NOTE

C H E M I S T R Y

p-BLOCK ELEMENTS
REVEALING SECRETS OF SILICATES

What you already know

• Preparation, properties, structures of oxides of carbon • CO-haemoglobin complex

• Synthesis gas and Producer gas • Silicon dioxide (Silica)
• Uses of CO2 • Structure and uses of SiO2

What you will learn

• Silicates • Preparation, properties and uses

• Classifications of silicates of silicones
• Silane, chlorosilane • Structure and uses of zeolites

Silicates

• Binary compounds of silicon with oxygen are called silicates, but O–

they also contain other metals in their structures.
• The electronegativity difference between O & Si is about 1.7. Si O–
Therefore, Si–O bond can be considered 50% ionic & 50%
covalent.
–
O
• The basic structural unit of silicates is SiO44– in which the silicon O–
atoms are bonded to four oxygen atoms in a tetrahedron fashion. Tetrahedral structure
of SiO44– anion
Classification of silicates

Ortho-
silicates
3D Sheet Pyro-
silicates silicates

2D Sheet Cyclic
silicates silicates
Chain
silicates

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–
– –
Si –
Ortho-silicates: They contain discrete SiO44– units, i.e. there is no – –
sharing of oxygen atom with one another. –
In given structure, the circles represent oxygen atoms and the dot –
represents the silicon atom.
Side view Top view
= Oxygen atom
= Silicon atom
Representation of ortho-silicates
– – –

–
Pyro-silicates: In pyro-silicates, two Si Si –
tetrahedral units are joined by sharing one – – –
–
oxygen atom between them. The general
formula for pyro-silicates is Si2O76–. – –
–
Representation of pyro-silicates

In case of pyro-silicates, negative charge will be present on the oxygen atoms which are
bonded to only one Si-atom.

Cyclic-silicates: In cyclic-silicates, two oxygen atoms per tetrahedron are shared to form closed
rings. The general formula of cyclic-silicates is (SiO32–)nor (SiO3)n2n–.
–

–
– – –
– –
–

– – – –
– – –
–
–

–
Si3O96– Si6O1812–
Representation of cyclic-silicates

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Chain-silicates

Simple chain Double chain

silicates silicates

– –
– –
Simple chain-silicates: Here, two
corners of each tetrahedron are shared
– – –
& they form a long chain of tetrahedron.
Its general formula is (SiO3)n2n–. – – –

Representation of simple chain silicates

– –
– –
Double chain silicates: In double chain – – –
silicates, two simple chains are joined
together by a shared oxygen. It is also – – –
known as amphiboles. Its general
– –
formula is (Si4O11)n6n–.
– –

Representation of double chain silicates

– –
– – –

2D-Sheet silicates: In these – – –

silicates, three oxygen atoms of each – – – –
tetrahedron are shared with the
adjacent SiO44– tetrahedrons. Its
general formula is (Si2O5)n2n–. – – – –
– – –

Representation of 2D-Sheet silicates

3D-Sheet silicates: These silicates involve all four oxygen atoms shared with the adjacent SiO44–
tetrahedral units.
Examples : Quartz, tridymite, cristobalite, feldspar, zeolite.

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Silanes

Silanes are silicon and hydrogen compounds i.e. hydrides of silicon. They refer to many
compounds with four substituents on silicon.

Si
H H
H

Silane(SiH4)

CI CI CI
H

Si Si Si Si
H H H CI CI CI CI
H CI H
CI CI

Monochlorosilane Dichlorosilane Trichlorosilane Tetrachlorosilane

Silicones

Silicones are synthetic organosilicon compounds having repeated R2SiO units held by Si–O–Si
linkages. Its general formula is (R2SiO)n, where R = alkyl or aryl group.
R R R

O Si O Si O Si O

R R R
Fig. 6: Representation of silicones
Preparation of silicones

Silicones can be prepared from the

following type of compounds only

R3SiCI R2SiCI2 RSiCI3

Silicones are formed by the hydrolysis of alkyl or aryl substituted chlorosilanes and their
subsequent polymerisation. When CH3Cl reacts with Si in the presence of Cu as the catalyst at
573 K, various types of methyl substituted chlorosilanes of formula MeSiCl3, Me2SiCl2, Me3SiCl and
small amount of Me4Si are formed.

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Cu
MeCl + Si
MeSiCl3 + Me2SiCl2 + Me3SiCl + traces of Me4Si
300 °C
Hydrolysis of (CH3)2SiCl2 followed by condensation polymerisation yields straight chain polymers.
CH3
Cu powder
2CH3 CI + Si CI Si CI
570 K

CH3

CH3 CH3
+2H2O
CI Si CI HO Si OH
–2HCI

CH3 CH3
CH3 CH3 CH3
Polymerisation
HO Si OH + HO Si OH + HO Si OH
–H2O
CH3 CH3 CH3
CH3 CH3

O Si O Si

CH3 CH3
n
Silicone
The chain length of the polymer can be controlled by adding (CH3)3SiCl which blocks the ends.

CH3 CH3 CH3 CH3

Polymerisation
n HO Si OH + HO Si CH3 O Si O Si CH3
–H2O
CH3 CH3 CH3 n CH3
Silicone
Properties of silicones
1. Silicones being surrounded by non-polar alkyl groups are water repelling in nature.
2. Generally, they have high thermal stability.
3. They have good electrical insulation (high dielectric strength).
4. They are chemically inert (resistant to oxidation and a high number of chemicals).

Uses of silicones
1. They are used as sealant, greases, electrical insulators and for water proofing of fabrics.
2. They are biocompatible and are also used in surgical and cosmetic implants.
3 Products with the same physical properties of oils, rubbers and resins can be produced
using s ilicones.

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Zeolites

• Zeolites are microporous, aluminosilicate minerals that are commonly used as commercial
adsorbent and catalysts.
• Zeolites are widely used as a catalyst in petrochemical industries for cracking of hydrocarbons
and isomerisation. Hydrated zeolites are used as ion exchangers in softening hard water.
• If Al-atoms replace a few Si-atoms in the 3D-network of SiO2, the overall structure is known as
aluminosilicate, and acquires a negative charge. Cations such as Na+, K+ or Ca2+ balance the
negative charge.
• ZSM-5 (A type of zeolite) is used to convert alcohol directly into gasoline.

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