ELECTRICAL CONDUCTIVITY
ELEMENTS
*on descending group 14, increase in both
number of occupied electron shells and
screening effect. Increase in screening effect is
larger than the increase in nuclear charge.
* This causes the effective nuclear charge to
decrease and force of attraction between the
nucleus and the valence electrons becomes
weaker. Thus, atomic radius increases.
*Increasing atomic radius causes the valence
electrons to be more delocalized. Thus, metallic
character increases.
Graphite contains delocalized electrons while
diamond does not. Thus, graphite is a good
conductor for electricity.
MELTING POINT
*melting point decreases down the group
Carbon, silicon and germanium have giant
covalent structure with strong covalent bonds
between atoms. A lot of energy is required to
break the covalent bonds. As a result, they have
high melting and boiling points. Atomic radius
increases from carbon to silicon to germanium.
Thus, the covalent bond becomes weaker from
carbon to germanium
Tin and lead are metals. Due to their large
atomic size, the metallic bonds are relatively
weak. Thus, their melting point and boiling
points are lower than the first three elements.
Lead has bigger atomic radius compared to tin,
its melting point is higher because lead has a
more close-packed structure than tin
TETRACHLORIDES OF GROUP 14
oxidation state. Lead(IV) compounds are good
*BOILING POINT OF TETRACHLORIDES
-exist as simple covalent molecules are held
together by weak van der Waals forces. They are
volatile liquids. As relative molecular mass
increases, van der Waals forces between
molecules become stronger. Thus, boiling point
increases.
*THERMAL STABILITY
-going down Group 14, atomic size of elements
increases. This causes the M-Cl bond length to
increase thus becomes weaker. Thermal stability
of tetrachlorides decreases down Group 14.
*HYDROLYSIS
-all tetrachlorides, except CCl4, are readily
hydrolysed by water to liberate white fumes of
hydrogen chloride
-SiCl4, GeCl4, SnCl4, PbCl4 use their empty d
orbitals of the central atom to form dative bonds
with water molecules
-CCl4 does not undergoes hydrolysis because
carbon atom does not have d orbitals to receive
lone pairs from oxygen atoms in water
molecules
RELATIVE STABILITY OF +2 AND +4 O.S
+4 oxidation state of C, Si, Ge and Sn is more
stable than +2 oxidation state. Hence, their +2
oxidation state are good reducing agents where
they can be oxidized readily to +4 oxidation
state
For Pb, +2 oxidation state is more stable than +4
oxidizing agents
An increasing E◦ value shows the tendency of
+4 oxidation state to be reduced to +2 oxidation
state increases down the group. This indicates a
decreasing stability of +4 oxidation state down
the group.
*INERT PAIR EFFECT ( usually for lead )
Valence electronic configuration of lead is 6s2
6p2
Energy difference between 6s and 6p subenergy
levels is high. Thus, it is difficult for 6s electrons
to be promoted to the 6p orbitals
The two 6s electrons will remain as an inert
pair that will not be involved in chemical
bonding. This is called an inert pair effect
Lead tends to form stable compounds with the
+2 oxidation state
*OXIDES OF GROUP 14 ELEMENTS
-form monoxides, MO and dioxides, MO2
-Tendency to form stable oxides decreases
down the group. Oxides become more basic on
going down the group because of increasing
metallic character
-Oxides with +4 oxidation state are more acidic
than oxides with +2 oxidation states
*BONDING, THERMAL STABILITY OF
MONOXIDES
CO, SiO exist as simple covalent molecules
while GeO, SnO and PbO are ionic with
covalent characteristics
Monoxides of carbon, silicon, germanium and
tin are easily oxidized to their dioxides while
lead monoxide is stable
CO: -neutral, toxic gas
-exist as simple covalent molecules
-oxidised readily to CO2 because +4 oxidation
state of carbon is more stable
SiO: -exist as simple covalent molecules
-exist only in gaseous phase at temperature
above 2000◦C. When cooled, it undergoes
disproportionation to form Si and SiO2.
GeO, SnO: -ionic with covalent character
-oxidised easily to their respective dioxides with
a more stable +4 oxidation state
PbO: - ionic, with covalent character
-stable yellow solid
-when heated in air to 400◦C, red oxide of
dilead(II) lead(IV) oxide, Pb3O4 is formed but
PbO is reformed at 470◦C
*ACID-BASE PROPERTY OF MONOXIDES
CO and SiO are neutral
GeO, SnO, and PbO are amphoteric (dissolved
in hot, dilute acids and hot, concentrated alkali)
*BONDING. THERMAL STABILITY OF
DIOXIDES
CO2, SiO2, GeO2, SnO2 are stable, PbO2 is
unstable
CO2: -thermally stable oxide, exist in room
temperature
-exist as simple covalent, non-polar molecule
where carbon atom is sp hybridized
SiO2: -thermally stable solid with high melting
point
-giant covalent lattice with structure similar to
diamond where silicon atom is sp3 hybridised
GeO2, SnO2: -thermally stable
-structure intermediate between giant covalent
and ionic
PbO2: -brown solid with a structure intermediate
between giant covalent and ionic
-thermally unstable and decomposes to PbO and
O2 when heated to 300◦C
*ACID-BASE PROPERTY OF DIOXIDES
CO2 and SiO2 are acidic. CO2 is slightly soluble
in water to form carbonic acid but SiO2 is
insoluble in water
CO2 dissolves in dilute alkalis to form
carbonates
SiO2 dissolves in hot, concentrated alkalis to
form silicates
GeO2, SnO2 and PbO2 are amphoteric