PRE – U CHEMISTRY

SEMESTER 2
CHAPTER 5 :
GROUP 14 & COMPOUNDS
 Physical properties of group 14 elements
Element Carbon Silicon Germanium Tin Lead
Classification Non–metal Metalloid Metal
Valence electron 2s²2p² 3s²3p² 4s²4p² 5s²5p² 6s²6p²
Atomic
0.77 1.17 1.22 1.48 1.55
radius(nm)
Melting point(°C) 3700 1410 936 232 328

Boiling Point(°C) 4620 2680 2820 2270 1730

First ionisation
1085 788 760 705 714
energy(kJ mol⁻¹)
Non-
Conductivity (Heat) Conductor
Diamond (X) conductor Good conductor of
Conductivity Graphite (√ ) heat and electricity
Semiconductor
(Electrical)
Stability of oxidation Stability of +4 oxidation state decrease
states Stability of +2 oxidation state increase
Introduction
• Group 14 is the only group which contain all 3 major classification of
elements: metal, metalloid and non metal
• The variation of Group 14 is based on the characteristic of each elements
Atomic radius
• Atomic radius increase when goes down to Group 14.
• When the number of electrons increases, the number of shell required to
fill in the electrons increase.
• This will increase the screening effect of the atom causing the effective
nuclear charge decrease.
• As the attraction forces between the outermost electron and the nucleus
decrease, atomic radius become larger.
3.1.2 Melting point

• As the metallic properties of Group 14 elements are different, it has

different molecular structure.
• Carbon, silicon and germanium have gigantic molecular structure. The
melting point decrease when goes down to from carbon to germanium.
This is due to bonding length of C – C ; Si – Si ; and Ge – Ge
• become longer, so the covalent bond become weaker as the length increase.
• As for tin (Stanum) and lead (Plumbum), they have strong metallic bond.
Lead has lower melting point than tin, as the arrangement of the metallic
atom of lead are more closely packed (faced centered cubic) than tin
(tetragonal structure) in solid lattice. The close packing of increase the
strength of the metallic bond in lead.
3.1.3 Ionisation energy
• Generally the 1st ionisation energy decrease when going down to Group
14.
• This is due to the increase of atomic size as the number of electron shells
filling in increased. When this happened, it will gradually increase the
screening effect thus decrease the effective nuclear charge of the atom.
When this occur, electron is easier to extract out from the atom.
• However the 1st ionisation energy of tin is lower than lead despite that
the atomic radius of Pb is larger than Sn. The electronic configuration of
Sn and Pb are as follow:
– Sn : 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p2
– Pb : 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p2 4f14 5d10 6s2 6p2
• This is due to the ineffective screening by 4f electrons in lead atom.
The nuclear charge of lead is far greater than tin. So, the effective nuclear
charge of lead will be slightly higher than tin, causing the ionisation
energy of lead is higher than tin.
3.1.4 Electrical conductivity
• Since carbon is a non metal, there’s no conductivity of carbon
(diamond) that occur on carbon. If the allotrope of carbon is graphite,
it can conduct electricity as it has one delocalised electron on carbon
(sp2 hybridisation).
• As for silicon and germanium, both of them are semiconductor as
they are metalloid. The conductivity of semiconductor can be
increase by increasing the temperature, or silicon doped with
germanium.
• As for tin and lead, since both of them are metal, they can delocalise
electron thus conducting electricity. The electrical conductivity
increase from tin to lead as the electron delocalised by lead is easier
than tin.
3.2 Chemical Properties of Group 14
3.2.1 Stability of +2 and +4 oxidation state of Group 14
• Group 14 elements can exhibit 2 oxidation states, which is +2 and +4
• The valence electron of Group 14 elements are
____ ____ ____ ____
ns2 np2
• Even though the number of valence electron of Group 14 is 4, but it will
never form M4+ ions due to its very high successive ionisation energy to
remove 4 electrons.
• Still, the +4 oxidation state involve the involvement in the 1 s and 3 p
orbital. Whenever the energy is absorbed

____ ____ ____ ____ ____ ____ ____ ____

ns2 np2 s p3
• This can be done at lower energy level as the gaps between the s and p is
not far. When goes down to Group 14, the stability of +4 decrease due to
the far level between the s and p orbital. For example, in lead, the 6s and 6p
is separated by large d10 and f14 orbital. This effect is called as inert pair
effect. This will cause +2 oxidation states to be more stable as the 2
electron is p orbital are easier to be removed.
• The graph below shows the relative stability of +2 and +4 oxidation state in
Group 14

C Si Ge Sn Pb
• From the graph, we can conclude that +4 more stable than +2 for carbon,
silicon, germanium and tin while +2 more stable than +4 for lead
• From the angle of electrochemistry, the standard reduction potential, E0red,
of +4 to +2 oxidation state of Group 14 elements is shown below
– Ge4+ (aq) + 2 e-
Ge2+ (aq) E0red = – 1.60 V
– Sn4+ (aq) + 2 e-
Sn2+ (aq) E0red = + 0.15 V
– Pb4+ (aq) + 2 e-
Pb2+ (aq) E0red = + 1.69 V
• As the E0red value become more positive, it mean from Ge2+ to Pb2+, the
stability increase, Sn2+ and Pb2+ are preferably to stay as +2 oxidation state.
Therefore, Pb4+ is a strong oxidising agent while Ge4+ is a strong reducing
agent.
• Pb4+ (aq) + 2 e-
Pb2+ (aq) (preferably to reduce) (oxidising agent)
• Ge2+ (aq)
Ge4+ (aq) + 2 e- (preferably to oxidise) (reducing agent)
• All Group 14 elements (except carbon) can make use of their empty
d-orbitals to form complex ions.
• Example : SiF62- ; GeCl62- ; SnCl62- ; PbCl62- .

• Central atom of Group 14 can use of the empty d orbital to expand

their valency, from 4 to 6.
carbon which contain only
• Carbon cannot form complex ions because ………………………….
2 shells can allocate a maximum of 8 electrons
……………………………………………………………….
3.2.2 Catenation
• Catenation is the ability of an element to form bonds between atoms of the
same element
• Carbon is unique in its ability to catenate to form stable long chain or even
ring compound.
• For catenation to occur, the metal M–M bond must be strong. The bond
energy of the M–M must must be similar in strength to those between M
and other particular element, e.g. M–O bond.

Element M–M M=M M≡M M–O

Carbon 350 610 840 360
Silicon 222 - - 464
Germanium 188 - - 360
• Carbon, with the smallest size formed the strongest M–M bonds, plus it is
as strong as in M–O bond.
• The M–M for other elements are too weak. Furthermore Carbon can form
double and even triple bond.
• So, only carbons are able to catenate to form series of long chain known
as organic compounds.
• However, for silicon, since the Si–O bonds are stronger than Si–Si, hence
Si–O catenates to form the following chain as found in SiO2.
• The ability to catenate decrease as the size of atom increase
3.3 Oxide of Group 14
• Group 14 elements form oxides with the formulae XO and XO2 in relation
with the +2 and +4 oxidation states.
• The tendency to form dioxides, XO2 , decreases down the group showing
the increases stability of the +2 oxidation states.

+2 oxidation state +4 oxidation state

Element Structure and State of Structure and State of
Formula Formula
bonding matter bonding matter
Simple Simple
Carbon CO covalent Gas CO2 covalent Gas
molecule molecule
Simple Solid with high
Unstable Giant covalent
Silicon SiO covalent SiO2 melting and
gas molecule
molecule boiling points
Germaniu Molecular/
GeO - - GeO2 Solid
m ionic
Solid with high
Ionic Ionic
Tin SnO Solid SnO2 melting and
compound compound
boiling points
Ionic Ionic Solid, Easily
Lead PbO Solid PbO2
compound compound decompose
3.3.1 Carbon Oxides
• Carbon monoxide, CO can be produced by passing carbon dioxide
gas,CO2, over heated carbon.
CO2 (g) + C (s) 2CO (g)
• An alternative method is by reducing the methanoic acid using
concentrated sulphuric acid.
• HCOOH (l) CO (g) + H2O (l)
• In industry, it is prepared in a big scale by passing steam over heated coke.
The mixture of hydrogen and carbon monoxide gases produced formed
‘water
water gas’ and used as fuel
C (s) + H2O (l)
CO (g) + H2 (g) [ Water gas ]
• Carbon monoxide is a toxic gas. Chemically, it is neutral and dissolves
partially in water. Carbon monoxide can exists in three possible structures.
The main covalent bond in the molecule is in sp hybridisation.
• It is toxic since it will combines with hemoglobin to
produce carboxyhemoglobin, which usurps the space in hemoglobin
that normally carries oxygen, but is ineffective for delivering oxygen
to bodily tissues. Furthermore, carbon monoxide is easily absorbed by
lung.
• All the structures of carbon monoxide show that oxygen atom possessing
lone pair of electrons. That is why carbon monoxide is a good ligand. In
a complex consisting of transition metals as the centre ion.
• The carbon monoxide molecules form ligands by donating a lone
pair of electrons through dative bonds. These complexes are known
as carbonyl compounds.
• Example : tetracarbonylnickel (II) ion, [Ni(CO)4]2+

2+
CO

Ni
OC CO
CO
Carbon dioxide, CO2.
• Carbon monoxide is an unstable molecule. In contact with air, it is easily
oxidised to carbon dioxide gas and released into the atmosphere.
2 CO (g) + O2 (g)
2 CO2 (g)
• Carbon dioxide, CO2, is a colourless and odourless gas. Unlike carbon
monoxide, carbon dioxide is non-toxic. It is slightly acidic and it forms
non-polar linear molecule with structure O=C=O. The main covalent bond
is also in sp hybridisation. The intermolecular forces are weak van der
waals’ forces. Carbon dioxide has a low boiling point and sublimes at low
temperatures. At room temperature pressure, carbon dioxide exists as a gas
• Common uses of carbon dioxide includes the following :
– Carbon dioxide used in fire extinguishers are stored under high
pressure. So, when the gas is suddenly released into the atmosphere,
sudden expansion and cooling of the gas causes a dense layer of
inflammable gas to form on top of the flame, blocking off oxygen
supply and thus halts burning.
– Carbon dioxide is also used in making aerated drinks and beverages
and in the manufacture of baking soda, NaHCO3.
– Solid carbon dioxide or dry ice is used as a refrigerant as well as for
producing ‘stage effects’ as it sublimes immediately to produce a cloudy
and misty environment
3.2.2 Silicon Oxides
• Two well known silicon oxides are silicon monoxides, SiO,and silicon
dioxide,SiO2.
• Silicon monoxide, SiO, is an unstable compound at room temperature.
When silicon dioxide, SiO2, and silicon, Si, are heated together under a
vacuum to a high temperature (1250ºC), silicon monoxide will be
produced. However, the reaction is reversible when the temperature cools
down. The reverse reaction is a disproportionation reaction in which the
same element, Si, is reduced and oxidised at the same time.
2 SiO (g) Si (s) + SiO2 (s)
Oxidation state : +2 0 +4
• Silicon dioxide, SiO2, is a very stable compound with high boiling and
melting points. It exists in three different forms at different temperatures.
The three forms, namely quartz, tridimite and cristobalite exist
simultaneously at different temperatures as shown below.
• In the silicon dioxide structures, each
silicon atom is connected to four oxygen
atoms and each oxygen atom shares two
tetrahedrons. The basic unit of the structure
is a SiO4 tetrahedron but since each oxygen
atom is shared between two basic units, the
empirical formula is again SiO2 with
coordination ratio of 4 : 2
• The cristobalite structure shows similarities
to the diamond structure. It is simply
inserting an oxygen atom in the middle of
each Si-Si bond.
• Silicon dioxide is an important component
in ceramics because of its unique
properties. It is inert to attacks from acids
and alkalis, do not corrode, hard but brittle
& stable as a lot of heat energy is required
to break the strong bonds. All these
properties resemble diamond in many
aspects
3.2.3 Germanium oxide
• Germanium (II) oxide, GeO, is obtained from the reduction of germanium
(IV) ion. Reduction must be carried out under inert conditions because any
presence of air will easily oxidise germanium (II) ions back to the more
stable germanium (IV) ions. As in the case of all divalent compounds of
germanium, disproportionation occurs during oxidation.
2 Ge (II) Ge (IV) + Ge
• Germanium oxide, like all the other lower metal oxides of the group, is
more basic and ionic than their dioxide counterparts. Germanium oxide
shows certain acidic properties, however tin (II) oxide and lead (II) oxide
are amphoteric. The basic properties become prominent with increase in
proton number.
• Germanium dioxide, GeO2, is more stable than germanium oxide.
Germanium dioxide shows both acidic and basic properties (amphoteric).
As going down Group 14, the acidic properties of the dioxide decreases
giving a decreasing order of acidity, GeO2 > SnO2 > PbO2.
GeO2 (aq) + 4 HCl (aq)
GeCl4 (aq) + 2 H2O (aq)
GeO2 (aq) + 2 NaOH (aq)
Na2GeO3 (aq) + H2O (l)
3.2.4 Tin Oxide

• Tin (II) oxide, SnO, is a deep green solid compound which is relatively
unstable at room temperature. When heated up in air, it is easily oxidised to
tin (IV) oxide, SnO2. Tin (IV) oxide exists naturally in the Earth’s crust as
a mineral ore from which tin can be mined or extracted from it. Carbon is
used to extract tin.
SnO2 (s) + C (s) Sn (s) + CO2 (g)
• Tin (IV) oxide, SnO2, is only slightly more stable than tin (II) oxide. Both
are amphoteric. Only Sn4+ can exist as free ions.
• Tin can exist in 2 oxides, which is tin (II) oxide (SnO) and tin (IV) oxide
(SnO2). Both of the oxides of tin are amphoteric oxide.
• When tin (II) oxide, SnO react with acid and base
SnO (s) + 2H+ (aq) Sn2+ (aq) + H2O (l)
SnO (s) + OH- (aq) + H2O (l) [Sn(OH)3]- (aq)
Trihydroxystannate (II) ion

• When tin (IV) oxide, SnO2 react with acid and base
SnO2 (s) + 4 H+ (aq) Sn4+ (aq) + 2H2O (l)
SnO2 (s) + 2 OH- (aq) + 2 H2O (l) Sn(OH)62- (aq)
Lead Oxide
• Lead exists in different states of oxides, lead (II) oxide, PbO, lead (IV)
oxide, PbO2, and trilead tetroxide, Pb3O4.
• Lead (II) oxide, PbO is the most stable form of all the lead oxides. All
the other oxides are unstable and easily decompose on heating to form the
more stable lead (II) oxides.
2PbO2 (s) 2 PbO (s) + O2 (g)
Brown Yellow
2Pb3O4 (s) 6 PbO (s) + O2 (g)
Red Yellow
• When lead (II) oxide is heated in air to a temperature of 400oC, it will form
Pb3O4 first. On further heating to 470oC, Pb3O4 will revert back to lead (II)
oxide.
3 PbO2 (s) + O2 (g) Pb3O4 (s) 6PbO (s) + O2 (g)
• Lead (IV) oxide is a powerful oxidising agent as it readily loses its oxygen
atom to form a more stable lead (II) oxide.
2 PbO2 (s) 2 PbO (s) + O2 (g)
• One of the example of this oxidising reaction is the oxidation of the iodide ion,I- to
iodine, I2.
• Trilead tetroxide is also known as ‘red lead’ because of its brilliant scarlet colour.
It consists of a mixture of two moles of lead (II) oxide and one mole of lead( (IV)
oxide. Thus, it behaves chemically like a mixture of the two. It is an oxidising
agent which easily reduced to its metal. It is used as a red pigment in
– oil paints,especially as a first coating for structural steelworks,
– putty with linseed oil for joints in pipes and plates,
– making glass and pottery-glazes, and matches
• Like tin oxide, Lead (II) oxide is also an amphoteric oxide. When react
with acid or base,
In acidic solution : PbO (s) + 2H+ (aq) Pb2+ (aq) + H2O (l)
In alkaline solution : PbO (s) + 2OH- (aq) + H2O (l) [Pb(OH)4]2- (aq)
Tetrahydroxyplumbate(II) ion
• Lead (IV) oxide is also an amphoteric oxide
In acidic solution : PbO2 (s) + 4 H+ (aq) Pb4+ (aq) + 2 H2O (l)
Cold, concentrated
In alkaline solution : PbO2 (s) + 2 OH- (aq) PbO32- (aq) + H2O (l)
Hot, concentrated Plumbate (IV) ion
3.4 Group 14 Chlorides
• All the Group 14 elements form
tetrachloride with formula MCl4
and have a tetrahedral structure.
• The MCl₄ are simple molecules which held together by weak van der
waals forces.Hence,all the compounds have low boiling points and are
liquids under room conditions.
• The stability of the MCl₄₄ compounds decreases down the group as the M-
Cl covalent bond becomes weaker when the atom becomes larger. This is
due to the bond energy decreases when the bond length becomes longer.
• The inert pair effect of bigger atoms like lead gives rise to stable +2
oxidation states. The electrons in the s orbitals show extra stability and are
harder to be removed. Ions like Pb²⁺ are stable compared to its Pb4+ ions.
• Tetrachloromethane or carbon tetrachloride,CCl₄,is very stable to heat
whereas lead (IV) chloride, PbCl₄, (yellow liquid) is unstable and will
slowly decompose to lead (II) chloride (white solid) and chlorine gas, even
at low temperatures.
PbCl4
PbCl2 + Cl2
3.4.1 Physical properties and thermal stability of Group 14 chloride
• All Group 14 chlorides are liquid at room temperature. They are mostly
volatile liquid with high vapour pressure
Tetrachloride CCl4 SiCl4 GeCl4 SnCl4 PbCl4

Melting points (oC) -23 -70 -50 -33 -15

• The melting points of Group 14 chlorides generally increase as the

molecular mass increase. Though, carbon tetrachloride shows greater
melting point than most of the Group 14 chlorides due to the short bond
length between C–Cl, which required a higher temperature is required to
overcome the forces of attraction between the CCl4 molecules.
the atomic size of Br and I are too big for
• MBr4 or MI4 does not exist as ………………………………………………
Carbon. So the product formed will not be stable. (steric hindrance)
………………………………….....................................................................
• When goes down to Group 14, the bond length of M – Cl increase as the
atomic size of group 14 increase. This will causes the covalent bond to be
weakened and decrease the stability.
• CCl4, SiCl4 and GeCl4 are stable at high temperature and does not
decomposed easily. Tin (IV) chloride, SnCl4 and lead (IV) chloride, PbCl4,
on the other hand, decomposed when heated
SnCl4 (l)

PbCl4 (l)
3.4.2 Hydrolysis of Group 14 chloride
• All Group 14 chloride can undergoes hydrolysis except carbon
tetrachloride, CCl4.

• Hydrolysis of Group 14 chloride involves the attachment of water

molecules in empty d-orbital first before the Cl is removed from the Si–Cl
bond. Then, the hydrogen atom from the water attract the chlorine atom
from SiCl4 away and left oxygen atom attached to silicon to form silicon
(IV) oxide
3.4.4 Freons
• Freon is a trade name given to a group of chlorofluorocarbon compounds
normally known as CFC.
• Freon is formed when one or more chlorine atoms from the
tetrachloromethane, CCl₄, is/are substituted by one or more fluorine
atom/atoms.
• The common freons produced are freon-11, freon-12, freon-13, and freon-
14. When only one chlorine atom is substituted by the fluorine atom, the
compound formed is known as trichlorofluoromethane, CFCl₃₃ or freon-11.
Freon-12 refers of two substitution of the chlorine atoms in CCl₄ to form
₂ ₂ Same as freon-11 and freon-12, freon-13, C₂F₃Cl₃
CF₂Cl₂. ₂ ₃ ₃ and freon-14,
₂ ₄ ₂ are all volatile liquids , readily liquefied, relatively inert, non-
C₂F₄Cl₂,
toxic and non-combustible.
• They are used as coolants in refrigerators and air conditioners. Large
quantities of CFC are also used as aerosol propellants in spray cans like
hair spray and insecticide.
• The harmful and destructive effects of these chlorofluoro compounds on
the ozone layer in the stratosphere have attracted much study on these CFC
compounds since the mid 1970s
• The harmful and destructive effects of these chlorofluoro compounds on
the ozone layer in the stratosphere have attracted much study on these CFC
compounds since the mid 1970s
• In the stratosphere, the UV radiation has a wavelength of 175-220nm that
is strong enough to dissociate the CFC compounds
CFCl3 (g)
CFCl2• + Cl•
• The chlorine radical, Cl●, is very reactive and will continue to attack the
ozone molecules in the stratosphere
Cl• + O3
ClO • + O2 ……………………….. (1)
ClO• + O
Cl• + O2 ……………………….. (2)
• Although the ClO• species acts only as an intermediate, its presence is
greatly responsible for the destruction and hence the depletion of the
ozone layer
• The ozone layer absorbs the harmful ultraviolet (UV) radiation from the
sun so that only a minimal amount penetrates through to reach the
atmosphere. Too much UV radiation is harmful as it causes skin cancer and
damages vegetation
3.5 Carbon composite in industry
• Composite compounds are formed when two or more materials are mixed
or combined together to give improved qualities over the original
substance. For example, substances like metal or alloy , ceramic and
polymer when combined together will form composites that display all the
good properties of the components
• Some common composite substances used in everyday like are concrete,
high fibre plastics, superconductors and photochromatic glass.
• Composite compound is one type of solid that does not have a crystal
lattice. Other such solid is the amorphous solid which include carbon black,
glass and polymer.
• Carbon composites are formed when amorphous carbon is heated to a high
temperature to form graphite fibres. This fibre then interwined with plastics
to form a structure which is strong, stretchable and yet chemically stable
known as carbon composites
• Kevlar is one of the synthetic graphite fibres that is considerable
importance in the plastic industry. It has high tensile strength and is more
modulus than fibreglass. Kevlar is used for structures that require stiffness,
high abrasion resistance and lightweight. Example of uses are Kevlar ropes
used as lightweight boat hulls such as in canoes and aircrafts, and also
canvas for tents.
• Kevlar maybe be used with epoxy or vinyl ester resin (polymer) as in
fabrics for high performance reinforcement in automotive and marine
applications. The firemen suits and the bulletproof jackets are all made of
this type of material.
Other composite compounds
• Concrete is another composite of Group 14 elements which is a mixture of
cement, sand, brick and water. Concrete is hard but brittle and is able to
withstand heavyweights. The structure of concrete can be further
strengthened by laying steel wires to hold the components cement, sand,
and brick closer together.
• Plastics, if strengthened by adding fiberglass to its structures, form a
composite material that has broad uses in the building industry and in
making sports equipment because composite material is light yet strong.
• Photochromatic glasses are formed when photochromatic chemicals like
silver chloride are added to transparent glass (silicon dioxide and silica ).
This type of glass turns darker under sunlight and will revert back to its
colourless state when out of the sun. This special property makes
photochromatics glasses suitable for making sunglasses as they protect
eyes from ultraviolet rays of the sun. Window screens of cars and glass
window of residential houses also make use of this property of
photochromatic glass to absorb unwanted rays so that the interior of cars
and houses remain cool.

• Ceramics and a few metal compounds are able to conduct electricity with
negligible resistance when cooled to a certain temperature. These are
superconductors and are normally used in high technology facilities like
the bullet train and some modern medical appliances.
3.6 Silicon and Silicates
• Silicon exists naturally in the Earth’s crust as - silicates,aluminosilicates
and silica.
• Basic structural unit of silicates, SiO44- (Silicon atom is surrounded by 4 O
atoms to form a tetrahedron).
• Silicon uses sp3 hybridisation in its bonding with oxygen.
• Different ways of arrangement will result in rings, single and double
chains, sheets and 3-D network.
• Basic understanding to define silicates structures:
(a) All structures are constructed from SiO4 tetrahedral.
(b) The tetrahedral are joined to each other by corners only.
(c) Resulting charges on the SiO44- anion depends on the number of
corners shared
• Most basic - consist only one simple SiO44- unit.
• The 4 electrons needed to complete the octet are obtained from metal
atoms (like Mg2+ and Ca2+) and give the anion its quadruple negative
charge. Examples:
(a) zircon,ZiSiO4
(b) olivine, Mg2SiO4
(c) garnet,Ca2Al2(Si3O9)
 Different Type of Silicates
Pyrosilicates
It’s formed when 2 SiO44- unit joined
together using an oxygen atom as
the bridging atom.
Also known as soro-silicates or
disilicates.
Examples:
(a) thortveitite,Sc2Si2O7.
(b) barycilite,Pb3Si2O7
Ring silicates / Cyclosilicates
It’s formed when 3 basic SiO44 -
units joined together by sharing 2
of its oxygen atoms in a compact
manner.
Unit cell - (SiO3)n2n- unit.
Examples:
(a) bentonite,BaTiSi3O9.
(b) beryl, Al2Be3Si6O18
3.6.1 Single Chain Silicates/Pyroxenes
• It’s formed when each SiO44- tetrahedral unit sharing 2 of its oxygen
atoms with the next unit to form a long chain of (SiO3)n2n-. 2 pyroxene
chains joined together by the corners will form amphiboles, with anionic
structure [(Si4O11)6-]n. structure : 2-dimensional. Si-O bond is strong
within the chain and weak between the chains. Hard but brittle (bonds
between the chains can easily be broken).
• Asbestos is an important amphibole.
– Resistant towards heat and fire, inert towards attacks from acids and
alkalis, fibrous (amphiboles sheets are separable),and not malleable.
• Tremolite is also an amphibole with formula Ca2Mg5(Si4O11)2(OH)2.
– can be cleft into strands,which is separated into thin fibres and later on
woven into cloth.
– *layered structure contributes to its hardness and brittleness
• Single chain in pyroxenes

• Double chain in amphiboles

3.6.2 Silicate sheets
• Silicate It’s formed when 3 corners of the SiO44- unit are shared by 3 other
units to form a 2-dimensional infinite sheet.
• Unit formula:(Si2O5)n2n- - found in clay substances like talc, mica and
kaolinite.
• Pyrophyllite is forrmed when 2 layers of SiO4 tetrahedral and 1 layer of
AlO6 octahedral are linked together in a ratio of 2:1.
– ideal composition:Al2Si4O10(OH)2.
• Talc is formed if the 2 aluminium ions in pyrophyllite are replaced by 3
magnesium ions.
– formula: Mg3Si4O10(OH)2.
– electrically neutral.
– it’s a giant molecule with strong covalent properties.
– The molecules in talc are arranged in parallel sheets giving the rise to
flaky textures
Mica/Aluminosilicates
• consists of anion sheets held together by cations (K+ or Mg2+) present in
between the sheets.
• Negative charge among the layers appears because 1/4 of the silicon ions
in pyrophyllite is being replaced by an aluminium ion-[Al3Si3O10(OH)2]-
• Example:muscovite (KAl2(OH)2[AlSi3O10]5-) *also known as white mica

Kaolin
• higher quality kaolinite (clay soils).
• It’s formed when some SiO2 units are removed from micas,
[Al3Si3O10(OH)2]-,so that one layer of SiO4
• tetrahedral share corners with one layer of AlO6 octahedral to form a ratio
of 1:1 ,Al2Si2O3(OH)4
• Clay is formed when it’s mixed with water.-making porcelain vases, cups,
china plates and white ceramic tiles.It can also be used to treat
indigestion
Montmorillonite
• Molecular formula: (Mg0.33Al1.67)(OH)2(Si2O5)20.33-.
• Consists of identical sheets.
• If one of the aluminium ion in it is replaced by one magnesium ion, the
resulting unit cell will have a positive charge which can be balanced out
by absorbing different ions into its structure.
• Forms semi-solid gel in the presence of water.
• Also acts as a cation exchange.(e.g. to exchange one mole of Na+ with
one mole of H+ so that the surface becomes acidic, one mole of
montmorillonite is required.
• At high temperature(150oC), montmorillonite loses its water molecules
and acidity. The layered structure of its silicate will collapse. Because of
this, zeolite is preferred to montmorillonite in industries especially when
the reactions required high pressure and temperature
3.6.3 Three – Dimensional Silicates / Framework Structure
• It’s formed when all the 4 angles of the silicate anion unit are shared by 4
other units to form 3-D lattice.
• It’s found in quartz and cristobalite.
• Basic formula: (SiO2)n with neutral lattice.
• Quartz is regarded as a giant covalent molecule.
• Besides quartz,all the other members are aluminosilicates because of the
presence of aluminium atoms in their structures.
• When silicon atoms are subsituted by aluminium atoms, the resulting
structure is a giant anion because of the difference in charges (Al3+and
Si4+).
• If 1/4 of the silicon atoms in 4 SiO2 is replaced by an aluminium atom, a
big anion with formula [AlSi3O8]- is formed.
• The negative charge will be neutralised by cations as in orthoclase,
K(AlSi3O8).
3.6.4 Silicones
• A group of polyorganosiloxanes containing the Si-C bond in long chains
of -Si-O-Si- structures with
• alkyl or aryl groups attached to the silicon atoms.
• It’s a long chain polymer and the structure varies when the conditions of
reaction (hydrolysis and polymerisation)change.
– includes forming cross-links between the polymer chains by different
alkyl groups.
– The type of alkyl groups attached can be determined by the types of
Grignard reagents used.
– Polymers with cross-link bridges are harder and withstand heat
better than single chain silicones.
• Silicones are prepared from silicon tetrachloride and methylmagnesium
iodide (Grignard reagent) in ether
Step 1 : Reaction of silicon tetrachloride with Grignard reagent
SiCl4 (l) + 2 CH3–MgI (l)
Si(CH3)2Cl2 + 2 MgClI

Step 2 : Dimethyldichlorosilane then undergoes hydrolysis to form hydroxyl

compound Si(CH3)2Cl2 (l) + 2 H2O
Si(CH3)2(OH)2 + 2 HCl
Step 3 : Product of hydrolysis undergoes condensation polymerisation to
displace water molecules
Application of silicones
• It’s non-toxic, colourless, odourless and resists to physical and chemical
changes caused by heat, cold and pressure.
• Has water repellant properties and is an electric insulator.
• Properties can be modified by attaching different organic groups to the
main structure framework
• Silicone fluids- is used as lubricant in areas with low temperature as well as
in hot areas.It’s used over waterproofing fabrics and in polish for cars and
furniture.
• Silicon rubbers- can be converted to elastomers by vulcanisation and cross-
linking of the chains.
• Resins- insulation in electric motors and transformers.
• It’s added to paints to increase the resistance against weather tear and heat.
• Form lacquers for coating frying pans so that food do not stick on the
surface.
• It’s also used as grease for lubricating glass tubes and burettes heads
3.7 Glass
• Solids are most stable in crystalline form. However, if the solid is formed
rapidly ( like sudden cooling of crystals), the crystals formed will not have
a regular lattice. This type of solid is known as amorphous or non-
crystalline.
• Glass is an amorphous solid as it does not have a regular three-dimensional
arrangement of atoms. Glass is commonly referred to an optically
transparent fusion product of inorganic materials cooled rapidly to a rigid
state without undergoing crystallisation.
• Fusion – process of mixing molten silicon dioxide, with its supplementary
compounds such as sodium oxide, boron oxide or certain transition metals
for colours and other properties.
• The main component of glasses is silicon dioxide, or simply sand. Other
components are boron oxide, aluminium oxide and others are only
supplementary additives, added to change the properties of the glasses
produced. Some important glasses with special purpose are listed below
• Quartz glass = silicon oxide SiO2. It has a low coefficient of thermal
expansion but its important property lies in its transparency to a wide range
of wavelengths. It is used in mirrors, glass rods and quartz lenses
• Pyrex = borosilicate glass = boron + silicon oxides which give the glass a
rather high coefficient of thermal expansion (more resistance towards
thermal expansion when heated or cooled quickly). As such, the glass will
not crack when heated to a high temperature or break when contracted in a
freezer. This type of glass is used as test tubes and boiling flasks in the
laboratory as well as cooking wares in the kitchen
• Soda glass = sodium silicate + calcium silicate. Soda glass is passive to
attack from chemical substances and is very brittle. Bottles made from
soda glass are used to store non-reactive drinks and sauces like cordials
and soya sauces. Since soda glass has a low melting point, it can be
moulded into desired shapes and sizes. Bulbs, window-panes, drinking
glasses, some cups and plates are made of soda glass. Products made from
soda glass are cheaper and breakable.
• Some laboratory apparatus like microscopic glass plate, glass dish and
glass tubing are all very fragile. The properties of soda glass can be
upgraded by adding some metal oxides like lead oxide or boron oxide to
enhance properties like colour and hardness
• Lead glass = flint glass = potassium silicate and lead silicate which
gives the glass a high refractive index. This type of glass is also known as
crystal glass because of its glittering appearance. It is used in decorative
glassware and windows. Lead glass is used in the laboratory as high
refractive lens and prisms for optical studies
• Bio glass = crown glass = phosphorus pentoxide + silicon oxide. It gives
a smaller refractive index than flint glass but can be combined with flint
glass to produce the desired refractive index. It is therefore important as
implants in medical surgery at it has almost the same composition as bones

• Water glass = fusion of sand, silicon oxide and sodium carbonate to

produce sodium silicates which are soluble in water. The molten water
glass is used to preserve eggs and as adhesives
3.9 Uses of Tin
1. This is a white metal with low melting point of 232 C. It is soft, ductile
and malleable. It is widely used to make tin foil and wires.
2. Tin forms several alloys with other metals. For example,
(a) bronze (90% copper, 10% tin) which is used in engines, electrical
fuse and door knobs
(b) pewter (75% tin, 25% lead) used for souvenirs
(c) solder ( 50% tin, 50% lead) used for soldering
3. Pure tin is used in making cans for storing food ( so called canned food )
and tubes for storing toothpaste, creams and medicines.
4. Almost half of the tin produced is used to plate iron or mild steel to
prevent the iron or steel from rusting. Tin plating is used in canned food as
well.
5. Thin sheets of tin are used as wrapping in cigarette boxes