11C11

The p-Block Elements

 The p-Block Elements

Group 13 Group 14
 11C11.1

Boron Family
 Introduction to Boron Family
• B, Al, Ga, In, Tl and Nh
• ns2np1
• Boron is a fairly rare element.

Orthoboric Acid Borax Kernite

• Borax occurs in Puga Valley (Ladakh) and Sambhar Lake (Rajasthan).

• Al is the most abundant metal and the 3rd most abundant element in
the earth’s crust.
Electronic Configurations of Group-13 Elements

2s22p1

3s23p1

4s23d104p1

5s24d105p1

6s24f145d106p1

7s25f146d107p1
 11C11.1

CV 2

Trends in General Properties of Group

13 Elements
 Trends in Atomic Size
• Poor screening of 3d-subshell
Zeff ↑ Trends in Atomic Size
Ga < Al 167 170
143 135
• Inert Pair Effect

Atomic Size (pm)

88
Zeff ↑
In ~ Tl

• Trend: 5 13 31 49 81

B < Ga < Al < In ~ Tl Atomic Number

 Trends in Ionisation Enthalpy
• Poor screening of 3d-subshell
Zeff ↑ Trends in Ionisation Enthalpy
801
Ga > Al

Ionisation Enthalpy (kJ/mol)

577 579 558 589
• Inert Pair Effect
Zeff ↑
In < Tl

• Trend: 5 13 31 49 81
Atomic Number
In < Al < Ga < Tl < B
 Trends in Electronegativity

• Due to poor shielding of d & f Trends in Electronegativity

subshell 2
1.7 1.8
Zeff ↑ 1.6

Electronegativity
1.5

EN ↑ down the group

• Trend:
5 13 31 49 81
Al < Ga < In < Tl < B Atomic Number
 11C11.1

CV 3

Properties of Group 13 Elements-I

 Physical Properties
• Boron is non-metallic, extremely hard and
black coloured solid.
• Due to very strong crystalline lattice, boron has
unusually high melting point.
• Rest of the members are soft metals with low
melting point and high electrical conductivity.
• Gallium has low melting point (303K) but high
boiling point (2676 K).
• Density of the elements increases down the
group.
 Oxidation State and Chemical Reactivity

➢ Small size and high I.E. mainly forms covalent bond.

➢ Most electropositive and shows O.S. + 3.

➢ Electropositive and shows O.S. + 3.

➢ Shows O.S. +3 and +1.

➢ Mainly shows O.S. +1 due to poor screening by 4f and 5d

subshell electrons (Inert Pair Effect).

Relative stability of +1 O.S. progressively increases down the group:

Al < Ga < In < Tl
 Oxidation State and Chemical Reactivity
• +3 oxidation state is highly oxidising in character.
• The compounds in +1 oxidation state are more ionic than those in +3
oxidation state.
TlCl > TlCl3
• B and Al form trivalent covalent compounds which are Electron Deficient.

`
H H H
H
B H N B
N
H H H
2 3
sp sp
H H H H
Planar Tetrahedral
Borane-Ammonia Adduct
 Oxidation State and Chemical Reactivity
• AlCl3 achieves stability by forming a dimer.
Cl Cl
Cl
Al

Al
Cl
Cl Cl
 Oxidation State and Chemical Reactivity
• AlCl3 achieves stability by forming a dimer.
Cl 221 pm Cl Cl

118° 79°

Cl Cl 206 pm Cl

• Trichlorides on hydrolysis in water form tetrahedral M OH 4

−.

BCl3 + 4 H2 O → B OH − + 3 HCl + H +
4
 ConcepTest
Ready for Challenge
Q. AlCl3 is an electron deficient compound but AlF3 is not . Give reason.
Q. AlCl3 is an electron deficient compound but AlF3 is not . Give reason.

Sol. AlF3 is an ionic compound.

Al3+ : 1s2 , 2s2 , 2p6 F −: 1s2 , 2s2 , 2p6

Complete Octet

AlCl3 is a covalent compound.

Cl

Al 6 electrons in valence shell of Al

Cl Cl
 11C11.1

CV 4

Properties of Group 13 Elements-II

 Reaction with Air

4 E s + 3 O2 g → 2 E2 O3 s

2 E s + N2 g → 2 EN s

• B is unreactive in crystalline form.

• Al forms a very thin oxide layer on the surface which protects the
metal from further attack.
• Amorphous B and Al on heating in air form B2 O3 and Al2 O3 respectively.

B 2 O3 Al2 O3 Ga2 O3 In2 O3 Tl2 O3

Acidic Amphoteric Basic

 Reaction with Acids and Alkalies

• B does not react with acids and alkalies even at moderate conditions.

• Al dissolves in dilute HCl and liberates dihydrogen:

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

• Al reacts with aqueous alkali and liberates dihydrogen:

2 Al s + 2 NaOH aq + 6 H2 O l → 2 Na+ Al OH 4
− aq + 3 H2 g
Sodiumtetrahydrox
yaluminate(III)
 Reaction with Halogens
2 E s + 3 X2 → 2 EX3 s

• TlI3 does not exist due to high I.E. of Tl and low E.A. of I.
• The monomeric trihalides, being electron deficient, are strong Lewis
acids, except AlF3 .
• In case of B, the order of acidic nature of trihalides is as follows:
BF3 < BCl3 < BBr3 < BI3
F Cl
Due to similar size Due to difference in
the extent of size the extent of
overlapping is high B overlapping is poor
B
Less electron High electron
F F deficiency
Cl Cl deficiency
Q. Why Al does not react with concentrated nitric acid?

Sol.

Al does not react with conc. HNO3 due formation of a protective oxide
layer.

Al2 O3 Protective Layer

Al
 Anomalous Behaviour of Boron
• Small Size
• High Electronegativity
• Absence of d-orbital
Diagonal Relationship
with Si

Some dissimilarities with rest

members of the group
 Diagonal Relationship with Si
• Both are non-metal.
• Both have high melting point.
• B2 O3 and SiO2 are acidic in nature:
B2 O3 + 6 NaOH → 2 Na3 BO3 + 3 H2 O
SiO2 + 2 NaOH → Na2 SiO3 + H2 O
• Halides of both B and Si are hydrolysed to form corresponding acids:
BCl3 + 3 H2 O → H3 BO3 + 3 HCl
SiCl4 + 4 H2 O → H4 SiO4 + 4 HCl
• Both forms carbides with carbon B4 C and SiC which are very hard
substances.
 Dissimilarities with Al
Boron Aluminium

• Non-metal • Metal
• Shows allotropy • Does not show allotropy
• High melting point ~2200℃ • Low melting point 660°C
• Maximum covalency is 4 • Maximum covalency is 6
• Forms stable hydrides: BH3 , B2 H6 • Forms unstable hydrides
• Forms covalent compounds only • Forms covalent as well as ionic
compounds

B8 B10 B12
Summary

• Trend in Atomic Size : B < Ga < Al < In ~ Tl

• Trend in Ionisation Enthalpy : In < Al < Ga < Tl < B
• Trend in Electronegativity : Al < Ga < In < Tl < B
• Nature of oxides :
B 2 O3 Al2 O3 Ga2 O3 In2 O3 Tl2 O3

Acidic Amphoteric Basic

• Acidic nature of Borontrihalides :

BF3 < BCl3 < BBr3 < BI3
Summary
H2 O
E2 O3 + EN E(OH)3 +NH3
E(OH)3 +HX

Air
H2 O
Halogens Steam
HX + EX3 Group 13 (E) E2 O3 + H2

Acid
H2 O
Al(OH)3 + CH4 Al4 C3 Na2 EO2 + H2
Salt + H2
 Borax
• Chemical Formula: Na2 B4 O7 . 10H2 O or Na2 B4 O5 OH 4 . 8H2 O.
OH
O OH
+
Na
B− B
O
O O
B B−
OH O Na+ OH
• Also known as Tincal or Suhaga (contains 45% Borax).

• Borax can also be prepared from Boric acid:

4 H3 BO3 + Na2 CO3 → Na2 B4 O7 + 6 H2 O + CO2
 Properties of Borax
• Borax is know to exist in three forms:

Prismatic form Octahedral form Borax Glass

(Jeweller’s Borax)

OH OH
O OH O OH
+ +
Na Na
B− B B− B
O O
O O O O
B B− B B−
OH O Na+ OH OH O Na+ OH

Na2 B4 O5 OH 4 . 8H2 O Na2 B4 O5 OH 4 . 5H2 O Na2 B4 O7

 Properties of Borax
• Basic in nature:
Na2 B4 O7 + 7 H2 O → 2 NaOH + 4 H3 BO3
Strong Weak
Base Acid

• Aqueous solution of Borax acts as a Buffer.

• Action of Heat:
Heat 740℃
Na2 B4 O7 . 10H2 O Na2 B4 O7 2 NaBO2 + B2 O3
Sodium Boric
metaborate anhydride

Borax Bead
(Glassy Mass)

• Borax bead test is used to identify Transition Metals in the laboratory.

 Borax Bead Test
• Mixture of Metal Salt and Borax Bead is heated in Bunsen burner.
• Metal metaborates are formed which are coloured in nature.
CoSO4 + B2 O3 → Co BO2 2 + SO3
Cobalt metaborate
Blue
Oxidising Flame

Reducing Flame

Co BO2 2
Bunsen Burner
 Borax Bead Test

Reducing
Oxidising Flame
Element Flame
Hot Cold Hot/Cold
Chromium Yellow-Red Green Green
Manganese Violet Violet Colourless
Nickel Brown Red-Brown Grey
Copper Blue Green-Blue Red-Brown
Cobalt Blue Blue Blue
 ConcepTest
Ready for Challenge
Q. What are the hybridisation of boron atoms in borax ?

Sol.
OH
sp3 O OH
B− B
O sp2
O O
B B−
OH O OH

sp2 sp3
 11C11.2

CV 2

Orthoboric Acid
 Orthoboric Acid
• Chemical Formula: H3 BO3 .
O O
• White crystalline solid. H H
B
• Highly soluble in hot water.
• Preparation of Orthoboric acid: O
a) From Borax: H

Na2 B4 O7 + 2 HCl + 5 H2 O → 2 NaCl + 4 H3 BO3

Borax Orhtoboric Acid

b) From Colemanite:
Ca2 B6 O11 + 2 SO2 + 11 H2 O → 2 Ca HSO3 2 + 6 H3 BO3
Colemanite Orhtoboric Acid
 Properties of Orthoboric Acid
• It has a layer structure in which planar BO3
units are joined by H-bonds.
• Weak aprotic acid:
−
H3 BO3 + H2 O → B OH 4 + H+

• Monobasic acid.

• Action of Heat:
100℃ 160℃ Strong Heating
4 H3 BO3 4 HBO2 + 4 H2 O H2 B4 O7 + H2 O 2 B2 O3 + H2 O
Metaboric Acid Tetraboric Acid Boric Anhydride
Q. Starting from boric acid how would you prepare?
a) Boric anhydride
b) Boron trichloride
c) Boron hydride
Sol. a) Boric anhydride
Strong heating
2 H3 BO3 B2 O3 + 3 H2 O

b) Boron trichloride
Strong heating 3 C + 3 Cl2
2 H3 BO3 B 2 O3 2 BCl3 + 3 CO

c) Boron hydride
Strong heating 3 Mg −Δ Dil. HCl
2 H3 BO3 B2 O3 Mg 3 B2 B2 H6 + 3MgCl2
Q. A certain salt ‘X’ gives the following results :
a) Its aqueous solution is alkaline to litmus.
b) It swells up to a glassy material Y on strong heating.
c) When conc. H2 SO4 is added to a hot solution of X, white crystal of Z
separates out.
Identify X, Y and Z. Also give the balanced chemical equation in each
case.
Sol.
a) Na2 B4 O7 + 7 H2 O → 2 NaOH + 4 H3 BO3
X (Borax) Strong Base

b) Na2 B4 O7 → 2 NaBO2 + B2 O3
X (Borax) Y (Glassy Bead)

c) Na2 B4 O7 + 5 H2 O + H2 SO4 → 4 H3 BO3 + Na2 SO4

X (Borax) Z (Boric Acid- White Crystal)
 Diborane

H H

B
H

H
B

H H
 Diborane

H 134 pm
H
H
120° 97°

H 119 pm
H H

• 3C − 2e− Bond
• Banana Bond
 Preparation of Diborane
a) Boron trichloride with LiAlH4 in Diethyl ether:

4 BCl3 + 3 LiAlH4 → 2 B2 H6 + 3 LiCl + 3 AlCl3

b) Diborane is produced on an industrial scale by the reaction of BF3 with

sodium hydride:
450 K
2 BF3 + 6 NaH B2 H6 + 6 NaF

c) Silent Electric Discharge:

Silent Electric Discharge
2 BCl3 + 6 H2 2 B2 H6 + 3 HCl
 Properties of Diborane
• Colourless.
• Highly Toxic.
• Disagreeable odour and causes headache.
• Boiling Point 180 K.
• Action of Heat:
Red Heat
B2 H6 2 B + 3 H2
• Combustion:
Combustion
B2 H6 + 3 O2 B2 O3 + 3 H2 O Δc H = −1976 KJmol−1
 Properties of Diborane
• Lewis Acid:
H
B2 H6 + 2 NMe3 → 2 BH3 . NMe3
H N H Borane Adduct
B B
B2 H6 + 2 CO → 2 BH3 . CO
N N Borane Adduct
H B H
Low Temperature
B2 H6 + 2 NH3 B2 H6 . 2NH3
H Borane Adduct
Borazine
(Inorganic Benzene) 200℃
3 B2 H6 . 2NH3 2 B3 N3 H6 + 12 H2
Borazine
 Properties of Diborane
• Lithium and Sodium tetrahydridoborates, also known as borohydrides.
• Prepared by the reaction of metal hydrides with B2 H6 in diethyl ether.
2 MH + B2 H6 → 2 M + BH4 –

M = Li or Na
• LiBH4 and NaBH4 are used as reducing agents in organic synthesis.
Q. Specify the coordination geometry around and hybridization of N and
B atoms in 1 : 1 complex of BH3 and NH3 :
(a) N : tetrahedral, sp3 ; B : tetrahedral, sp3
(b) N : pyramidal, sp3 ; B : pyramidal, sp3
(c) N : pyramidal, sp3 ; B : planar, sp2
(d) N : pyramidal, sp3 ; B : tetrahedral, sp3

Pause the video

Time duration : 2 minutes
Q. Specify the coordination geometry around and hybridization of N and
B atoms in 1 : 1 complex of BH3 and NH3 :
(a) N : tetrahedral, sp3 ; B : tetrahedral, sp3
(b) N : pyramidal, sp3 ; B : pyramidal, sp3
(c) N : pyramidal, sp3 ; B : planar, sp2
(d) N : pyramidal, sp3 ; B : tetrahedral, sp3

Sol. H H
H
B sp3 Tetrahedral
Tetrahedral sp3 N
H
H H

Hence the correct option is a) N : tetrahedral, sp3 ; B : tetrahedral, sp3

 Uses of Group 13 Elements
Boron as:

Refractory Material Bulletproof Jacket Aeroplane Components

• Boron-10 (10B) isotope has high ability

to absorb neutrons, hence metal
borides are used in nuclear industry
as protective shields and control rods.
 Uses of Group 13 Elements
Borax and Orthoboric Acid as:

Fibre Glass

Glass Wool

Heat Resistant Glass

 Uses of Group 13 Elements
Aluminium as:

Wire Pipes and Tubes

Utensils Foil
Summary

NaBO2 + B2 O3

Δ
160℃
Na2 B4 O7 HBO2 H4 B4 O7

Δ 100℃ Δ
HCl Strong Heat Na or K
Na2 B4 O7 . 10H2 O H3 BO3 B2 O3 B
H2 SO4
C + X2
NH4 Cl NaOH
BX 3
BN + B2 O3 NaBO2
 11C11.3

Carbon Family
 Carbon Family
• C, Si, Ge, Sn, Pb and Fl
• Carbon is the 17th most abundant element by mass in the earth’s crust.

Coal Graphite Diamond

• Two stable isotopes: 12C and 13C.

• Radioactive isotope: 14C with half-life 5770 years and used for carbon
dating.
 Carbon Family
• Silicon is the 2nd most abundant element by mass (27.7 %) in the earth’s
crust.

Silica Sand Silicates

• Germanium exists only in traces.

• Tin occurs mainly as cassiterite, SnO2 and lead as galena, PbS.
• Flerovium is synthetically prepared radioactive element
Electronic Configurations of Group-14 Elements

2s22p2

3s23p2

4s23d104p2

5s24d105p2

6s24f145d106p2 Inert Pair Effect

7s25f146d107p2 Radioactive
 11C11.3

CV 2

Trends in General Properties of Group

14 Elements
 Trends in Atomic Size
• Considerable increase in
covalent radius from C to Si Trends in Atomic Size
140 146
118 122

• Si to Pb a small increase in

Atomic Size (pm)

77
radius
• Poor screening of d & f-subshell

• Trend: 6 14 32 50 82
C < Si < Ge < Sn < Pb Atomic Number
 Trends in Ionisation Enthalpy

• The Δi H1 of group 14
members is higher than the
Trends in Ionisation Enthalpy
1086
corresponding members of

Ionisation Enthalpy (kJ/mol)

786 761
group 13. 708 715

• Inert Pair Effect

Zeff ↑
Sn < Pb
6 14 32 50 82
• Trend: Atomic Number

Sn < Pb < Ge < Si < C

 Trends in Electronegativity

• The EN values for elements

from Si to Sn are almost the Trends in Electronegativity
same. 2.5

1.9

Electronegativity
1.8 1.8 1.8
• Inert Pair Effect
Zeff ↑
Sn < Pb

• Trend:
6 14 32 50 82
Sn ~ Ge ~ Si < Pb < C Atomic Number
 11C11.3

CV 3

Properties of Group 14 Elements-I

 Physical Properties
• All members of group 14 are solids.

C Si Ge Sn Pb

Non-Metal Metalloid Metal

4373 M.P. & B.P.

3550 M.P. B.P.

Temperature (K)
3123 2896
• M.P. and B.P. of group 14
2024
1693
elements are much higher than 1218
600
505
those of corresponding elements
of group 13. 6 14 32 50 82
Atomic Number
 Oxidation State and Chemical
Reactivity
• High I.E. mainly forms covalent bond in + 4 O.S.

• Higher members show O.S. +2 due to poor screening by 4f

and 5d subshell electrons (Inert Pair Effect).

• Relative stability of +2 O.S. progressively increases down the

group: Ge2+ < Sn2+ < Pb2+
− 2e−
Ge2+ Ge4+ Reducing Agent

Less Stable More Stable

+ 2e−
Pb4+ Pb2+ Oxidising Agent
Less Stable More Stable
 Oxidation State and Chemical
Reactivity
• Carbon cannot exceed its covalency more than 4, because of the
absence of d-orbital in them.
• Halides undergo hydrolysis and have tendency to form complexes like,
SiF62– , GeCl6 2– , Sn OH 6
2–

• Hybridisation of the central atom is sp3 d2 .

11C11.3

PSV 1
Q. Why Trimethylamine CH3 3 N is more basic than Trisilylamine SiH3 3 N
?
Sol.

H3 Si

sp3
N sp2 N SiH3
CH3 CH3

CH3 H3 Si

Due availability of vacant d-orbitals in Si,

back bond is formed between Si and N
 11C11.3

CV 4

Properties of Group 14 Elements-II

 Reaction with Oxygen
EO Monoxide
E + O2
EO2 Dioxide

EO: CO SiO GeO SnO PbO

Neutral Acidic Amphoteric

EO2 : CO2 SiO2 GeO2 SnO2 PbO2

Acidic Amphoteric
 Reaction with Halogens
EX2 Dihalide (Except C)
E + X2
EX4 Tetrahalide
(Except PbBr4 & PbI4 )
• EX4 are covalent in nature except SnF4and PbF4 . X
• The thermal stability of tetrahalide decreases down
sp3
the group:
E
CX4 > SiX4 > GeX4 > SnX4 > PbX4 X X
CF4 > CCl4 > CBr4 > CI4 X
• Stability of dihalide increases down the group: Tetrahedral
SiX2 < GeX 2 < SnX2 < PbX2
 Hydrolysis of Halides
• Except Carbon halides, other halides are easily hydrolysed.

Cl
O Cl
H OH
H
Si
Cl Cl Si Si
Cl OH OH OH
Cl
OH OH

Silicic Acid
 Reaction with Water
• C, Si and Ge are unaffected by cold water.
• On red heating, these elements except lead decompose steam.
C + H2 O → CO + H2
Si + 2 H2 O → SiO2 + 2 H2
Sn + 2 H2 O → SnO2 + 2 H2
• Lead is unaffected by water because of the formation of protective
oxide layer.
Q. In SiF62− and SiCl2−
6 which one is known and why?

(a) SiF62− because of small size of F

(b) SiF62− because of large size of F
More
(c) SiCl2−
6 because of small size of Cl repulsion
between
(d) SiCl2−
6 because of large size of Cl surrounding Cl
atoms
Sol. F Cl
F F Cl Cl
Due small size of F atoms
Si there are less repulsion Si
between surrounding F
F F atoms Cl Cl
More stable molecule Cl
F

Hence the correct option is a) SiF62− because of small size of F

 Anomalous Behaviour of Boron
• Small Size
• High Electronegativity
• Absence of d-orbital

Some dissimilarities with rest

members of the group
 Catenation
• Tendency to link with one another through covalent bonds to form
chains and rings.

C C C C

• Down the group the size increases and electronegativity decreases

hence, tendency to show catenation decreases.
C > Si > Ge > Sn
• Lead does not show catenation.
 Formation of 𝛑 − Bonds
• Form pπ– pπ multiple bonds with itself and with other atoms of small
size and high electronegativity.
π bond

H H
2 σ(sp2 − sp2 )
sp sp2
C sp2 sp2 C
2
sp sp2
H H
π bond

• Heavier elements do not form pπ– pπ bonds because their atomic

orbitals are too large and diffuse.
 Anomalous Behaviour of Carbon
• CO2 is gas while other dioxides are solids.
• Monoxide of carbon is quite stable and neutral.
• Maximum covalency of carbon is 4.
• CCl4 does not undergo hydrolysis.
Q. Bond energy is highest for:
a Sn − Sn
b C−C
c Si − Si
d Ge − Ge

Sol. Due to smaller bond length of C − C bond the bond energy is

higher.

Correct option is b) C − C.
Summary

• Trend in Atomic Size : C < Si < Ge < Sn < Pb

• Trend in Ionisation Enthalpy : Sn < Pb < Ge < Si < C
• Trend in Electronegativity : Sn~ Ge ~ Si < Pb < C
• Nature of oxides :
EO: CO SiO GeO SnO PbO

Neutral Acidic Amphoteric

EO2 : CO2 SiO2 GeO2 SnO2 PbO2

Acidic Amphoteric
Summary

EO + EO2
EX 2 + EX 4 EO + EO2 + H2
Air O2

Group 14 (E)

HCl
ESO4 + H2 Na2 EO3 + H2
ECl2 + H2
Except C & Si Except C
Except C & Si
 Allotropes of Carbon

Graphite Diamond Fullerenes

 Graphite

• sp2 and 2-D layered structure.

• Weak vander waal forces between two layers.
• Soft, dark greyish crystalline structure.
• Good conductor of Heat and Electricity.
335 pm
• Density 2.5 g/ml.
• Thermodynamically most stable form of carbon.

142 pm
 Diamond

• sp3 and 3-D structure.

• Hardest naturally known substance.
• Bad conductor of Electricity.
• Highly inert.
• Used as an abrasive for sharpening hard tools
 Fullerenes
• sp2 and football like structure.
• Made by the heating of graphite in an electric
arc in the presence of inert gases.
• Purest form of carbon.
• C-60 is named as Buckminster Fullerene.
• It contains 20 six- membered rings and 12
five-membered rings.
• The remaining electron at each carbon is delocalised in molecular
orbitals, which in turn give aromatic character to molecule.
 Coal
• Crude form of carbon.

Peat Lignite Bituminous Anthracite

55-60% 60-68% 70-88% 90-95%

• In India, the common variety of coal is Bituminous.

 Carbon Monoxide
• Formed when C is oxidised in limited supply of oxygen:
2 C g + O2 g → 2 CO g
• Pure CO is prepared by dehydration of formic acid with concentrated
H2 SO4 at 373 K:
H2 SO4 −Δ
HCOOH CO + H2 O
• On commercial scale it is prepared by the passage of steam over hot
coke:
C s + H2 O g → CO g + H2 g

Water Gas or Synthesis Gas

 Properties of Carbon Monoxide
• Colourless, odourless and almost water insoluble gas.
• It is a powerful reducing agent and reduces almost all metal oxides:
Fe2 O3 + 3 CO → 2 Fe + 3 CO2
ZnO + CO → Zn + CO2
• CO molecule reacts with certain metals when heated to form metal
carbonyls, Example: Ni CO 4

C O

• Highly poisonous nature.

 Carbon Dioxide
• Prepared by complete combustion of carbon and carbon containing
fuels in excess of air:
C + O2 → CO2
y y
Cx Hy + x + O2 → x CO2 + H2 O
4 2
• In the laboratory it is prepared by the action of dilute HCl on CaCO3 :
CaCO3 + 2 HCl → CaCl2 + H2 O + CO2
• On commercial scale it is obtained by heating limestone:
Δ
CaCO3 CaO + CO2
 Properties of Carbon Dioxide
• Colourless and odourless gas.
• Less soluble in water.
• With water, it forms carbonic acid, H2 CO3 :
H2 CO3 ⇌ HCO−
3 +H
+

HCO− 2−
3 ⇌ CO3 + H
+

• H2 CO3 /HCO–3 buffer system helps to maintain pH of blood between 7.26

to 7.42.
• It combines with alkalies to form metal carbonates:
Ca OH 2 + CO2 → CaCO3 ↓ +H2 O
Milky white ppt.
 Properties of Carbon Dioxide
• Photosynthesis:
Chlorophyll−hν
6 CO2 + 12 H2 O C6 H12 O6 + 6 O2 + 6 H2 O
• Increment in the CO2 content of the atmosphere
leads to increase in green house effect.
• Resonating Structures of CO2 :

O C O O C+ O− O− C+ O
11C11.4

PSV 1
Q. What is producer gas?

Sol.

When carbon is heated with air, a mixture of CO and N2 is produced:

2 C s + O2 g + N2 g → 2 CO g + N2 g

Producer Gas

• Used primarily as an industrial fuel for iron and steel manufacturing.

Q. If CO2 is passed in excess into lime water, the milkiness first formed
disappears due to:
a) reversal of the original reaction
b) formation of volatile calcium derivative
c) the solution getting heated by exothermic reaction
d) formation of water soluble calcium bicarbonate
Sol. Ca OH 2 + CO2 → CaCO3 ↓ +H2 O
Milky white ppt.

CaCO3 + CO2 + H2 O → Ca HCO3 2

Water Soluble
Hence the correct option is d) formation of water soluble calcium
bicarbonate.
 11C11.4

CV 3

Silica and Silicones

 Silica
• Silicon dioxide, commonly known as silica.
• SiO2 is a covalent, three-dimensional network solid.

• Occurs in several crystallographic forms:

Quartz Cristobalite Tridymite

 Silica
• Silica is almost nonreactive due to very high Si—O bond enthalpy.
SiO2 + 2 NaOH → Na2 SiO3 + H2 O
SiO2 + 4 HF → SiF4 + 2 H2 O
• Quartz is extensively used as a piezoelectric material.

Produces internal charge under high mechanical stress

• Silica gel is used as a drying agent.

• SiO2 is acidic in nature and used as flux in metallurgy.
 Silicones
• Organosilicon polymers.
• − R 2 SiO − is the repeating unit.

Cu powder + 2 H2 O
2 R − Cl + Si R 2 SiCl2 R 2 Si OH 2
570 K − 2 HCl
Dialkyldichlorosilane Dialkylsilandiol

R R R R
− −
− −

Polymerisation

− −

− −
HO − Si − OH HO − Si − OH −O − Si − O − Si − O −
R R R R
n
Silicone

• The chain length of the polymer can be controlled by adding CH3 3 SiCl.
 Silicones
R R
• Water repelling in nature.

− −
− −
−O − Si − O − Si − O −
• High thermal stability.
R R
• Resistant to oxidation and chemical reagents. n

• Used as sealant, greases, electrical insulators and for water proofing of

fabrics.
• Due to biocompatibility it is used in surgical and cosmetic implants.
Q. When Silica is treated with sodium carbonate, then which of the
following gas is liberated ?

a) CO c) CO2
b) O2 d) O3

Sol. Silica is acidic in nature.

SiO2 + Na2 CO3 → Na2 SiO3 + CO2 ↑
Hence the correct option is c) CO2 .
 ConcepTest
Ready for Challenge
Q. Which of the following is correct?
a) Silicones are organosilicon polymers containing Si − O − Si linkage.
b) R 3 SiCl on hydrolysis gives R 3 Si − O − SiR 3
c) Both a & b
d) None

Sol. R 3 SiCl + H2 O → R 3 SiOH + HCl

Correct option is a) Silicones are organosilicon polymers containing

Si − O − Si linkage.
 11C11.4

CV 4

Silicates and Zeolites

 Silicates
• Formed by heating metal oxide or metal carbonates with sand.
Fused with sand
Na2 CO3 Na4 SiO4 + Na2 SiO3 n ⋯
• Basic structural unit of silicates is SiO4−
4 .

Orthosilicate

Examples:

Zircon: ZrSiO4 Olivine: Mg 2 SiO4 Phenacite: Be2 SiO4

 Silicates
Pyrosilicate: Two units of SiO4−
4 joined along a corner

Si2 O6−
7

Examples:

Thortveitite: Sc2 Si2 O7 Hemimorphite: Zn3 Si2 O7 Zn OH 2 . H2 O

 Silicates
Cyclic or Ring Silicates:
SiO2−
3 n or SiO3 2n−
n

Examples:

Benitoite: BaTiSi3 O9 Beryl: Be3 Al2 Si6 O18

 Silicates
Chain Silicates:

2n− 6n−
SiO3 n Si4 O11 n

Examples:

Jadeite: NaAl SiO3 2 Tremolite: Ca2 Mg 5 Si4 O11 2 OH 2

 Silicates
Two Dimensional Sheet Silicates:
Si2 O5 2n−
n

Examples:

Talc: Mg Si2 O5 2 Mg OH 2 Kaolin: Al2 OH 4 Si2 O5

 Silicates
Three Dimensional Silicates:

All 4 O-atoms are involved in sharing with adjacent SiO4−

4 tetrahedra

Examples: Quartz, Tridymite, Fledspars, Zeolites

 Zeolites
• Zeolites are 3-D Aluminosilicates.
• Al-atoms replace Si-atoms in Silica structure.
• Acquires negative charge.

• Shape selective catalyst.

• ZSM-5 (A type of zeolite) widely used as a catalyst in petrochemical
industries for cracking of hydrocarbons and isomerisation.
• Zeolites are used as ion exchangers in softening of “hard” water :
2 NaZ + Ca2+ → CaZ + 2 Na+
Summary
Allotropes of Carbon

Graphite Diamond Fullerenes

• SiO2 is a covalent, three-dimensional network solid.

• Silicones are organosilicon polymers.

R R
− −

− −
−O − Si − O − Si − O −
R R
n
 Summary
Silicates

Orthosilicates Pyrosilicates Chain Silicates

Cyclic Silicates

2-D Sheet Silicates

• Zeolites are 3-D Aluminosilicates