Group IVA

Silicon (Si)
Group IVA
Introduction
Introduction

Introduction
• The 2nd most abundant element in the earth
• as SiO2 (sand, quartz, flint and agate)

• as silicate substances
 Group IVA
Extraction
Extraction

Extraction
1. Reducing SiO2 (sand) by Coke 
- Electrical furnace
  SiO2(s) + C(s)  Si(s) + 2CO
 
In the process, excess silica is used to prevent the
formation of SiC (silicon carbide)

The reaction:
SiO2 + 2C  SiC + 2CO
2SiC + SiO2  3Si + 2CO
 
 Group IVA
Extraction
Extraction

2. To obtain pure Si
(i) Reducing SiCl4 by Na
SiCl4(l) + 4Na(s)  Si(s) + 4NaCl
  Other metal halides formed are removed by
washing with HCl.
 
(ii)Zone refining process; (99.999% pure)
The Si obtained from (i) is refined by
heating the rod from one end and
slowly moved to the other end. The
impurities will move simultaneously
with the heating. The end that contains
the impurities is cut off
 Group IVA
Properties
Properties

Characteristics
 
• Crystalline Si has metallic luster and grayish
color.
• Having diamond lattice
• High melting point (1414oC)
• Inert elements but attack by halogen
• Does not dissolve in any acids (except HF)
Si(s) + 6HF(l)  H2SiF6(aq) + 2H2(g)

• Dissolve in base
Si(s) + 2OH(aq) + H2O  SiO32(aq) + H2(g)
 Group IVA
Cpds
Cpds--Oxides
Oxides

Compounds of Silicon
Oxides
Oxides
• Silicon dioxide, SiO2
- Exists as polymeric tetrahedral SiO2
½
O

Si ½  (SiO2)x
O O
OOx No.: Si = +4, O= 2 
• Si – O, 50% ionic due to the difference in the
electronegativity Si(1.8) and O(3.5)
• As a whole the molecule is a covalent
macromolecule with the formation
of polymorph.
 Group IVA
Cpds
Cpds--Oxides
Oxides
Example of polymorph of SiO2 crystals

-quartz -tridymite -cristobalite

840 K 390 470
-430 K -550 K
1140 K 1740 K
β-quartz -tridymite -cristobalite

1990 K
1070-1270 K
Liquid Silica
Amorphous silica
Slow cooling

Glass silica
Group IVA
Cpds
Cpds--Oxides
Oxides

QUARTZ
 The most stable tetrahedral polymorph

 -Quartz is an optic active polymorph

due to the formation of a spiral helical
chain of -Si-O-Si-O-which run
throughout the crystal. As the chain
may be right or left handed the 2 forms
obtained will be non-superimpose
 Colorless quartz called rock crystal, cut
both IR and UV radiation.

Use for making optical lenses and

prisms, gemstones(citrine, amethyst

Cristobalite & tridymite have diamond lattice of Si

atoms with O atoms midway between 2 Si atoms
Group IVA
Cpds
Cpds--Oxides
Oxides

Preparation of SiO2
1. Hydrolysis of SiCl4
SiCl4 + 4H2O  4HCl + H4SiO4
1270K
H4SiO4 SiO2

2. Acidification of water glass

Na2SiO3 + 2HCl  2NaCl + H2SiO3
1270K
H2SiO3 SiO2

Physical properties:
• Inert at low temperature but becomes reactive at
elevated temperature
• Becomes strong acidic oxide at elevated temp.
Group IVA
Cpds
Cpds--Oxides
Oxides

Cont. Properties
• Dissolve in HF only
SiO2(s) + 6HF(aq)  H2SiF6(aq) + 2H2O(l)
• Dissolve in alkali
SiO2(s) + Na2CO3(aq)  Na2SiO3(aq) + CO2
Water glass
SiO2(s) + 2NaOH(aq)  Na2SiO3(aq) + H2O(l)

Silicon tetrachloride SiCl4 fumed in wet air, forming a white solid.

The solid can only be dissolved in HF(aq) and NaOH(aq). Identify
the white solid and write the equation of the reactions of SiCl4 in
wet air and the dissolution of the white solid in HF(aq) and
NaOH(aq).
 Group IVA
Cpds
Cpds--Oxides
Oxides

• Silicate, (SiO4)4-
- SiO2 + metal oxides / metal sulphate / metal carbonate
e.g.:
Sodium silicate , Na2SiO3 
SiO2 + Na2CO3  Na2SiO3 + CO2

- Structure: polymorph (SiO4)4 - contains tetrahedral SiO4

join through Si-O-Si bonds.

½
O

Si ½ 
O O
O Si in the centre linked to 4
Tetrahedral SiO4 O atoms covalently
Group IVA
Cpds
Cpds--Oxides
Oxides
• Type of silica and silicates
No of O
Type Unit being Structure Example
shared
Be2SiO4, fenacite
O-
Zn2SiO4, willemite
Si
Ortho SiO44- 0 -O ZrSiO4, zircon
-O O-
(M2+)2SiO4, olivin
M2+=Mg2+, Fe2+, Mn2+

-O O-
- O Si
Si2O Si O- Sc2Si2O7, tortveitite
6-
Pyro 7 1 O
-O O-

-O O-
Si3O 6- 2 -O Si
O
Si O-
BaTiSi3O9, benitoite
9
O
Si
O
Al2Be3Si6O18, beryl
-O O-
Cyclic 2
Si6O1812-
Group IVA
Cpds
Cpds--Oxides
Oxides

No of O
Type Unit being Structure Example
shared
Chain MgSiO3, enstatite
-O O- -O
- single SiO32- O-
LiAl(SiO3)2, spodumen
2 O
Si
O O
Si
O O
Si
-O
Si CsAl(SiO3)2, pollucite
-O O- O-

- double Ca2(OH)5Mg5[Si4O11]2
Si4O116- 2 or 3 tremolin
Na2(OH)2Fe5[SiO11]2,
crocidolite

Mg3(OH)2[Si2O5], talc
Layer Si2O52- (soap rock)
3
LiAl[Si2O5], petalite

3- -quartz
dimension SiO2 4
Cristobalite
Group IVA
Cpds
Cpds--Oxides
Oxides
• Samples of the silicate minerals
Emerald, a green beryl (Be3Al2Si6O18)
with about 2% Cr3+ions substituting for
Al3+,-cyclic anion Si6O1812 type
silicate

Diopside (CaMgSi2O6) –
infinitely extended chain anion Si2O64
type silicate

Asbestos is a fibrous material

because of its chain structure- double-
stranded chain anion (Si4O116)n type
silicate

Mica cleaves into thin sheets because

of its two-dimensional layer structure.
The layer anion (Si4O104)n in mica is
formed by the sharing of three O
atoms per SiO4 tetrahedron
Group IVA
Cpds
Cpds--Oxides
Oxides

• Aluminosilicate
Aluminosilicate : 3-dimensional silicate
• Occurs when Al atom substitutes Si in the
silicate framework
• Framework becomes negatively charge
[(SiO4)n(AlO4)m]m
[(+4)+4(-1)]+[(+3)+4(-1)] = -1
• Excess charges are balanced by cations from
Group IA and IIA or from Transition Metals (Na+,
K+, Ca2+, Mg2+ , Fe3+ , etc)
 
 Group IVA
Cpds
Cpds--Oxides
Oxides

 Examples: 
1. Feldspar : KAlSi3O8 , ortoclas
NaAlSi3O8 , albite

2. Zeolite : Hydrated aluminosilicate crystals having open structure

framework which contains cages, channels and pores of regular
dimensions

Formula :
M n/y[(SiO2)x(AlO2)y].zH2O
[ ] = aluminosilicate framework
M = cations balancing aluminosilicate framework
z = No. of H2O molecule occupying the pores, channels and cages
Group IVA
Cpds
Cpds--Oxides
Oxides

• Zeolite Characteristics
- Regular size of pores and channels
- (4 – 12 Å in molecular ranges size) : molecular
sieves to separate molecules of different sizes
- Cation balancing framework zeolite can be
exchangeable; ion exchanger
- If the cation is exchanged with H+, the zeolite
becomes strong acidic solid catalyst : acidic
heterogeneous catalysts in many organic
reactions
Group IVA
Cpds
Cpds--Oxides
Oxides

• Sodalite Framework

 cages-
Pore
aperture
(4668)- 2.8 Å
Secondary building unit

Joint by four member ring of SBU

Group IVA
Cpds
Cpds--Oxides
Oxides

Type of Zeolite Function Uses

A, X, Y,
Clinoptilolite, Ion Exchanger Water softener in detergent
Mordenite

Separation of Gases in
industrial process, gas
Molecular Sieves chromatography, drying
A, X, Carbazite
and adsorbent agents

HC cracking, isomerization,
alkylation,
Heterogeneous
Y, ZSM-5, Beta Friedel Crafts acylation etc.
Catalysts
Group IVA
Cpds
Cpds--Oxides
Oxides

Zeolite A (LTA)

ZSM-5 (MFI) Zeolite A (LTA) Zeolite Y (FAU)

Group IVA
Cpds
Cpds--Oxides
Oxides

• Silicate Glass

Metal silicate
Sand + Alumminosilicate silicate glass
Borosilicate
 

Characteristics of Glass
- Not a true solid
- is a supercooled liquid having very high viscosity that

free flow of the liquid is not possible

- Has no melting point - amorphous
- On heating  soften  turn semisolid  clear liquid.
- Inert by most chemicals but attacked by F2, HF and
Group IVA
Cpds
Cpds--Oxides
Oxides

Production
- Soda glass is a mixture of calcium silicate (CaSiO3)
and sodium silicate (Na2SiO3)
CaCO3 + Na2CO3 + sand  soda glass
SiO2 + CaCO3  CaSiO3 + CO2
SiO2 + Na2CO3  Na2SiO3 + CO2

- Coloring glass
Fe3+ yellow glass Co2+ - blue
Fe2+ green Cu+ - red
Cr3+ green bottle Cu2+ - peacock blue
Mn2+ violet
 Group IVA
Cpds
Cpds--Oxides
Oxides

Types of Glasses
• Soft glass : Ordinary soda-lime, easily fusible glass which
is used for making bottles and window glasses.

• Hard glass : Potash-lime glass, used for glass apparatus,

is resistant to chemicals and melts with difficulty.

• Flint glass : Lead-potash-lime glass with high refractivity,

used for making prisms, lenses and optical devices.

• Jena glass : Zinc-barium-borosilicate glass, low thermal

expansion, used for heat shock resistant apparatus.

• Pyrex or Corning glass : Sodium-aluminium-borosilicates,

similar to Jena glass.
 Group IVA
Cpds
Cpds--Oxides
Oxides

• Crooke’s glass : Cuts off uv rays. The whole of CaO is

replaced by PbO, BaO, ZnO and MgO.

• Quartz glass : Pure silica does not crack even if the red
hot vessel is plunged straight into water.

• Ground glass : is soft glass, the surface of which has

been grounded by emery and turpentine.

• Reinforced glass : has a net work of wires embedded in it

and does not shatter easily. Safety or shatter proof glass is
obtained by joining two or more layers of glass with a
transparent adhesive layer and then cementing them under
pressure
Group IVA
Cpds
Cpds--Oxides
Oxides
Past year:

Type : Double chain silicate

Oxygen : 4
Si in the centre linked to 4
Example : asbestos O atoms covalently
Group IVA
Cpds
Cpds--Silicones
Silicones

Silicones
Silicones
• Silicones are organosilicon compounds having
heterocatenated Si-O-Si-O bonds in chains, rings and
branches.
• The chain consists of Si-O-Si-O with alkyl/aryl (R)
group bonded to Si atom 

Past year:
What is silicones?
 Group IVA
Cpds
Cpds--Silicones
Silicones
• Preparation:
  Hydrolysis of alkyl/aryl silicon halides (e.g. R3SiX,
R2SiX2, RSiX3) followed by condensation

Types of Silicones
• Type of silicones polymer depends on the type of initial
aryl/alkyl silicon halide
 1. Disilicone - Initial R3SiX
- hydrolysis
R3SiX + H2O  R3SiOH + HX

- condensation
R3SiO-H + HO-SiR3  R3Si – O – SiR3 + H2O
disilicone
Group IVA
Cpds
Cpds--Silicones
Silicones

2. Chain silicone - initial R2SiX2

- Hydrolysis:
R2SiX2 + 2H2O  R2Si(OH)2 + 2HX

- Condensation: R R

HO Si OH + HO Si OH
R R
Past year:
H2O
Write the mechanism
to obtain the R R R R
polymer type
chain silicone? HO Si O Si O Si O Si O-
R R R R
 Group IVA
Cpds
Cpds--Silicones
Silicones
R R

3. Branched silicone HO Si OH + HO Si OH
– initial RSiX3 O O
H H
H H
- Hydrolysis
O O
RSiX3 + H2O
HO Si OH HO Si OH
 RSi(OH)3 + 3HX
R R
 
- Condensation nH2O
R R R R

HO Si O Si O Si O Si O-
O O O O

HO Si O Si O Si O Si O-
R R R R
Group IVA
Cpds
Cpds--Silicones
Silicones

Propreties of Silicone
• Thermally stable up to 500 – 600 K
• has low viscosity which changes with temperature.
• Silicone rubbers remain elastic even at low temperatures.
• The presence of alkyl groups makes the silicones water repellent
(hydrophobic).
• Inert towards chemical attack or oxidation
Uses of Silicone
• As lubricants (linear chain-polydimethyl-silixane, PDMS),
• Low temperature hydraulic fluids (linear chain PDMS)
• In cosmetics
• Breast implant shell (cross-linked PDMS)
• Silicone wax put on the surface of the car for water
repellent.
 Group IVA
Cpds
Cpds--Halides
Halides

Silicon
Silicon Halides,
Halides, SiX
SiX44
•  All SiX4 (X= F, Cl, Br, I) exist
• With Cl, a series of chloride SinCl(n+2) up to Si6Cl14 are known
• All halides (except SiF4) are unstable and undergone
hydrolysis in water
SiX4 + 2H2O(l)  SiO2(s) + 4HX(aq)
X = Cl, Br, I
 
With SiF4 undergone partially hydrolysis
2SiF4 + 2H2O  SiO2(s) + H2SiF6(aq) + 2HF(aq)
 Group IVA
Cpds
Cpds--Halides
Halides

Hydrolysis occurs through the formation of dative bonding

from O atom of water to the Si of SiX4

X X X X
H - HX
Si O Si
X X H X O-H
- HX

H
X
O - 2HX
Si H O Si O
X O
Group IVA
Cpds
Cpds--Hydrides
Hydrides

Silicon
Silicon Hydride,
Hydride, SiH
SiHxx
• Also known as Silanes
• Form catenation, SiH4, Si2H6, Si3H8, …up to Si6H14
(similar to hydride of C, hydrocarbon)
 
Preparation
•  Stock’s reaction
Mg2Si(s) + H+(aq)  Mg2+(aq) + SiH4(g) +
H3Si-SiH3 + etc
The silanes are separated by fractional distillation

• SiCl4(l) + LiAlH4  SiH4(g) + LiCl(s) + AlCl3(l)

 Group IVA
Cpds
Cpds--Hydrides
Hydrides

Propreties

• Exist in the form of gas and volatile liquid

• Burn in air spontaneously
• Hydrolysis in water and alkali
SiH4(g) + 2H2O  H4Si(OH2)2  SiO2 + 4H2O
SiH4 + 2OH + H2O  SiO32(aq) + 4H2O
  Hydrolysis is spontaneous due to high Si-O bond
energy. It proceeds through the formation of 6-coordinate
intermediate SiH4.2H2O in which silicon uses the 3d
orbitals to accommodate the electron pairs from water
molecules