.90 7.31 11.85 (gm/cm3)

Tl

In

Density
Ga

Al
B

Atomic Number
Atomic and Physical Properties

Ionisation Enthalpy

B > Al > Ga > In > Tl

TI Expected

B > > Ga > > Actual

801 589 579 577 558 (kJ/mol)

Atomic and Physical Properties

B > TI > Ga > Al > In

801 589 579 577 558 (kJ/mol)

Ionization Enthalpy
B
Tl
Ga

Al
In

Atomic Number
Atomic and Physical Properties

Reason

81Tl – [Xe] 4f14 5d10 6s2 6p1

Due to poor shielding of ‘d’ and ‘f’ electrons of Tl, Zeff increases.
Correct order of atomic radius is :

(A) Al > Ga (B) B > Al

(C) Ga > In (D) In > Tl

Solution

B < Al < Ga < In < Tl

88 pm 135 pm 143 pm 167 pm 170 pm

Ans. A
Which of the following is metal

(A) B (B) Al (C) Ga (D) B and C Both

Solution

B Al Ga In Tl

Non-metal Metal

Ans. D
Which is most abundant metal on earth curst ?

(A) B (B) Al (C) Fe (D) Zn

Solution

Ans. B
In group 13, element with minimum value of first ionisation
energy is
(A) B (B) Ga (C) In (D) Tl

Solution

B > TI > Ga > Al > In

801 589 579 577 558 (kJ/mol)

Ans. C
 Chemical Properties
Oxidation State

5B
– [He] 2s2 2p1 +3

13Al – [Ne] 3s2 3p1 +3

31Ga – [Ar] 3d10 4s2 4p1 + 3, + 1

49In – [Kr] 4d10 5s2 5p1 + 3, + 1

81Tl
– [Xe] 4f14 5d10 6s2 6p1 + 3, + 1
No. of poor shielding e- ↑ Zeff ↑

B3+ > Al3+ > Ga3+ > In3+ > Tl3+ Stability of higher O.S. ↓

B+ < Al+ < Ga+ < In+ < Tl+ Stability of lower O.S. ↑
Chemical Properties

➢ The compounds in +1 oxidation state, are more ionic than

those in +3 oxidation state.

➢ In trivalent state, molecules are electron deficient.

➢ Molecules have tendency to accept a pair of electrons to

achieve stable electronic configuration and thus, behave as
Lewis acids.

➢ The tendency to behave as Lewis acid decreases with the

increase in the size down the group.
Chemical Properties

➢ BCl3 easily accepts a lone pair of electrons from ammonia

to form BCl3.NH3.

NH3
Cl

B Cl + NH3 B
Cl
Cl Cl
Cl
Planar Tetrahedral
Chemical Properties

➢ AlCl3 achieves stability by forming a dimer

Why BCl3 does not form dimer ?

Chemical Properties

➢ AlCl3 achieves stability by forming a dimer

➢ Due to steric crowding

 Chemical Properties
Reaction with air (N2 & O2)

(a) Reaction with Oxygen

2E + 3O2 ⎯→D 2E O (s)
2 3

B2O3  Acidic
Al2O3  Amphoteric
Ga2O3 / Ga2O  Amphoteric
In2O3 / In2O  Basic
Tl2O3 / Tl2O  Basic

(b) Reaction with Nitrogen

D
E + N2 ⎯→ 2 EN (s)
 Chemical Properties
Reaction with Halogen

These elements react with halogens to form trihalides (Except TlI3)

D
2E + 3X2 ⎯→ 2EX3(s) {X = F, Cl, Br, I}
 Chemical Properties
Reactivity towards Acid and Alkalis

Boron does not reacts with acids and alkalies.

Al, Ga, In and Tl react with both non-oxidizing and oxidizing acids to
evolve H2.

𝟐𝐀𝐥 𝐬 + 𝟔𝐇𝐂𝐥 𝐚𝐪. ⎯→ 𝟐𝐀𝐥𝟑+ 𝐚𝐪. + 𝟑𝐂𝐥− 𝐚𝐪. + 𝟑𝐇𝟐 𝐠

Al does not reacts further with conc HNO3 due to formation of passive
oxide layer.
 Chemical Properties
Reactivity towards Acid and Alkalis

Al and Ga dissolve in aqueous NaOH liberating H2 and forming salts.

𝟐𝐀𝐥 𝐬 + 𝟐𝐍𝐚𝐎𝐇 𝐚𝐪. + 𝟔𝐇𝟐 𝐎 𝐥 ⎯⎯→ 𝟐𝐍𝐚𝐀𝐥𝐎𝟐 . 𝟐𝐇𝟐 𝐎 + 𝟑𝐇𝟐 (𝐠)

𝐒𝐨𝐝𝐢𝐮𝐦 𝐦𝐞𝐭𝐚 𝐚𝐥𝐮𝐦𝐢𝐧𝐚𝐭𝐞
𝐎𝐫 𝟐𝐍𝐚 𝐀𝐥 𝐎𝐇 𝟒

𝟐𝐆𝐚 𝐬 + 𝟐𝐍𝐚𝐎𝐇 𝐚𝐪. + 𝟔𝐇𝟐 𝐎 ⎯⎯→ 𝟐𝐍𝐚 𝐆𝐚 𝐎𝐇 𝟒 + 𝟑𝐇𝟐 (g)

‘In’ and ‘Tl’ do not react with alkali

 Chemical Properties
Reactivity towards Acid and Alkalis

Al and Ga dissolve in aqueous NaOH liberating H2 and forming salts.

𝟐𝐀𝐥 𝐬 + 𝟐𝐍𝐚𝐎𝐇 𝐚𝐪. + 𝟔𝐇𝟐 𝐎 𝐥 ⎯⎯→ 𝟐𝐍𝐚𝐀𝐥𝐎𝟐 . 𝟐𝐇𝟐 𝐎 + 𝟑𝐇𝟐 (𝐠)

𝐒𝐨𝐝𝐢𝐮𝐦 𝐦𝐞𝐭𝐚 𝐚𝐥𝐮𝐦𝐢𝐧𝐚𝐭𝐞
𝐎𝐫 𝟐𝐍𝐚 𝐀𝐥 𝐎𝐇 𝟒

𝟐𝐆𝐚 𝐬 + 𝟐𝐍𝐚𝐎𝐇 𝐚𝐪. + 𝟔𝐇𝟐 𝐎 ⎯⎯→ 𝟐𝐍𝐚 𝐆𝐚 𝐎𝐇 𝟒 + 𝟑𝐇𝟐 (g)

‘In’ and ‘Tl’ do not react with alkali due to basic nature.
Which family of elements form electron deficient trihalides ?
(A) Group 13 (B) Group 14

(C) Group 15 (D) All

Solution

Ans. A
For which element +1 oxidation state is more stable?
(A) B (B) Ga

(C) In (D) Tl

Solution

Ans. D
 Compounds of Boron

Borax (Na2B4O7 .10H2O)

It is a white crystalline solid.

It contains tetranuclear units [B4O5(OH)4]2- and therefore correct formula

is Na2[B4O5(OH)4].8H2O
 Compounds of Boron

Structure

Na2 [B4O5(OH)4].8H2O

H
O Tetrahedral 2– → B-O-B linkage = 5

B → Total B-O bonds = 14

O O
2Na+ → Two sp2 hybridised Boron
HO B O B OH . 8H2O
O O → Two sp3 hybridised Boron
Trigonal
planar B
→ Non planar
O
H
 Compounds of Boron

Properties

(a) 𝐇𝐲𝐝𝐫𝐨𝐥𝐲𝐬𝐢𝐬

Less soluble in cold water due to stable H-bonds.

But more soluble in hot water.

Borax dissolves in water to give an alkaline solution.

Na2B4O7 + 7H2O ⎯⎯→ 2NaOH + 4H3BO3
(strong base) (weak acid)
 Compounds of Boron

Properties

(b) 𝐇𝐞𝐚𝐭𝐢𝐧𝐠 𝐞𝐟𝐟𝐞𝐜𝐭

On heating borax first loses water molecules and swells up. On further
heating it turns into a transparent liquid which solidifies into glass like
material.

D D
Na2B4O7.10H2O ⎯⎯→ Na2B4O7 ⎯⎯→ 2 NaBO2 + B2O3
740 °C
Transparent Glassy Mass
 Compounds of Boron

Borax Bead Test

Borax Bead Test is used to detect the presence of Transition Metal Ions.

Borax react with certain metal salt such as Ni2+,Co2+, Cr3+,Cu2+, Mn2+ etc. to
form colored Metal Metaborates.

The color of Metal Melaborate can be used to identify the metallic cations in
salt.

Co2+ ⇒ Dark blue

Mn2+ ⇒ Purple Pink
Cu2+ ⇒ Blue
Cr3+ ⇒ Green
 Compounds of Boron

Borax Bead Test

100°𝐶 740°𝐶
Na2B4O7.10H2O ⎯⎯→ Na2B4O7 ⎯⎯→ NaBO2 + B2O3
Swell up
Transparent Glassy Mass
(Borax Bead)

Active part of Borax bead is B2O3.

D
B2O3 + Metal Oxide ⎯⎯⎯⎯→ Metal Metaborate
(Colored)
 Compounds of Boron

Borax Bead Test

 Compounds of Boron

Uses of Borax

In borax bead test In purifying gold

 Compounds of Boron

Uses of Borax

As flux during In production of glass

welding of metals
 Compounds of Boron

Orthoboric acid (H3BO3 )

Method of preparation of Boric Acid

Na2B4O7 + H2SO4 + 5H2O 4H3BO3 + Na2SO4

Conc.

Na2B4O7 + 2HCl + 5H2O 2NaCl + 4B(OH)3

BCl3 + 3H2O H3BO3 + 3HCl

 Compounds of Boron

Structure in solid state

Layered Structure (two dimensional) due to Hydrogen Bonding

H
O
H B
O O
H H
O O
H
H B H
O O O
H
H B H B
O O O O
H H
 Compounds of Boron

Properties

Less soluble in cold water but more soluble in hot water.

Heating effect of boric acid :

H3BO3 100°C
⎯⎯→ HBO2 140°C
⎯⎯→ D
H2B4O7 ⎯⎯→ B2O3
Red hot

Metaboric acid Tetra boric acid Glassy mass

 Compounds of Boron

Properties

It is weak monobasic Lewis acid, it is not a protonic acid.

B(OH)3 + 2H2O [B(OH)4]– + 𝐇𝟑+ O Ka = 5.8 × 10-10

H
H
O
|
O O
B H B–
O
H
 Compounds of Boron

Test of Borate Radical 𝐁𝐎𝟑−

𝟑

When boric acid is heated with ethanol, the evolved gas is burned
forming a green edged flame.

H3BO3 + 3C2H5OH ⎯⎯→ B(OC2H5)3 + 3H2O

Ethyl Borate
(Volatile and burns with green edged flame)
 Compounds of Boron

Test of Borate Radical 𝐁𝐎𝟑−

𝟑
 Compounds of Boron

Uses of Boric Acid

It is also used in glass, enamel It is an antiseptic and its water

and pottery industry. solution is used as an eyewash.
Solution of Borax is

(A) Acidic

(B) Basic

(C) Neutral

(D) Non of these

Solution

Na2B4O7 + 7H2O ⎯⎯→ 2NaOH + 4H3BO3

(strong base) (weak acid)

Ans. B
Numbers 𝐁 − 𝐎 − 𝐁 linkages in borax is

(A) 3

(B) 4

(C) 5

(D) 2
H
O 2–
Solution
B
O O
2Na+ HO B O B OH . 8H2O
O O
B

O Ans. C
H
 Compounds of Boron
Diborane (B2H6)

Preparation

(a) 4BF3 + 3LiAlH4 ⎯⎯→ 2B2H6 + 3LiF + 4AlF3

(b) Lab method

2NaBH4 + I2 ⎯⎯→ B2H6 + 2NaI + H2
450 k

(c) Industrial method

2BF3 + 6NaH ⎯⎯→ B2H6 + 6NaF
 Compounds of Boron

Structure

H H H

B B
H H H

H H

B
H 97° H
120° B

H H
 Compounds of Boron

Structure

Hybridisation state of boron is sp3and it is a non planar molecule.

All four terminal Ht and two B atoms are present in same plane & both
bridging Hb atoms are present in perpendicular plane.
 Compounds of Boron

Structure

Bridge ‘Hb’ is attracted by two ‘B’ atoms, hence difficult to replace.

B2H6 is an electron deficient molecule act as a Lewis Acid.

 Compounds of Boron

Properties

Diborane is a colourless, highly toxic gas with a boiling point of 180 K.

Diborane catches fire spontaneously upon exposure to air.

It burns in oxygen releasing an enormous amount of energy.

B2H6 + 3O2 ⎯⎯→ B2O3 + 3H2O
DH = – 1976 kJ mol–1

Boranes are readily hydrolyzed by water to give boric acid.

B2H6(g) + 6H2O(l) ⎯⎯→ 2B(OH)3(aq) + 6H2(g)
 Compounds of Boron

Properties

Reaction with MeOH

B2H6 + 6MeOH ⎯⎯→ 2B(OMe)3 + 6H2

B2H6 forms metal hydridoborates with metal hydrides.

2MH + B2H6 ⎯⎯→ 2M+ [BH4]– (M = Li & Na)

[LiBH4] and [NaBH4] are used on reducing agents in

organic synthesis.
 Compounds of Boron

Properties

B2H6 reacts with Lewis base so it act as a Lewis acid.

It undergoes two type of cleavage (when reacts with Lewis base):

(A) Symmetrical Cleavage (B) Unsymmetrical Cleavage

H H H H H H

B B B+ B–

H H H H H H
2 BH3 BH2+ BH4-
(Ionic pair)
 Compounds of Boron

Properties

(A) Symmetrical Cleavage

With weak base like CO and large groups like Amines (CH3)3N, Pyridine and
Tetrahydrofuran (THF). It forms borane adducts.

(i) B2H6+ 2 CO ⎯⎯→ 2 [ BH3←CO ]

(ii) 2(CH3)3N + B2H6 ⎯⎯→ 2 [ H3B ←N(CH3)3 ]

 Compounds of Boron

Properties

(B) Unsymmetrical Cleavage

With strong bases like ammonia (NH3 ) and amines [CH3NH2 , (CH3)2NH ]

Low
Temperature
(i) 3B2H6 + 6NH3 3[B2H6.2NH3 ] or 3[H2B(NH3)2]+ [BH4]–
 Compounds of Boron

Properties

(B) Unsymmetrical Cleavage

T = 200°C
3[H2B(NH3)2]+ [BH4]– B3N3H6 + 12H2 ↑
(Borazole
/ Borazine
/ Inorganic Benzene)

H H

H B- H H B- H
N+ N+ N+ N+

B- B- B- B-
H N+ H H N+ H
H H
 Compounds of Boron

Properties

(B) Unsymmetrical Cleavage

T > 200°C
B3N3H6 (BN)x (Boron Nitride / Borazone / Inorganic graphite)

B- B-
N+ N+ N+

B- B- B-
N+ N+
Hybridization of atoms in inorganic graphite is

(A) sp2 only (B) sp3 only

(C) sp2 and sp3 (D) No hybridization

Solution

B- B-
N+ N+ N+

B- B- B-
N+ N+

Ans. A
Boron form covalent compound due to-

(A) Higher ionization energy (B) Lower ionization energy

(C) Small size (D) Both (A) and (C)

Solution

Ans. D
 Compounds of Boron

Uses of Boron

B10 isotope absorbs neutrons, so metal borides are used in nuclear

industry as protective shields and control rods.

Boron fiber is used to prepare bullet proof vests and light composite
material for aircraft.
 Compounds of Boron

Uses of Aluminium

Al is used in construction of airplane and pipes.

Aluminium has high electrical and thermal conductivity.

ADVANCED LEVEL ILLUSTRATIONS
AND
CONCEPTS
 Compounds of Aluminium

Alum

These are double sulphate with their general formula

M2SO4.M’2(SO4)3.24 H2O

Where M = Monovalent Radical Like Na+, K+, NH4+

M’ = Trivalent Radical Like Al+3, Cr+3, Fe+3
Compounds of Aluminium

Alum

The different alums are :

(i) Potash Alum K2SO4. Al2(SO4)3. 24 H2O

(ii) Chrome Alum K2SO4. Cr2(SO4)3. 24 H2O

(iii) Iron Alum (NH4)2SO4. Fe2(SO4)3. 24 H2O

(iv) Ammonium Alum (NH4)2SO4. Al2(SO4)3. 24 H2O

Compounds of Aluminium

Alum

All Alums are Isomorphous.

In Alum each ion is surrounded by 6 Water molecules.

Lithium does not form alum because Li ion is too small to have a
coordination number of Six.
Compounds of Aluminium

Uses of Alum

Act as coagulant Purification of water

Compounds of Aluminium

Uses of Alum

Tanning of leather Mordant in dying

Compounds of Aluminium

Uses of Alum

Antiseptic
In the reaction B2O3 + C + Cl2 → A + CO. The A is-

(A) BCl3 (B) BCl2

(C) B2Cl2 (D) CCl2

Solution

Ans. A
The hardest substance amongst the following is

(A) Be2C (B) Graphite

(C) SiC (D) B4C

Solution

Ans. D
Aluminium is a self-preserving metal, because

(A) It is not tarnished by air

(B) A thin film of basic carbonate on its surface

(C) A non-porous layer of oxide is formed on its surface

(D) It is not affected by salt water

Solution

Ans. C
Which one of the following is correct statement?

(A) The hydroxide of Aluminum is more acidic than that of boron.

(B) The hydroxide of Boron is basic, while that of Aluminum is

amphoteric.

(C) The hydroxide of Boron and Aluminum are amphoteric.

(D) The hydroxide of Gallium and Aluminum are amphoteric.

Solution

Ans. D
 Compounds of Boron

Preparation of boron

(i) Preparation of B2O3 from Borax or Colemanite

Na2B4O7 + HCl/H2SO4 ⎯→ NaX + H2B4O7

∆
H2B4O7 + 5H2O ⎯→ 4H3BO3 B2O3 + H2O

(ii) Reduction of B2O3

B2O3 + Na/K/Mg/Al ⎯→ B + Na2O/K2O/MgO/Al2O3

 Compounds of Boron

Preparation of borax

2CaO · 3B2O3 + 2Na2CO3 ⎯⎯⎯→ 2CaCO3  + Na2B4O7 + 2NaBO2

Colemanite
Filtered
– CaCO3 (as residue)

NaBO2 + Na2 B4O7 ·10H2O Concentrated

in filtrate as residue and allowed to Na2 B4 O7 + NaBO2
crystallise out
and filtered in solution

CO2 passed and

[4NaBO2 + CO2 ⎯⎯→ Na2B4O7 + Na2CO3]
crystallise out again
Na2B4O7 ·10H2O 
 Compounds of Boron

Preparation of sodium peroxy borate

O—O
H3BO3 + H2O2 + NaOH ⎯⎯→ (HO)2 B B (OH)2 . 6H2O
O—O

Uses

Sodium peroxy borate used in washing powder as

brightener
Why boric acid behave as strong acid in presence of cis diol (sugar,
glycerol, mannitol)

Solution

On adding cis diol, equilibrium shift in forward direction hence it

behave as strong acid

C OH HO OH HO C
-
B
C OH HO OH HO C

C O O C
-
B
O C –4H2 O
C O
Introduction Group-14 (Carbon Family)  ns2np2

C Non-metal

Si
Metalloids
Ge

Sn

Flerovium Pb Metal
(Latest element)

Fl
Occurrence Of Element (Group 14)

Carbon

Carbon is the 17th most abundant element by mass in the earth’s

crust .

Three isotopes C12 , C13 & C14 .

C-14 is radioactive with half life 5770 years.

Occurrence Of Element (Group 14)

Silicon

2nd most abundant element by mass in the earth’s crust.

Present in silica & silicates.

Occurrence Of Element (Group 14)

Germanium

Germanium exists only in traces.

Occurrence Of Element (Group 14)

Tin

Tin occurs mainly as cassiterite, SnO2

Occurrence Of Element (Group 14)

Lead

Lead occurs mainly as galena, PbS.

Which is correct regarding oxidation sate of Pb.

(A) Stability of Pb+2 > Pb+4 (B) Pb+4 has strong oxidizing nature

(C) PbI4 is not stable (D) All

Solution

Ans. D
Atomic and Physical Properties (Group 14)

Atomic Properties
Atomic and Physical Properties (Group 14)

Atomic Radius

Increases down the group.

C < Si < Ge < Sn < Pb

77 118 122 140 146 (in pm)

Atomic Radius
Pb
Sn

Ge
Si

Atomic Number
Atomic and Physical Properties (Group 14)

Ionisation Energy

C Si Ge Sn Pb Expected

C > Si > Ge > Pb > Sn Actual

1086 786 761 715 708 (kJ mol-1)
Atomic and Physical Properties (Group 14)

Ionisation Energy

C > Si > Ge > Pb > Sn Actual

1086 786 761 715 708 (kJ mol-1)

Ionisation Energy
Si

Ge

Pb
Sn

Atomic Number
Atomic and Physical Properties (Group 14)

Ionisation Energy

C > Si > Ge > Pb > Sn Actual

1086 786 761 715 708 (kJ mol-1)

Why ionisation energy order is Pb > Sn ?

Atomic and Physical Properties (Group 14)

Ionisation Energy

C > Si > Ge > Pb > Sn Actual

1086 786 761 715 708 (kJ mol-1)

Zeff. order Pb > Sn

Atomic and Physical Properties (Group 14)

Electronegativity

C Si Ge Sn Pb Expected

C > Pb > Si ≃ Ge ≃ Sn Actual

2.5 1.9 1.8 1.8 1.8
Atomic and Physical Properties (Group 14)

Electronegativity

C > Pb > Si ≃ Ge ≃ Sn Actual

2.5 1.9 1.8 1.8 1.8

Electronegativity
C

Si Pb
Ge Sn

Atomic Number
Atomic and Physical Properties (Group 14)

Melting Points

C Si Ge Sn Pb Expected

C > Si > Ge > Pb > Sn Actual

4373 1693 1218 600 505 ( in K )
Atomic and Physical Properties (Group 14)

Melting Points

C > Si > Ge > Pb > Sn Actual

4373 1693 1218 600 505 ( in K )

Melting Points
Si

Ge
Pb

Sn

Atomic Number
Atomic and Physical Properties (Group 14)

Boiling Point

C > Si > Ge > Sn > Pb

5600 3550 3123 2896 2024 ( in K )

of Diamond

Boiling Point
Si

Ge

Sn

Pb

Atomic Number
Atomic and Physical Properties (Group 14)

Metallic nature

C < Si < Ge < Sn < Pb

Non-metal Metalloid Metal

Select the member (s) of group 14 that

(i) Forms the most acidic dioxide,

(ii) Is commonly found in +2 oxidation state.

(iii) Used as semiconductor.

Solution
(i) Carbon

(ii) Lead

(iii) Silicon and Germanium

Maximum melting point among all elements is for

(A) C (B) Si (C) B (D) Al

Solution

C > Si

4373K 1693K

B > Al

2453K 933K Ans. A

Arrange

(1) C—C (2) Si — Si (3) Ge — Ge (4) Sn — Sn

(A) Bond length (B) Bond Energy

Solution

(A) Bond length

C – C < Si – Si < Ge – Ge < Sn – Sn

(B) Bond Energy

C – C > Si – Si > Ge – Ge > Sn – Sn
348 297 260 240 kj mol-1

Order of catenation Ans. A

C >> Si > Ge ~ Sn
Chemical Properties (Group-14)

Electronic Configuration & Oxidation State

6C – [He] 2s2 2p2 +2

14Si – [Ne] 3s2 3p2 +2

32Ge – [Ar] 3d10 4s2 4p2 + 2, + 4

50Sn – [Kr] 4d10 5s2 5p2 + 2, + 4

82Pb – [Xe] 4f14 5d10 6s2 6p2 + 2, + 4

No. of poor shielding e- ↑ 𝒁𝒆𝒇𝒇↑

C4+ > Si4+ > Ge4+ > Sn4+ > Pb4+ Stability of higher O.S. ↓

C2+ < Si2+ < Ge2+ < Sn2+ < Pb2+ Stability of lower O.S. ↑
Chemical Properties (Group-14)

Oxides

Reactivity towards oxygen :

Forms two type of oxides, Monoxide (EO) and Dioxide (EO2)

E + O2 EO / EO2

Monoxide (EO) Dioxide (EO2)

Neutral CO CO2
SiO SiO2
Acidic GeO GeO2
SnO SnO2
Amphoteric PbO PbO2
 Chemical Properties

Complex formation tendency

Except carbon all these elements have complex forming tendency.

They form complexes by accepting electrons in the vacant d-orbitals from

atoms or ions having lone pair of electrons.

Sn(OH)4 + 2OH– ⎯⎯→ [Sn(OH)6]2–

 Chemical Properties

Reactivity towards water

Carbon, silicon and germanium are not affected by water.

Tin decomposes steam to form dioxide and dihydrogen gas.

∆
Sn + 2H2O SnO2 + 2H2↑
Steam

Lead is unaffected by water, probably because of a protective oxide film

formation
 Chemical Properties

Reactivity towards halogen

Forms MX2 and MX4 types (X = F, Cl, Br, I)

Except carbon, all other members react directly with halogen.

Most of the MX4 are covalent in nature

SnF4 and PbF4 are ionic in nature

Which of the following does not exists

(A) CCl62– (B) SiF62–

(C) SnCl62– (D) GeCl62–

Solution

Ans. A
[SiF6]2– is known whereas [SiCl6]2– not. Give possible reasons.

Solution

The main reasons are :

(i) Six large chloride ions cannot be accommodated around Si4+ due to
limitation of its size.

(ii) Interaction between lone pair of chloride ion and Si4+ is not very strong.
 Allotropes Of Carbon

Allotropy

Different forms of an element

Allotropic forms

Crystalline Form

Amorphous Form
 Allotropes Of Carbon

Crystalline Form

Diamond Graphite Fullerene

 Allotropes Of Carbon

Amorphous Form

Coal C-lamp black Charcoal, Coke

 Allotropes Of Carbon

Crystalline Allotropes

Diamond

Natural allotrope

Each carbon bonded with four other carbon atom

sp3 hybridisation

tetrahedral structure

Insulator due to absence of free electrons

 Allotropes Of Carbon

Crystalline Allotropes

Diamond

Hard due to presence of strong sigma bond and 3D structure

Density = 3.51 gm/cm3

High melting point (giant molecule)

Bond length (C-C) = 154pm

 Allotropes Of Carbon

Crystalline Allotropes

Diamond

Kinetically most stable allotrope.

Good conductor of heat.

DHf ° of diamond is 1.9 kJ/mol.

Hardest natural substance

Uses : - • Abrasive
• Manufacturing of tungsten filament
 Allotropes Of Carbon

Crystalline Allotropes

Graphite

Natural allotrope

Each carbon bonded with three other carbon atom

sp2 hybridisation

Hexagonal layer structure

 Allotropes Of Carbon

Crystalline Allotropes

Graphite

Good electrical conductor due to presence of delocalised electrons

Soft due to presence of weak van der Waals forces between two layers

Density = 2.22 gm/cm3

Low melting point

 Allotropes Of Carbon

Crystalline Allotropes

Graphite

Thermodynamically most stable form of allotrope.

DHfo of graphite is taken as zero.

Used as high temperature lubricant.

Allotropes Of Carbon

Dangling Bond

Diamond and Graphite are not the purest allotropes of carbon because
some surface carbon atoms have free valency.

These carbon atoms form new bonds with impurities.

These new bonds are known as Dangling Bond.

 Properties

Crystalline Allotropes

Fullerene

Artificial allotrope of carbon

Made by heating graphite in electric are in the presence of inert

gas such as He or Ar.
 Allotropes Of Carbon

Crystalline Allotropes

Fullerene

C-60 & C-70 are common forms of fullerene.

Other fullerene contains even number of ‘C’ atoms upto 350 or above

C-60 is also known as Buckminster fullerene (Bucky ball)

12 pentagonal rings
There are 32 rings
(in C60) 20 hexagonal rings
Crystalline Allotropes

Fullerene

Each carbon atom bonded with 3 other carbon by two single & one
double bond

sp2 hybridisation & aromatic in nature

It is a purest allotrope of carbon. (Dangling bond absent)

DHf ° of C6O is 38.1 Kj/mol

In diamond hybridization of ‘C’ is

(A) sp (B) sp2

(C) sp3 (D) None

Solution

Ans. C
Which of the following has sp3 hybridization of atoms

(A) Diamond (B) SiC

(C) A and B both (D) None

Solution

C Si
C

Ans. C
 Compounds of carbon

Carbon monoxide

Preparation

By dehydration of formic acid.

𝐂𝐨𝐧𝐜.𝐇𝟐𝐒𝐎𝟒
HCOOH CO + H2O
𝟑𝟕𝟑𝐊
Formic acid

when steam is passed over red-hot coke then

Water Gas or synthesis gas is obtained.

𝟒𝟕𝟑𝐊 𝐭𝐨 𝟏𝟐𝟕𝟑 𝐊
C + H2O CO + H2
 Compounds of carbon

Carbon monoxide

Preparation

when air (instead of steam) is passed over

coke then Producer Gas is obtained.
𝟏𝟐𝟕𝟑𝐊
C + O2 + N 2 CO + N2

When conc. H2SO4 is heated with K4 [Fe(CN)6].

K4 [Fe(CN)6] + 6H2SO4 + 6H2O 2K2SO4 + FeSO4 + 6CO +3(NH4)2SO4

(powder) (conc.)
 Compounds of carbon

Carbon monoxide

Properties

CO is neutral in nature.

It burns with blue flame.

It is poisonous in nature and forms Carboxyhemoglobin.

It can act as oxidising as well as reducing agent.

 Compounds of carbon

Carbon monoxide

Properties

It is absorbed in ammoniacal Cu2Cl2 solution.

Cu2Cl2 + 2CO + 4H2O 2 [Cu2Cl2 (CO)(H2O)2]

 Compounds of carbon

Carbon monoxide

Properties

It is absorbed in ammoniacal Cu2Cl2 solution.

Cu2Cl2 + 2CO + 4H2O 2 [Cu2Cl2 (CO)(H2O)2]
 Compounds of carbon

Carbon monoxide

Properties

Estimation of CO is done by I2O5

CO + I2O5 I2 + CO2

I2 +Na2S2O3 Na2S4O6 + N
 Compounds of carbon

Carbon monoxide

Properties

Detection of CO is done by PdCl2(aq.)

CO + PdCl2 + H2O CO2 + Pd + 2HCl

Black metallic
deposition
 Oxides of group-14

Uses of CO

It is a powerful reducing agent that is why used in extraction at many metal

from their oxide.

∆
Fe2O3(s) + 3CO(g) 2Fe(s) + 3CO2(g)

Used as metal purifier.

e.g. Mond’s process for ‘Ni’

𝟓𝟎 − 𝟔𝟎°𝐂 𝟐𝟎𝟎 − 𝟐𝟑𝟎°𝐂

Ni(s) + CO(g) [Ni(CO4](g) Ni(s) + 4CO(g)
Impure Pure
 Oxides of group-14

Carbon Dioxide (CO2)

Preparation

Complete combustion of carbon containing compounds.

CH4 + O2 ⎯→ CO2 + H2O

In the laboratory it can be conveniently made

by the action of dilute hydrochloric acid on
marble chips.

CO32–(aq) + 2H+(aq) ⎯→ CO2(g) + H2O(l)

 Oxides of group-14

Carbon Dioxide (CO2)

Preparation

Industrially it is produced as a by-product during the manufacture of

quicklime and in fermentation processes.

∆
CaCO3(s) CaO(s) + CO2(g)

C6H12O6(aq.) (glucose) 2C2H5OH(aq) + 2CO2(g)

 Oxides of group-14

Carbon Dioxide (CO2)

Physical Properties

CO2 is a colourless, odourless and heavy gas.

 Oxides of group-14

Carbon Dioxide (CO2)

Physical Properties

It is slightly soluble in water under ordinary pressure but at high pressure,

the solubility is high.

Dry Ice is obtained when CO2 is cooled under pressure - 50 to 60 atm.

When solid CO2 is allowed to evaporate in air under

1 atm pressure, it changes directly in to gaseous
state without liquifying.
 Oxides of group-14

Carbon Dioxide (CO2)

Chemical Properties

Weakly acidic oxide.

𝐂𝐎𝟐 + 𝐍𝐚𝐎𝐇 𝐍𝐚𝟐 𝐂𝐎𝟑

It do not burn and does not support burning.

When dissolved in water, it forms H2CO3 (Carbonic Acid).

𝐂𝐎𝟐 𝐠 + 𝐇𝟐 𝐎 𝐇𝟐𝐂𝐎𝟑(𝐠)
 Oxides of group-14

Carbon Dioxide (CO2)

Chemical Properties

H2CO3 is weak dibasic acid, cannot be isolated in solid state.

𝐇𝟐 𝐂𝐎𝟑 𝐚𝐪. 𝐇𝟑+ 𝐎 𝐚𝐪. + 𝐇𝐂𝐎−

𝟑 𝐚𝐪.

𝐇𝐂𝐎𝟑− 𝐚𝐪. 𝐇𝟑+ 𝐎 + 𝐂𝐎𝟐−

𝟑 𝐚𝐪.

H2CO3\HCO− 3 butter system helps to maintain

PH of blood system between 7.26 to 7.42.
 Oxides of group-14

Carbon Dioxide (CO2)

Chemical Properties

CO2 is present up to 0.03% by volume in the atmosphere is removed by

photosynthesis.
hv
6CO2 + 12H2O C H O + 6O2 + 6H2O
Chlorophyll 6 12 6
 Oxides of group-14

Carbon Dioxide (CO2)

Chemical Properties

CO2 can act as a reducing agent.

2Mg(s) +𝐂𝐎𝟐 𝐠 𝟐𝐌𝐠𝐎 𝐬 + 𝐂

 Oxides of group-14

Carbon Dioxide (CO2)

Chemical Properties

CO2 turns lime water milky

Ca(OH)2 (aq.) +𝐂𝐎𝟐 𝐠 𝐂𝐚𝐂𝐎𝟑 +

𝐇𝟐𝐎
white

CaC𝐎𝟑 + 𝐇𝟐𝐎 + 𝐂𝐎𝟐 𝐂𝐚 𝐇𝐂𝐎𝟑 𝟐 (𝐚𝐪. )

 Oxides of group-14

Uses of CO2

It is used as fire extinguisher.

2NaHCO3 + H2SO4(aq) Na2SO4(aq) + 2CO2↑ + 2H2O

 Oxides of group-14

Uses of CO2

Used in aerated drinks.

It is employed in Solvay Process

Solid CO2 is used as refrigerant.

It is used to manufacture Urea.

CO2 + 2NH3 CO(NH2 )2 + H2O

Select the correct option(s)?

(A) In CO2 molecule hybridization of ‘C’ is sp.

(B) CO2 two p𝝅-p𝝅 bonds are present.

(C) CO2 is a nonpolar molecule but having polar bond.

(D) Following structures are resonating structure of CO2

O–C  O  O=C=O  O  C–O

Solution

Ans. A,B,C,D
 Silicon and its compounds

Silicon

‘Si is 2nd most abundant (27.2%) element in earth’s crust.

Elemental ‘Si’ is very hard having diamond like structure.

Melting point (1793K) and Boiling point (3550K) is high

Exists in three isotopic forms.

Si
28 29 30
Si14 Si14 Si14
most
abundant
 Silicon and its compounds
Chemical Properties

SiF4(ℓ) Si3N4(s)

Red hot O2
SiO2(s) + 2H2(g) Si SiO2(s)
H2O 1173K

2773K
C(s)
SiC(s)
Carborundum
 Silicon and its compounds
Chemical Properties

Carborundum (SiC) is an extremely hard substance (next to diamond )

used in cutting tool and as a refractory material.

C
Si
 Silicon and its compounds

Silicon Dioxide (SiO2)

SiO2

Crystalline Form Silica

Amorphous Form Kieselguhr

 Silicon and its compounds

Silicon Dioxide (SiO2)

Structure

Si O Si O Si O Si

O O O O

Si O Si O Si O Si

O O O O

Si O Si O Si O Si
 Silicon and its compounds

Silicon Dioxide (SiO2)

SiO2 is inert due to strong Si-O-Si bonds,

but it is reactive towards HF and NaOH.

(i) SiO2 + NaOH Na2SiO3

(Sodium silicate)

(ii) SiO2 + 4 HF SiF4 + H2O

SiF4 + 2 HF H2SiF6 Etching of Glass
(Hexafluoro silicic acid)
 Silicon and its compounds

Silicon Dioxide (SiO2)

Quartz extensively used as a piezoelectric material

Silica gel is used as a drying and as a support for chromatographic

materials and catalysts.

Kieselguhr, an amorphous from of silica is used in filtration plants

 Silicon and its compounds

Silicon Dioxide (SiO2)

Uses

Quartz extensively used as a piezoelectric material.

 Silicon and its compounds

Silicon Dioxide (SiO2)

Uses

Silica gel is used as a drying and as a support for chromatographic

materials and catalysts.
 Silicon and its compounds

Silicon Dioxide (SiO2)

Uses

Kieselguhr, an amorphous from of silica is used in filtration plants

 Silicon and its compounds

Silicones

Silicones are organosilicon polymer which

contain −R2SiO− as a basic unit.
 Silicon and its compounds

Silicones

Properties

Silicones are chemically inert due to presence of strong sigma bond and
polymeric structures.

Silicones have water repelling nature due to presence of alkyl group.

Silicones are insulator due to absence of free electrons.

 Silicon and its compounds

Silicones

Preparation

Cu Hydrolysis
Alkyl halide + Si Alkyl chloro silane Silinoles
∆

Polymerisation
Silicones
Condensation

Cu R Si Cl3 Hydrolysis R Si (OH)3

RCl + Si R2 Si Cl2 R2 Si (OH)2
∆ R3 Si Cl R3 Si (OH)

Polymerisation
Silicones
Condensation
 Silicon and its compounds

Types of Silicones

Dimer silicone

Linear silicone

Cyclic silicone

Crosslinked silicone
 Silicon and its compounds
Dimer silicone

Unit : R3SiCl

–HCl
R3Si — Cl + H — OH R3Si — OH + H — O — SiR3

–H2O

R3Si — O — SiR3

Note

R3SiCl is a chain terminating unit.

 Silicon and its compounds

Types of Silicones

Dimer silicone

Linear silicone

Cyclic silicone

Crosslinked silicone
 Silicon and its compounds
Linear silicone

Unit : R2SiCl2 R R
–2HCl
HO — H + Cl — Si — Cl + H — OH HO — Si — OH

R R
R R R
–H2O
H — O— Si —OH + H — O— Si —OH + H — O— Si —OH

R R R R R

O — Si — O — Si— O
n
R R
Note
(R2SiO)n
R3SiCl is used to control the length of linear chain silicone.
 Silicon and its compounds

Types of Silicones

Dimer silicone

Linear silicone

Cyclic silicone

Crosslinked silicone
 Silicon and its compounds
Cyclic silicone

Cyclic structure having 3, 4, 5 and 6 silicon atoms within the ring

Unit : R2SiCl2
R R
| –HCl |
HO — H + Cl — Si — Cl + H — OH HO — Si — OH
| |
R R
R R
Si
R R
O O
H H Si
H H O O
O
|
O | |
| R Si Si R

|
R Si Si R
| O |
|

|
| OH
|
R
HO R R
R
 Silicon and its compounds

Types of Silicones

Dimer silicone

Linear silicone

Cyclic silicone

Crosslinked silicone
 Silicon and its compounds
Crosslinked silicone

Unit : RSiCl3
R R
–3HCl
HO — H + Cl — Si — Cl + H — OH HO — Si — OH

Cl + H — OH OH

R R

O — Si — O — Si— O
R
- H2O O O
n HO — Si — OH
O — Si — O — Si— O
OH
R R
 Silicon and its compounds

Uses

Used as sealant and greases.

 Silicon and its compounds

Uses

Used in surgical and cosmetic implants.

Used in making toys

 Silicon and its compounds

Uses

Used as electrical insulators

Used for water proofing of fabrics

The straight chain polymer is formed by :-
(A) Hydrolysis of (CH3)2SiCl2 followed by condensation
polymerisation
(B) Hydrolysis of (CH3)3SiCl followed by condensation
polymerisation
(C) Hydrolysis of CH3SiCl3 followed by condensation
polymerisation
(D) Hydrolysis of (CH3)4 Si by addition polymerisation

Solution R R

O — Si — O — Si— O
n
R R
Ans. A
Which of these is not a monomer for a high molecular mass silicone
polymer ?

(A) PhSiCl3

(B) MeSiCl3

(C) Me2SiCl2

(D) Me3SiCl

Solution

Ans. D
CO is
(A) An acidic oxide
(B) A basic oxide
(C) An amphoteric oxide
(D) A neutral oxide

Solution

Ans. D
Estimation of CO is done by
(A) I2
(B) I2O5
(C) Na2S2O3
(D) NH3

Solution

Estimation of CO is done by I2O5.

CO + I2O5 I2 + CO2

I2 + S2O32- S4O62- + I-
Ans. B
CO2 can be used as
(A) Fire extinguisher
(B) In cold storages
(C) In soda water
(D) All

Solution

Ans. D
Solid CO2 is called as
(A) Dry ice
(B) Dry oxide
(C) Dry bleach
(D) Dry soda

Solution

Ans. A
CO2 dissolves in H2O to give
(A) Basic solution
(B) Acidic solution
(C) Neutral solution
(D) Bitter taste solution

Solution

Ans. B
 Silicates

Silicates

Silicates are metal derivatives of silicic

acid, H4SiO4 or Si(OH)4,

12-01-2023 310
 Silicates

Silicates

Preparation

Silicates are formed by heating metal oxide or metal carbonates with sand.

Fused with sand

Na2CO2 Na4SiO4 , Na2(SiO3)n , etc.
SiO2

12-01-2023 311
 Silicates

Silicates

A large number of silicates minerals exist

in nature.

Example Feldspar, Zeolites, Mica and Asbestos.

12-01-2023 312
 Silicates

Silicates

Two important man – made silicates are

glass and cement.

12-01-2023 313
 Silicates

Silicates

Silicates are the product (s) of hetro

catenation of Si – O bond.

12-01-2023 314
 Why Si – O bond shows tendency of hetro catenation?

Solution

Consider the following 𝝅 bond formation 3p – 2p overlaps.

Si – O P–O S–O Cl – O

2p 2p
3p
3p

12-01-2023 315
 Why Si – O bond shows tendency of hetro catenation?

Solution

Si – O < P – O < S – O < Cl –0 (p bond formation tendency)

Si – O > P – O > S – O > Cl – O (Polymerisation/ Hetro–catenation tendency)

Si – O show tendency of hetro – catenation because 𝜋 – bond is relatively

ineffective / weak.

12-01-2023 316
 Silicates

Basic unit

Basic structural unit is SiO4–4 ( Silicate, i.e. derived from silicic acid ).

- 4H+
H4SiO4 ⎯⎯→ SiO44–

O–
O–
Si
O– O–
O– –O
sp3 O–
O–

12-01-2023 317
 Silicates

Basic unit

Basic structural unit is SiO4–4 ( Silicate, i.e. derived from silicic acid ).

- 4H+
H4SiO4 ⎯⎯→ SiO44–

O–
O–
Si
O– O–
O– –O
sp3 O–
O–

➢ In all silicates, oxidation state of ‘Si’ is +4 and ‘O’ is –2

➢ All silicates are sp3 hybridised and non-planar
12-01-2023 318
 Silicates

Types of Silicates

➢ Ortho Silicate (Neso Silicate)

➢ Pyro Silicate (Sore Silicate or Di-Silicate)

➢ Cyclic Silicate (Ring Silicate)

➢ Single chain Silicate (Pyroxene Silicate)

➢ Double chain Silicate (Amphibole Silicate)

➢ 2-D Sheet Silicate (Sheet Silicate or Phylo Silicate)

➢ 3-D Silicate (Tacto Silicate)

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 Silicates

Types of Silicates
O–

Ortho Silicate
O–
➢ Only single unit. –O O–
➢ Number of oxygen atom(s) shared
per basic tetrahedral unit = 0

➢ Contribution of oxygen atom(s)

per basic tetrahedral unit = 4

➢ General Formula : SiO44–

Example Zircon (ZrSiO4)

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 Silicates
Pyro Silicate
➢ Two basic unit.
➢ Number of oxygen atom(s) shared per basic tetrahedral unit = 1
➢ Contribution of oxygen atom(s) per basic tetrahedral unit = 3.5
➢ General Formula : Si2O76–

O- –
O–
O –O
O–
O–
–O –
O O–
O–
O–

O–
Example Hemimorphite Zn3Si2O7 · Zn(OH)2 · 2H2O
12-01-2023 321
 Find out the value of x in :
Mg𝒙Si2O7

Solution

𝟐𝒙 + 𝟒 × 𝟐 − 𝟕 × 𝟐 = 𝟎
𝒙=𝟑

Ans. 𝒙 = 𝟑

12-01-2023 322
 Silicates
Single chain Silicate

➢ n number of unit.

12-01-2023 323
 Silicates
Single Chain Silicate
O– O– O–

O– O– O–
O O O O O O ⟹
⟹ O O
O– O–
➢ n number of unit.
➢ Number of oxygen atom(s) shared per
basic tetrahedral unit = 2
➢ Contribution of oxygen atom(s) per
basic tetrahedral unit = 3
➢ General Formula : (SiO32–)n

Example Kinoite Ca2Cu2Si3O10

12-01-2023 324
 Find the molecular formula of four membered pyroxene silicate.

Solution
O– O–

O– O– O– O–
–O
O O O O–

= 𝐒𝐢𝐎𝟐−
𝟑 𝟒 + 𝐎𝟐−

= 𝐒𝐢𝟒𝐎𝟏𝟎−
𝟏𝟑

➢ General Formula : (SiO32–)n

➢ Molecular Formula : (SiO32–)n + O2-

Ans. 𝐒𝐢𝟒𝐎𝟏𝟎−
𝟏𝟑

12-01-2023 325
 Silicates
Double Chain Silicate
➢ n number of unit.
O– O– O–

O– O– O–
O O O O O O
O O
O– O–

⟸ ⟹
O– O–
O O
O O O O O O
O– O– O–
O– O– O–

12-01-2023 326
 Silicates
Double Chain Silicate
O– O– O–

O– O– O–
O O O O O O
O O
O– O–

⟸ ⟹
O– O–
O O
O O O O O O
O– O– O–
O– O– O–

➢ n number of unit.
➢ Number of oxygen atom(s) shared per
basic tetrahedral unit = 2 and 3
Example
➢ Contribution of oxygen atom(s) per
basic tetrahedral unit = 2.5 Ca2Mg5(Si4O11)2(OH)2
➢ General Formula : [(Si4O11) -6] n Tremolite asbestos
12-01-2023 327
 Silicates
Cyclic Silicate O–
➢ n number of unit. O–
O O
O–
O

O– O
O–

➢ General Formula : (SiO3–2)n

➢ No. of oxygen shard per tetrahedral = 2
Example
➢ Contribution of oxygen atom(s) per
basic tetrahedral unit = 3 Beryl Be3Al2Si6O18
12-01-2023 328
 Silicates
Cyclic Silicate
O–
n=3
O–
O O

O– O–
O– O–
O

➢ Molecular formula = Si3O9–6

➢ No. of oxygen shard per tetrahedral = 2
➢ Contribution of oxygen atom(s) per basic tetrahedral unit = 3
➢ Total no. of O-shared = 3
12-01-2023 329
 Silicates
Cyclic Silicate
O–

n=4 O–
O O
O– O– O– O–
O
O
O–

O–

−8
➢ Molecular formula = Si4O12
➢ No. of oxygen shard per tetrahedral = 2
➢ Contribution of oxygen atom(s) per basic tetrahedral unit = 3
➢ Total no. of O-shared = 4
12-01-2023 330
 Silicates
Cyclic Silicate O–

O–
n=5 O O
O– O–
O– O–

O
O– O O–

O– O–

−10
➢ Molecular formula = Si5O15
➢ No. of oxygen shard per tetrahedral = 2
➢ Contribution of oxygen atom(s) per basic tetrahedral unit = 3
➢ Total no. of O-shared = 5
12-01-2023 331
 Silicates
Cyclic Silicate O–

O–
n=6 O– O O O–
O–

O
O

O– O– O–
O
O–
−12
➢ Molecular formula = Si6O18
O–
➢ No. of oxygen shard per tetrahedral = 2
➢ Contribution of oxygen atom(s) per basic tetrahedral unit = 3
➢ Total no. of O-shared = 6
12-01-2023 332
 Silicates

⟹
Sheet Silicate
O
➢ n number of unit.
O–
O O O
O O
O– O–

⟸ ⟹
O– O–
O O
O O
O–

➢ General Formula : (Si2O5–2)n

⟹
➢ No. of oxygen shard per tetrahedral = 3
➢ Contribution of oxygen atom(s) per basic Example

12-01-2023
tetrahedral unit = 2.5 Talc (Mg3(OH)2(Si2O5)333
2)
 Silicates
3D Silicate

➢ n number of unit.
Si O Si O Si O Si O

O O O O

Si O Si O Si O Si O

O O O O

Si O Si O Si O Si O

➢ General Formula : (SiO2)n

➢ Contribution of oxygen atom(s) per basic tetrahedral unit = 2
➢ Number of oxygen atom(s) shared per basic tetrahedral unit = 4
Example Silica (SiO2)n
12-01-2023 334
 Silicates

Name the type of the structure of silicate in which one oxygen atom of
[SiO4]4– is shared ?

(A)Linear chain silicate

Solution

Ans. C

12-01-2023 335
 Silicates

Name the type of the structure of silicate in which one oxygen atom of
[SiO4]4– is shared ?

(A)Linear chain silicate (B)Sheet silicate

Solution

Ans. C

12-01-2023 336
 Silicates

Name the type of the structure of silicate in which one oxygen atom of
[SiO4]4– is shared ?

(A)Linear chain silicate (B)Sheet silicate

(C)Pyro silicate

Solution

O– O–
O– O O–
O– O–
Ans. C

12-01-2023 337
 Silicates

Name the type of the structure of silicate in which one oxygen atom of
[SiO4]4– is shared ?

(A)Linear chain silicate (B)Sheet silicate

(C)Pyro silicate (D)Three dimensional

Solution

Ans. C

12-01-2023 338
 Silicates

Which one of the following anions is present in the chain structure of

silicates :
(B) SiO44– (B) Si2O76–
(C) (Si2O52–)n (D) (SiO32–)n

Solution

Ans. C

12-01-2023 339
 ADVANCED LEVEL ILLUSTRATIONS
AND
CONCEPTS

12-01-2023 340
 Zeolites

Zeolites

Zeolites are aluminosilicate of Na+, K+ or Ca2+

Uses

Hydrated Zeolites are used as ion exchangers in softening of hard

water.

As catalyst in petrochemical industries for cracking of

hydrocarbons and isomerisation.

ZSM-5 (A type of Zeolite) used to convert alcohols into gasoline.

12-01-2023 341
 Hydrides

Hydride

CH4 SiH4 GeH4 SnH4 PbH4

Bond strength : Decreases ↓

Thermal stability : Decreases ↓

Reducing strength : Increases ↑

Acidic strength : Increases ↑

12-01-2023 342
 Glass

Glass

➢ Transparent, supercooled liquid or amorphous solid.

➢ It has no sharp melting point.

➢ It is man - made silicate.

➢ Glass has no definite chemical formula but can be represented by formula.

xM2O. yM’O. 6SiO2

M : Monovalent Metal
M’ : Bivalent Metal

12-01-2023 343
 Which of the following attacks glass

A. HCl

B. HF

C. HI

D. HBr

Solution

SiO2 + 4 HF SiF4 + H2O

SiF4 + 2 HF H2SiF6 Etching of Glass
(Hexafluoro silicic acid)

Ans. B

12-01-2023 344
 Carborundum is

(A) SiC (B) AlCl3 (C) l2 (SO4)3 (D) (BN)X

Solution

Si

Si
Si Si
Si
Ans. A

12-01-2023 345
 Hybridization of ‘Si’ in SiO2 is

(A) sp (B) sp2 (C) sp3 (D) All

Solution

Si O Si O Si
sp3 O O O

Si O Si O Si

O O O

Si O Si O Si

Ans. C

12-01-2023 346
 Most stable hybrids among the following is
(A) CH4
(B) SiH4
(C) GeH4
(D) SnH4

Solution

CH4 SiH4 GeH4 SnH4 PbH4

Bond strength : Decreases ↓

Thermal stability : Decreases ↓ Ans. A

12-01-2023 347
 ADVANCED LEVEL ILLUSTRATIONS
AND
CONCEPTS

12-01-2023 348
 Carbides

Carbides

A binary compound of carbon with an element

of lower or comparable electronegativity

12-01-2023 349
 Carbides

Carbides

Types

Ionic Carbides

Covalent Carbides

Interstitial Carbide
12-01-2023 350
 Carbides

Carbides

A binary compound of carbon with an element of lower or comparable

electronegativity

There are three types of carbides.

(A) Ionic Carbide ( Salt Like Carbide)

These are formed by IA, IIA, IIIA group elements . These are of three types:

(i) Methanides (C-4 Units) : Produce CH4 on reacting with water.

Be2C + H2O 2 Be(OH)2 + CH4
Al4C3 + H2O 4 Al(OH)3 + CH4

12-01-2023 351
 Carbides

Carbides

There are three types of carbides.

(A) Ionic Carbide ( Salt Like Carbide)

These are formed by IA, IIA, IIIA group elements . These are of three types:

(ii) Acetylides (C2–2 Units) : Produce C2H2 on reacting with water.

CaC2 + H2O Ca(OH)2+ C2H2

12-01-2023 352
 Carbides

Carbides

There are three types of carbides.

(A) Ionic Carbide ( Salt Like Carbide)

These are formed by IA, IIA, IIIA group elements . These are of three types:

(iii) Allylides (C3–4 Units) : Produce C3H4 on reacting with water.

Mg2C3 + 4H2O 2Mg(OH)2 + C3H4
(Propyne)
CH3-C ≡ CH

12-01-2023 353
 Carbides

Carbides

(B) Covalent Carbide (Giant Molecular Carbide)

(i) Compounds of carbon with element having similar electronegativity.

(ii) These are polymeric, extremely hard, thermally stable and chemically inert.

Si C Si C
Example
C Si C Si

(i) Norbide (B4C)

Si C Si C
(ii) Carborandum (SiC )

SiC (Diamond Like Structure)

12-01-2023 354
 Carbides

Carbides

(C) Interstitial Carbide

(i) Transition Metal like Ti, Zr, Hf, V, Nb and Mo form these Carbides.

(ii) These Metal with small sized and less reactive elements such as C, H, B and
N forms interstitial compound.

Trapped Carbon
Transition Metal in interstitial sites

(iii) These are non stoichiometric compounds.

12-01-2023 355
 Carbides

(C) Interstitial Carbide

Example

➢ ZrC (Zirconium carbide)

➢ VC (Vanadium carbide)
➢ WC (Tungsten carbide)

12-01-2023 356
 Tin and It’s Compounds

Tin (Sn)

Physical Properties

➢ Soft metal

➢ Highly malleable and ductile

➢ Found in there allotropic forms

Grey tin ⇌ White tin ⇌ Rhombic tin

5.8 7.8 7.6 (Density gm/cc)

➢ White tin is most stable forms

➢ On bending tin sheet it produces a sound known as ‘Cry of Tin’

12-01-2023 357
 Tin and It’s Compounds

Tin (Sn)

Chemical Properties

‘Sn’ is amphoteric hence reacts with acid and base both.

12-01-2023 358
 Tin and It’s Compounds

Tin (Sn)

Chemical Properties

Reaction with Acid

➢ Sn + HCl → SnCl2 + H2 ↑
(hot/conc.)

➢ Sn + H2SO4 → SnSO4 + H2 ↑
(dil.)

➢ Sn + 4H2SO4 → Sn(SO4)2 + 2SO2 ↑ + 4H2O

(conc.)

➢ 4Sn + 10 HNO3 → 4Sn(NO3)2 + NH4NO3 + 5H2O

(dil.)

➢ Sn + 4HNO3 → H2SnO3 + 4NO2 + H2O

12-01-2023 (conc.) 359
 Tin and It’s Compounds

Tin (Sn)

Chemical Properties

Reaction with Base (NaOH or KOH)

➢ Sn + 2 NaOH + H2O → Na2SnO3 + 2H2 ↑

12-01-2023 360
 Tin and It’s Compounds

SnO and SnO2

Preparation

SnO
➢ Sn2+ (aq.) + OH– → Sn (OH)2 (Dark
gray)
SnO. xH2O
O2 ∆

SnO2
(white)

12-01-2023 361
 Tin and It’s Compounds

SnO and SnO2

Preparation

➢ By heating oxy salts.

SnC2O4 ∆ SnO + CO2 + CO

SnSO4 ∆ SnO2 + SO2 ↑

12-01-2023 362
 Tin and It’s Compounds

SnO and SnO2

Chemical Properties

Both are amphoteric oxides, hence reacts with acid and base both.

➢ SnO + HCl → SnCl2 + H2O

➢ SnO + NaOH → Na2SnO2 + H2O

➢ SnO + NaOH → Na2SnO3 + Sn + H2O

Hot / Conc.

12-01-2023 363
 Tin and It’s Compounds

SnO and SnO2

Chemical Properties

Does not react with acids except conc. H2SO4

➢ SnO2 + H2SO4 → Sn(SO4)2 + 2H2O

➢ SnO2 + NaOH → Na2SnO3 + H2O

12-01-2023 364
 Tin and It’s Compounds

SnCl2

Preparation

∆
Sn + HCl (g) SnCl2 + H2
∆
Sn + HgCl2 SnCl2 + Hg

∆
Sn + HCl (aq) SnCl2 (aq) + H2 ↑

SnCl2. 2H2O

D
D

SnO + HCl Sn(OH)Cl SnCl2 (Only)

12-01-2023 365
 Tin and It’s Compounds

SnCl2

➢ SnCl2 (S) exist as a polymeric chain

➢ Structure (solid)
•• •• ••
Sn Sn Sn
Cl | Cl | Cl | Cl
Cl Cl Cl

➢ Exist as monomer at ≃ 1100° C.

12-01-2023 366
 Tin and It’s Compounds

Chemical Properties

1. SnCl2 act a reducing agent

+2
SnCl2
HgCl2 Hg

MnO4– H+ Mn2+

Cr2O72– H
+
Cr3+

I2 I–

Fe3p Fe2+
+4
H2SO3 S2–
+4
SnCl4
12-01-2023 367
 Tin and It’s Compounds

Chemical Properties

2. A piece of Sn is always added to preserve the solution o SnCl

∆
Sn + Cl2 SnCl4
(air)

SnCl4 + Sn → SnCl2

12-01-2023 368
 Tin and It’s Compounds

SnCl4

Preparation

1. Sn + 2Cl2 → SnCl4
2. Sn + 2HgCl2 → SnCl4 + 2Hg

➢ It is a colorless volatile liquid.

➢ Exists as monomer

12-01-2023 369
 Tin and It’s Compounds

SnCl4

Chemical Properties

1. SnCl4 + 2H2O → SnO2 + 2HCl

2. SnCl4 + 2HCl → H2 [SnCl6]

3. SnCl4 + 2NH4Cl → NH4 [SnCl6] (Pink salt)

5H2O
4. SnCl4 SnCl4 .5H2O
(Liquid) Semisolid
(Butter of tin)

12-01-2023 370
 Which carbide gives CH4 on hydrolysis

(A) Be2 (B) CB4 (C) Csi (D) CAl4C3

Solution

Be2C + H2O 2 Be(OH)2 + CH4

Ans. A

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 Lead and It’s Compounds

Lead (Pb)

Soft metal

Highly malleable but not very ductile

Does not show allotropy

Readily obtained in crystalline state by the process of prepetition.

(CH3COO)2 Pb + Zn → Pb+ (CH𝟑COO)𝟐 Zn

12-01-2023 372
12-01-2023 373
 Lead and It’s Compounds

Lead (Pb)

Chemical Properties

With water
2Pb + O2 + 2H2O → Pb(OH)2
This phenomena is know as plumbo solvency.

With air
∆ 400−5000𝑐
Pb O2 PbO Pb3O4
𝑂2

12-01-2023 374
 Lead and It’s Compounds

Lead (Pb)

Chemical Properties

Pb is amphoteric reacts with acid and base both

With Acid

1. Pb + HCl → PbCl2 + H2 ↑
(Hot & Conc)

2. Pb + 2H2SO4 → PbSO4 + SO2↑ + 2H2O

(Hot & Conc)

3. 3Pb + 4HNO3 → Pb(NO3)2 + 2NO2↑ + 2H2

( Conc)

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Lead (Pb)

Chemical Properties

Pb is amphoteric reacts with acid and base both

With Base

Pb + 2NaoH → Na2PbO2 + H2 ↑

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Oxides of lead

PbO (Lead monoxide) (litharge)

PbO2 (Lead dioxide)

Pb2O3 (Lead monoxide)

Pb3O4 (Lead Tetra oxide)

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PbO

Preparation

300𝑜𝐶 877𝑜𝐶
2Pb + O2 2PbO 2PbO
fused
Massicot Litharge
(yellow powder) (Red – yellow crystalline)
picture picture

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Properties of PbO

→ PbO is a amphoteric in nature

PbO + 2HNO3 → Pb(NO3)2 + H2O
PbO + NaOH → Na2PbO2 + H2O

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Preparation of PbO2

𝐟𝐮𝐬𝐞𝐝 𝐰𝐢𝐭𝐡
→ PbO + KClO3 2PbO2 + KCl
𝐊𝐍𝐎𝟑

Properties of PbO

(1) PbO2 is amphoteric Oxide

PbO2 + 4HCl → PbCl2 + Cl2 + H2O
(Hot & Conc)

PbO2 + 2H2SO4 → 2PbSO4 + 2H2O + O2

(Hot & Conc )

PbO2 + 2NaOH → Na2PbO3 + H2O

(Hot & Conc )

Note PbO2 does not react with HNO3 . Insoluble in water & HNO3

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Properties of PbO

(2) PbO2 is a powerful oxidising agent

PbO2
SO2 𝑺𝑶𝟐−
𝟒

Mn2+ 𝐌𝐧𝐎−
𝟒

𝐂𝟐𝐎𝟐−
𝟒
CO2

Cl– Cl2

Pb2+

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Preparation of Pb2O3

PbO + NaOCl Pb2O3 + NaCl

(Yellow powder)

Properties of Pb2O3

It is a mixed oxide (PbO.PbO2)

Pb2O3 + 2HNO3 Pb (NO3)2 + PbO2 + H2O

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Preparation of Pb2O3

PbO + O2 Pb3O4
(Scarlet red)

Properties of Pb2O3

It is a mixed oxide (2PbO.PbO2)

Pb3O4 + 4HNO3 PbO2 + 2Pb (NO3)2 + 2H2O

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