GROUP - 14 ELEMENTS

CARBON FAMILY
Introduction
C, Si, Ge, Sn, Pb is element of group 14. C is widely
distributed in nature in

free as well as in combined state. it has valencey 4. we can

say C is most

versatile element in the world. organic chemistry is devoted

to carbon

containing compunds.

Generally Si is present in nature in form of silica. Ge exists

only in traces.

Sn exists in cassiterite and Pb in form of galena.

Ge and Si is semiconductor of electricity so they use in

making transistors.

# GENERAL PHYSICAL PROPERTIES OF

CARBON
FAMILY
(1) ELECTRONIC CONFIGURATION

(2) COVELENT AND ATOMIC RADIUS

There is cosideriable increase in covelent radius from C to Si
and small
increase from Si to Pb is observed.

The atomic radii of Group 14 elements are less than the

corresponding
elements of Group 13. However, the atomic radii increase
down the family.
Explanation :
The decrease in atomic radii is due to increase in effective
nuclear charge
on going from Group 13 element to Group 14 element within
the same
period.
As a result , the outermost electrons are attracted more
strongly
towards the nucleus and therefore , atomic radius decreases.
Within the
group, atomic radii increase on going down the group, due to
the increase
in the number of electron shells.

(3) IONIZATION ENTHALPY

FIRST I.E OF CARBON FAMILY > FRIST I.E OF BORON FAMILY
OF CORROSPONDING ELEMENT.
In carbon family -
small decrase in I.E from Si to Sn
slight increase in I.E from Sn to Pb

Explanation :
The higher ionisation enthalpies are due to the higher
nuclear charge and
smaller size of atoms of Group 14 elements. While moving
down the
group, the ionisation enthalpies decrease. This is due to the
increase in
atomic size and screening effect which overweigh the effect
of increase in
nuclear charge. Therefore, the outermost electron becomes
less and less
tightly held by the nucleus and ionisation enthalpy
decreases.

(4) ELECTRONEGATIVITY
The value decreases from C to Pb but not in a regular
manner probably
due to filling of d-orbitals III and Sn and f-orbitals In Pb.

(5) OXIDATION STATES

Group - 14 elements exhibit +2 and +4 oxidation state. The
compounds of
Pb in +4 oxidation state are powerful oxidising agents since,
+2 oxidation
state of Pb is more stable dueto inert pair [Link]
compounds in +2
oxidation state are ionic in nature and in + 4 oxidation state
are covalent in
nature (According to Fajan‟s rule).

FAJAN's RULE - Thid is used to predict whether a chemical

bond will be
covalent or ionic, and depend on the charge on the cation
and the relative
sizes of the cation and anion.

(6) PHYSICAL PROPERTIES

 C and Si are non-metals, Ge is a metalloid and Sn and Pb
are metals.

C is black. Si is light-brown, Ge is greyish, Sn and Pb are

silvery white.

The atoms of group -14 form covalent bonds with each other
and
therefore , there are strong binding forces between their
atoms in both
solid and liquid states. Consequently, the melting and
boiling points of
group 14 elements are much higher in comparison to Group
13
elements.

On moving down the group, the boiling points decrease.

The melting points and boiling points decrease from carbon

to Lead.

Carbon and silicon have very high melting and boiling points
due to
their giant structure.

Density increases with increase m atomic number due to

increase
in mass per unit volume down the group.

# CHEMICAL PROPERTIES OF CARBON

FAMILY
Carbon and silicon mostly show shown +4 oxidation state.
Germanium
forms stable compounds in +4 state and only few
compounds in +2 state.
Tin forms compounds in both oxidation states (Sn in +2state
is a reducing
agent). Lead compounds in +2 state are stable and in and in
+4 state are
strong oxidizing agents.

Carbon cannot exceed its covalence more than 4, other

elements of the
group can do so. It is because of the presence of d-orbital in
them. Due to
this , their halides undergo hydrolysis and have a tendency
to form
complexes by accepting electron pairs from donor species.
For example,
the species like [SiF6]2-, [GeCl6]2- , [Sn(OH)6]2- exist where
the
hybridization state of central atom is sp3d2.

(1) REACTIVITY TOWARDS OXYGEN

All elements of group-14 when heated in presence of oxygen
then They
form two types of oxides. mono-oxides of the type MO. e.g.,
CO (neutral) , GeO(distinctly acidic) SnO, PbO (amphoteric)
and
dioxides of the type MO2.
acidic oxides ---> CO2, SiO2
amphoteric oxides ---> GeO2, SnO2, PbO2
CO2 is linear gas at ordinary temperature. Solid CO 2 is known
as dry ice.

(2) REACTIVITY TOWARDS WATER

# C, Si, and Ge not affected by water.

# Tin reaction with water-

Sn + 2H2O ----> SnO2 + 2H2 ( tin decompose to steam)

# Lead is not react with water due to formation of protective

oxide film.

(3) REACTIVITY TOWARDS HALOGEN

Group - 14 elements can form halides of formula MX 2
and MX4 (where
X is F, Cl, Br , I ). Except carbon , all other members
react directly with
halogen under suitable condition to make halides.

Most of the MX4 are covalent in nature.

Exceptions are SnF4 and PbF4 which are ionic in nature.

PbI4 does not exist because Pb – I bond initially formed

during the
Reaction does not release enough energy to unpair 6s2
electrons and
exciteone of them to higher orbital to have four
unpaired electrons
around lead atom.

Stability of dihalides increases down the group.

Considering the thermal and chemical stability , GeX 4 is

more stable than
GeX2 , whereas PbX2 is more stable than PbX4.

Q: CCl4 is not lewis acid but other halides shows lewis acid
behaviour.
why?
answer:
 Except CCl4 , other tetrachlorides are easily hydrolysed by
water because
the central atom can accommodate the lone pair of
electrons from
oxygen atom of water molecule in d-orbital.
Example --
SiCl4 undergoes hydrolysis by initially accepting lone pair
of electrons
from water molecule in d-orbitals of Si , finally leading to
the formation
of Si(OH)4 as shown below.

(4) ANOMALOUS BEHAVIOUR OF CARBON

Carbon also has unique ability to form pπ– pπ multiple bonds

with itself
and with other atoms of small size and high
electronegativity.

Few examples of multiple bonding are: C=C,

C ≡ C, C = O, C = S, and C ≡ N. Heavier elements do not
form pπ– pπ bonds
because their atomic orbitals are too large and diffuse to
have effective
overlapping.

Carbon atoms have the tendency to link with one another

through
covalent bonds to form chains and rings. This property is
called
catenation. This is because C—C bonds are very strong. C--C
bond energy
is 348 KJ/mol.

The order of catenation is C > > Si > Ge ≈ Sn. Lead does not
show
catenation.
Lead does not show catenation Because it has large atomic
orbitals which cannot easily form bond.

(5) ALLOTROPES OF CARBON

Elemental carbon exists in several crystalline and

amorphous forms. The

allotropes of carbon are diamond, graphite and fullerenes.

1. DIAMOND
Structure

In diamond , carbon is sp3 hybridised. Each carbon is

tetrahedrally

linked to neighbouring carbon atoms through four strong C-

C, sp3

hybridised, s - bonds.

Properties

Diamond is the purest form of carbon.

The C- C bond length in diamond is 154 pm.

Since diamond exists as a three dimensional net work solid ,

it is

the hardest substance known with high density and melting

point.

Since all the electrons are firmly held in C- C , s - bonds,

there are

no free electrons in a diamond crystal. Therefore diamond is

a bad

coductor of electricity.

Because of its high refractive index (2.5) , diamond can

reflect and

Reflect light. Therefore diamond is a transparent substance.

Uses

Because of its hardness, diamond is used for cutting glass,

making

borers for rock drilling and for making abrasives.

When diamond is cut and polished, brilliant light is refracted

from

its Surface That is why diamond is used for making precious

gems

and jwellery.

It is used for grinding and polishing of hard materials.

Diamond is used for making dies for drawing thin wires from

metals.

2. GRAPHITE

Structure

Graphite has a layer structure in which each carbon atom is

bonded to

three other carbon atoms to form a hexagonal sheet. Each

carbon atom

forms three sigma bonds by means of sp2 hybid orbitals.

The remaining unhybridised p-orbital of each carbon atom
having an
electron overlaps with its counterparts on adjacent carbon
atoms in the
same layer to form p-bonds.

The hexagonal sheets are held together by weak van der

Waal’s forces. It
is easy for one layer to slide over another, graphite is soft
and slippery
material with excellent lubricating properties. The p-
electrons within the
layer are free to move and this accounts for the electrical
conductivity of
graphite.

Uses of Graphite
Graphite is used to make electrodes for electrolytic cells.

Being soft and greasy , it is used to lubricate the parts of the

machines.

Graphite crucibles can withstand very high temperatures and

can
be used for high melting substance.

Graphite is used to moderate the fast moving neutrons in

nuclear
Reactors.

3. FULLRENES

Fullerenes were originally made by the evaporation of

graphite using a
laser. A more practical method involves the heating of
graphite in an
electric arc in the presence of inert gas such as helium or
argon.

The sooty material formed by condensation of vapourised C n

small molecules consists of mainly C60 with smaller quantity
of C70
and traces of fullerenes consisting of even number of carbon
atoms
upto 350 or above. Fullerenes are the only pureform of
carbon.
Fullerenes are cage like molecules. C60 molecule has a shape
like soccer
ball and called Buckminsterfullerene.

It contains twenty six- membered rings and twelve five

membered rings. A
six membered ring is fused with six or five membered rings
but a five
membered ring can only fuse with six membered rings. All
the carbon
atoms are equal and they undergo sp2 hybridisation. Each
carbon atom
forms three sigma bonds with other three carbon atoms.

This ball shaped molecule has 60 vertices and each one is

occupied by one
Carbon atom and it also contains both single and double
bonds with
C–C distances of 143.5 pm and 138.3 pm respectivaly.

It is very important to know that graphite is

thermodynamically most
stable allotrope of carbon and, therefore, ΔHf of graphite is
taken as zero.
ΔHf values of diamond and fullerene, C60 are 1.90 and 38.1 kJ
/mol,
respectively.

Application of fullerene

They are good lubricants because the balls can roll between
surface.

Alkali compounds of C60 (A3C60) are super conducting

materials even
at the high temperature of order 40-50 K.

COMPUND OF CARBON

1. CARBON MONOXIDE (CO)

In CO molecule, there are one sigma and two π bonds

between carbon and
oxygen, :C ≡ O: . Because of the presence of a lone pair on
carbon, CO
molecule acts as a donor and reacts with certain metals
when heated to
form metal carbonyls.

PRAPERATION METHOD
Direct oxidation of C in limited supply of oxygen or air yields
carbon
Monoxide.
2C(s) + O2 ----------> 2 CO
This type of incomplete combustion occurs during burning of
petrol or
diesel in automobiles and therefore , CO is always present in
automobile exhausts. It is also present in volcanic gases and
gases
coming out offurnaces.

On small scale pure CO is prepared by dehydration of formic

acid with
Concentrated H2SO4 at 373 K
HCOOH ------------> H2O + CO

On commercial scale CO is prepared by the passage of

steam over hot
coke. The mixture of CO and H2 thus produced is known as
water gas.
C(s) + H2O(g) -----> CO(g) + H2(g) ( 473--1273 K )

When air is used instead of steam, a mixture of CO and N2 is

produced, which is called producer gas.
2C(s) + O2(g) + 4N2 (g)---> 2CO + 4N2 ( at 1273 K )

Water gas and producer gas are very important industrial

fuels.
 PROPERTIES
It is a neutral oxide.

It is a colourless and odourless gas which is only slightly

soluble in
water.

Carbon monoxide is highly poisonous (toxic) in nature. Its

toxic nature
Is due to its ability to form a stable complex with the
haemoglobin.
Which is about 300 times more stable than the oxygen-
haemoglobin
Complex. This prevents haemoglobin in the red blood
corpuscles from
Carrying oxygen round the body.

CO is used in the extraction of many metals from their

oxides ores.
CO can be easily oxidised to CO2 , it acts as a powerful
reducing agent.
As such it reduces many metal oxides to their respective
metals.

ZnO(s) + CO(g) ------> Zn(s) + CO2(g) (Heating)

Fe2O3(s) + 3CO(g) -----> 2Fe(S) + 3CO2(g) (Heating)

2. CARBON DIOXIDE ( CO2 )

Structure
In CO2 molecule, carbon is sp-hybridised, it forms two s-
bonds with two
oxygen atoms and two pπ - pπ multiple bonds. As a result ,
CO2 is linear,
monomeric covalent compound.

This structure predicts that both the carbon-oxygen bond

length in CO2
should be equal and should have a typical bond length of
122 pm.
However, experimentally , it has been found that the carbon-
oxygen bond
length in CO2 is only 115 pm. This can be explained , if
carbon dioxide is
considered to a resonance hybrid of the following structures:

Method of praperation

It is prepared by complete combustion of carbon and carbon

containing fuels in excess of air.

C(s) + O2(g) -------> CO2(g) (combustion)

CH4(g) + 2O2(g) ---> CO2(g) + 2H2O(g) (combustion)

For commercially carbon dioxide is prapered by heating of

lime
stone.
 Properties

It is a colourless and odourless gas. Its low solubility in water

makes it
of immense biochemical and geo-chemical importance. With
water, it forms carbonic acid, H2CO3

CO2 + H2O -----> H2CO3 (carbonic acid)

H2CO3 is a weak dibasic acid and dissociates in two

steps:

This buffer system helps to maintain pH of blood between

7.26 to 7.42

Photosynthesis :
Carbon dioxide is absorbed by plants. In the presence of
chlorophyll and
sunlight , the absorbed carbon dioxide combines with water
to form
 glucose and starch, which is used as food by plants. This
process is
called photosynthesis.

By this process plants make food for themselves as well as

for animals
and human beings. Unlike CO, it is not poisonous. But the
increase in
combustion of fossil fuels and decomposition of lime stone
for cement
manufacture increases the CO2 content of the atmosphere.
This may
lead to increase in green house effect and thus raise the
temperature of
atmosphere which might have serious consequences.

SILICONE AND IT'S COMPUND

 SILICONE DIOXIDE ( SiO2 )

95% of earth’s crust is made up of silica and and silicates.

Silicon
dioxide ,commonly known as silica , occurs in several
crystallographic
forms. Quartz ,( Quartz is extensively used as a
piezoelectric material; it
has made possible to develop extremely accurate clocks),
cristobalite
andtridymite are some of the crystalline forms of silica.

3-D structure of Silica

Silicon dioxide is a covalent, three-dimensional network solid

in which
each silicon atom is covalently bonded in a tetrahedral
manner to four
oxygen atoms. Each oxygen atom in turn covalently bonded
to another
silicon atoms.
Each corner is shared with another tetrahedron. The entire
crystal may be
considered as giant molecule in which eight membered rings
are formed
with alternate silicon and oxygen atoms.

Properites
Silica in its normal form is almost nonreactive because of
very high Si—O
bond enthalpy. It resists the attack by halogens, dihydrogen
and most of
the acids and metals even at elevated temperatures.
However, it is
attacked by HF and NaOH.

SiO2 + 2NaOH → Na2SiO3 + H2O

SiO2 + 4HF → SiF4 + 2H2O

SILICONES
what are the silicones ?
Silicones are polymeric compounds containing Si-O-Si
linkages. These
are polymers , which contain R2SiO repeating units. These
have the
general formula (R2SiO)n.
These may be linear, cyclic or crossed linked.
These have very high thermal stability and are called high
temperature
polymers.

Praperation

These are obtained by the reaction of alkyl halides with

silicon in the
presence of metallic copper which acts as catalyst.

2CH3Cl + Si -----> (CH3)2SiCl2 ( in presence of Cu powder

at 570 K )

(CH3)2SiCl2 + 2H2O ------> (CH3)2Si(OH)2 + 2HCl

Polymerization
Example -

The chain length of the polymer can becontrolled by adding

(CH3)3SiOH
which blocks the ends.

Properities
Silicones being surrounded by non-polar alkyl groups are
water repelling
innature. They have in general high thermal stability, high
dielectric
strengthand resistance to oxidation and chemicals.

SILICATES

Some of the examples are feldspar, zeolites, mica and

asbestos. The basic
structural unit of silicates is (SiO4)4- in which silicon atom is
bonded to
four oxygen atoms in tetradron fashion.
In silicates either the discrete unit is present or a number of
such units are
joined together via corners by sharing 1 , 2 , 3 or 4 oxygen
atoms per
silicate units. When silicate units are linked together, they
form chain ,
ring , sheet or three-dimensional structures. Negative charge
on silicate
structure is neutralized by positively charged metal ions. If
all the four
corners are shared with other tetrahedral units , three
dimensional
network is formed.
Two important man-made silicates are glass and cement.

Zeolites

Q: Explain the Zeolites formation?

If aluminium atoms replace few silicon atoms in three
dimensional
network of silicon dioxide, overall structure known as
aluminosilicate ,
acquires a negative charge. Cations such as Na+, K+ or
Ca2+ balance the
negative charge.
Examples are feldspar and zeolites.
Zeolites are widely used as catalyst in petrochemical
industries for
cracking of hydrocarbons and isomerisation , e.g., ZSM-5 (a
type of
silicate) used to convert alcohols directly into gasoline.

Hydrated zeolites are used as ion exchangers in softening of

‘hard water’