Group IV or 14

The elements in group IV/IVA or 14 –

carbon, silicon, germanium, tin and
lead
They show a gradation from C, which
is non-metallic,
to Pb, which, though its oxides are
amphoteric,
is mainly metallic in nature.
 Group IV or 14
The ‘diagonal line’ usually drawn
through the p-block to separate
metallic from non-metallic
elements, passes between Si and
Ge.
This imply that that Si is non-
metallic and Ge is metallic.
However, this distinction is not
definitive.
 Group IV or 14
In the solid state, Si and Ge possess
a covalent diamond-type lattice,
but their electrical resistivity are
significantly lower than that of
diamond.
This indicate metallic behaviour.
Silicon and germanium are classed
as semi-metals
hence have semiconducting
properties.
 Group IV or 14
All members of group 14 exhibit
an oxidation state of +4,
but the +2 oxidation state
increases in stability as the group
is descended.
There are no stable compounds
of carbon and silicon in +2
oxidation state.
 Group IV or 14
 Only tin and lead are capable of
forming +2 ions which occur both in the
solid state and in solution.
 Carbenes exemplify the C(II) state but
exist only as reaction intermediates
 Silicon dihalides are stable only at high
temperatures
 Group IV or 14
 The Ge(II) and Sn(II) states are well
established.
 Pb(II) is more stable than the Pb(IV)
state.
 Pb resembles its periodic neighbours, Tl
and Bi, with the inertness of the 6s
electrons-inert pair effect.
 WHAT IS INERT PAIR
EFFECT?
 The tendency of elements of higher
atomic number to retain the s
electrons is termed inert pair effect.
 It is a general feature of the last
member of each of groups 13, 14 and
15.
 GROUP 14 ELEMENTS: THE CARBON FAMILY

Element symbol electron configuration

Carbon C
[He]2s22p2
Silicon Si
[Ne]3s23p2
Germanium Ge
[Ar]3d104s2 4p2
Tin Sn
[Kr]4d105s2 5p2
Lead Pb [Xe]4f14
5d106s2 6p2
 PROPERTIES OF
GROUP 14 ELEMENTS

Property C Si Ge Sn Pb

Atomic 6 14 32 50 82
number
 PROPERTIES OF
GROUP 14
Outer
ELEMENTS
2s 2p2 2
3s 3p 2
4s 4p 2
5s 5p2 2 2 2 6s26p2

electrons

Physical Solid Solid Solid Solid Solid

state (25

oC, 1 atm)
 PROPERTIES OF
GROUP 14 ELEMENTS
I. E. (kJ/mol)

M(g) →M(g)+ e- 1086 786. 760 708 715

M+(g)→M2+(g) + e- 2353 1577 1537 1411 1450

 PROPERTIES OF GROUP 14
ELEMENTS

M2+(g)→M3+(g) + e- 4618 3228 3301 2942 3080

M3+(g)→M4+(g) + e- 6512 4355 4410 3928 4082

 Atomic and physical properties: group 14 elements
Property Elements
Carbon Silicon Germanium Tin Lead
Atomic number 6 14 32 50 82
Atomic mass(g/mol) 12.01 28.09 72.60 118.71 207.2
Electronic configuration [He]2s22p [Ne]3s23p2 [Ar]3d104s24p2 [Kr]4d105s25p [Xe]4f145d10
2 2
6s26p2
Covalent radius/pm 77 118 122 140 146
Ionic radiusM4+/pm _ 40 53 69 78
Ionic radius M2+/pm _ _ 73 118 119
Ionization 1086 786 761 708 715
enthalpy/Kjmol-1
(∆iH)
Electronegativity 2.5 1.8 1.8 1.8 1.9
Density/g cm-3 3.51 2.34 5.32 7.26 11.34
Melting point/K 4373 1693 1218 505 600
Boiling point/K _ 3550 3123 2896 2024
Electrical resistivity/ohm 1014-1016 50 50 10-5 2 X 10-5
cm
 Oxidation number
Oxidation state:-

• Carbon and silicon have +4 oxidation state.

• C & Si have very rare +2 compounds.

• Ge, Sn & Pb show both +2 and +4 oxidation states.

• The +2 state is more stable than +4 state as we go

down the group.
 CATENATION
Bond C─C Si─Si Ge─Ge Sn─Sn

• Bond
The enthalpy
property(Kjmol 348 222to the formation
167 155 chains and
-
1)
of self linkage leading of long
rings is termed catenation.

• Carbon has a greater tendency of self linking than other elements.

• Catenation tendency follows the order :C >> Si > Ge ≈

Sn >> Pb
• The M─M bond enthalpy decreases steadily from C to Sn. Therefore, the
catenation tendency also decreases down the group.
 Formation of Multiple bonds :-
pi bonding
• Carbon forms stable multiple bonds with itself
and with other elements.
• >C=C< , ─C≡C─ , >C=O, >C=N, ─C≡N,
>C=S
• Other elements of this group show no tendency
to form pi bonds.
• Few compounds containing multiple bonds
have been isolated.
• Effect of pi bonding on the structure may be
seen in graphite.
 Hydride formation

• Covalent hydrides of the type MH4 are known

for all group 14 elements except lead.

• Tendency of hydride formation decreases in

going from C to Pb.

• Carbon forms a large number of cyclic and

acyclic hydrides known as hydrocarbons.
 Hydride formation

• Silicon and germanium form fewer

hydrides of the general formula

SinH2n+2 & GenH2n+2 known as silanes

and germanes respectively.

 Oxide formation-

• Group 14 elements form three types of oxides:-

• MO(monoxide) MO2(Dioxide)

• M2O3 (MO+MO2)(Mixed oxide)

• All elements of group14 expect silicon form

monoxides of the formula MO.

• While CO is neutral, all other oxides are basic in

character.
 Oxide formation-

• Carbon monoxide(CO) is the most

important monoxide.

• All group14 elements form dioxides

having the formula MO2.

• These oxides differ in their

properties and structures.
 Halide formation
• Elements of group14 form the following
types of halides: MX4 type eg., CCl4
(carbon tetrachloride)

MHX3 type eg., CHCl3

(Chloroform)

MX2 type eg., SICl2

(Silicon dichloride)
 Halide formation

• The stability of dihalides increases down the

group

• Tetrahalides of the type MX4 are known for all

the elements of group 14.

• Tetrahalides are tetrahedral and covalent.

• The tetrahalides of all elements except of

carbon undergo hydrolysis.
 SOURCES
Important sources of carbon are
coal and crude oil
Also deposits of natural gas, which
is mainly methane, CH4
 ALLOTROPES
 Carbon occurs as several allotropes,
which have very different structures
and properties.
 There are two crystalline forms of
carbon – diamond and graphite.
 Many amorphous (non-crystalline)
forms of carbon are known
 ALLOTROPES
Soot, coke, animal charcoal,
sugar and lampblack are
examples of amorphous form
of carbon
 STRUCTURE OF
GRAPHITE
Graphite is the most stable allotrope
of carbon.
In graphite, the carbon atoms form
planar sheets of fused six membered
rings
Each carbon atom uses SP2 hybrids to
bond to other carbons within the sheet
 STRUCTURE OF
GRAPHITE
Its remaining PZ orbital forms an
extensive delocalized π-system over
the sheet.
Graphite layers slide over each
other easily because the attraction
between adjacent sheets is weak
(vandaar waal gap)
 GRAPHITE
 High-purity graphite does not readily
burn, even at elevated temperatures.
 Hence the reason why it is used in
nuclear reactors and for high-
temperature crucibles for melting
metals.
 At very high temperatures and
pressures (roughly 2000 °C and 5 GPa),
it can be transformed into diamond.
GRAPHITE
 STRUCTURE OF DIAMOND
 In contrast, diamond has an infinite
three-dimensional network structure
 it has the highest known thermal
conductivity because it distributes the
thermal motion in three dimensions
efficiently. And can be used to identify
fake carbon.
built up from tetrahedral carbon
atoms forming strong covalent
bonds with each other.
Diamond
 USES
 As a result of the structural differences between
diamond and graphite, there is remarkable
differences in their physical properties and uses.

 For instance

 Diamond is the hardest known substance

 It has commercial value as a gemstone

 It has applications in cutting tools and abrasives

 PROPERTIES
 The dominant industrial use of diamond is
cutting, drilling (drill bits), grinding (diamond
edged cutters), and polishing
 The properties of graphite that are exploited
commercially are its inertness, high thermal
stability, electrical and thermal conductivities
 ability to act as a lubricant.
 PROPERTIES and
USES
 Its thermal and electrical properties
make graphite suitable as a refractory
material

 and for uses in batteries and fuel cells.

 PROPERTIES and
USES
The delocalised π-bond readily
explains the conductivity and colour
of graphite,
This properties are absent in
diamond because it has no such
delocalised bonding.
 Oxidizing and reducing
properties
 The elements in +2 oxidation state can
act as reducing agent while those in +4
oxidation state they can act as oxidizing
agent.
 Reducing agent
 M2+ ———> M4+ + 2 e‾
 Oxidising agent
 M4+ + 2e‾ —–> M2+
 2 FeCl3 + SnCl2 ——-> 2 FeCl2 + SnCl4
 Tendency to form pi-pi
bonds
carbon has a strong affinity to form
multiple bonds either with itself or
with the other atoms of similar size
such as oxygen and nitrogen.
This is attributed to small size and
higher electronegativity.
 Tendency to form pi-pi
bonds
The ability to form π-π multiple bond
decreases as the group is descended
due to corresponding increase in size
and decrease in electronegativity of
the atom.
Maximum covalency and tendency to
form complexes
 Due to the absence of d-orbitals, carbon
maximum coordination number is 4.
 However, Si, Ge , Sn and Pb show a
coordination that is greater than 4 due to the
availability of vacant d-orbital
 They can form pentacoordinated and
hexacoordinated complexes.[SiF6]‾, [PbCl6]2-,
[GeCl6]2-.
 Reactivity towards oxygen

 All the elements of group 14 when heated in oxygen

forms monoxide (MO) or dioxide (MO2).
 SiO is formed by reduction of SiO2 with Si i.e.
 SiO2 + Si ——–> 2 SiO
 Lead forms another oxide called trilead tetroxide
 It is obtained by heating PbO with excess of air or
oxygen
 6PbO + O2 —-> 2 Pb3O4 In excess oxygen at 673 K.
 Reactivity towards halogens

 The elements of group 14 form halides

of the formula MX4 and MX2.
 The thermal stability of these halides
decreases with the increasing atomic
number or the size of the halogen
atom.PbCl4 is stable, PbBr4 is unstable
while PbI4 is unknown
 The Reactivity towards water

 Carbon, silicon and germanium do not

decompose water at all. Tin decomposes steam
to form tin dioxide and dihydrogen gas.
 Sn (s) + 2 H2O (g) ———> SnO2 (s) + 2 H2 (g)
 Lead is not affected by water due to the
formation of protective film of lead oxide on its
surface.
 Fullerenes
In recent years there has been an
explosion of research into new
Molecular allotropes of carbon
called fullerenes, typified by the
first compound discovered, C60
 Carbon nanotubes

 There are also called carbon

nanotubes, ‘buckytubes
 It consist of a graphite-like tube,
capped at both ends by a fullerene
hemisphere.
Carbon nanotubes
Carbon nanotubes
Carbon nanotubes
 USES OF CARBON
NANOTUBES
Carbon nanotubes are used for
cleaning polluted water.
Boosting solar energy storage by a
factor of 10,000.
Used as efficient electrical
transmission lines.
Molecular syringes, probes, and
bioelectronic noses.
 SILICON
After oxygen, silicon is the most
abundant element in the earth's
crust.
It occurs extensively as the oxide,
silica, in various forms
 GREENHOUSE EFFECT
 The greenhouse effect is a natural process
that warms the Earth's surface.
 Theincrease in combustion of fossil fuels and
decomposition of limestone for cement
manufacture have given rise to increase in
the CO2 content of the atmosphere.
 Thishas lead to an ‘enhanced greenhouse
effect’, raising the temperature of the
atmosphere. Global warming
 GREENHOUSE EFFECT
The most abundant greenhouse
gases in Earth's atmosphere are:
Water vapor, Carbon dioxide and
methane.
Others are Nitrous oxide,
Ozone,
Chlorofluorocarbons (CFCs)
Hydrofluorocarbons
 USES OF GROUP 14
ELEMENTS
Diamond
• Jewellery
• Manufacturing tools
Graphite
• Lubricant at high temperature
• Manufacturing lead pencils
 USES OF GROUP 14
ELEMENTS
Coal
• Fuel
• Manufacturing coal tar, coke and
coal gas
• Manufacturing synthetic petrol
 USES OF
SILICON
• Electronic devices such as

transistors, diodes and chips

• For producing ferrosilicon

• As a deoxidiser in steal industry

 USES OF
GERMANIUM
• Semiconductor devices

• Making prisms, lenses and windows

in instruments based on IR

• As catalyst
 USES OF TIN

• For tinning of copper and brass utensils

• For making tin foils for wrapping cigarettes

• For making alloy:- solder, bronze and gun metal

• SnO2 coated glass is scratch resistant i.e. aircraft windows

• Used in agriculture to control fungi such as potato blight

 LEAD
Introduction
• Most common compounds:- PbCl2, PbO2,
Pb(NO2)2, Pb3O4, Pb(CH3)4
Physical Properties
• Lead is a soft, malleable and poor metal
• It is also counted as one of the heavy
metals
• Metallic lead has a bluish-white color
after being freshly cut, but it soon
tarnishes to a dull grayish color when
exposed to air
 Uses of LEAD
• For making water pipes

• Lead storage battery

• For making bullets, shots, etc

• Alloys:- solder

• Used for preparing high refractive index glasses