GROUP IV

CARBON TO LEAD
The Group IV elements show very clearly the trend from non-metals through metalloids to
metals on descending the group. The elements are, in order of increasing atomic number; carbon
(C), silicon (Si), germanium (Ge) tin (Sn) and lead (Pb). Carbon is a non-metal, silicon and
germanium are metalloids and tin and lead are metals. All have the valence shell electronic
structure of ns2np2.
The predominant oxidation number of the elements is +4 but going down the group the stability
of the state with oxidation number +2 increases. Compounds in which the elements have
oxidation number +2 tend to be predominantly ionic and those in which the element has
oxidation number +4 tend to be predominantly covalent in character. Passing down the group, the
strength of the covalent bonds formed with other elements decreases and there is an increasing
tendency to show a covalency of 2. The behaviour of later members of the group showing a
valency of 2 less than the group valency through a failure to use their s electrons, is called the
inert pair effect.
These s electrons are not easily removed as the nuclear pull on them is very strong. The d
orbitals do not effectively shield these electrons from the attraction of the nucleus as s and p
orbitals do.
Tin (II) compounds are reducing agents because tin (IV) is the more stable oxidation state of tin,
but lead (IV) compounds are oxidizing agents because lead (II) is the more stable oxidation state
for lead.

PHYSICAL PROPERTIES
The physical structures of the elements of Group IV are suggested by their melting points and
electrical conductivities. The carbon allotropes, diamond and graphite are solids with a giant
covalent structure. In diamond, each atom is bonded to four other atoms by single covalent
bonds. Graphite has a layered structure with each carbon atom bonded to three others. Such
structures are associated with high melting points. The electrical conductivity of diamond is very

low confirming the lack of delocalized electrons. Graphite has an electrical conductivity 1015
times greater than diamond due to presence of delocalized valence electrons.
Silicon and germanium have similar structures to diamond. However, their electrical
conductivities are 1014 (Sn) and 1011 (Ge) times greater than that of diamond. These elements are
semi-conductors.
Tin and lead are metals and they have high electrical conductivities.

THE TETRACHLORIDES OF GROUP (IV) ELEMENTS

BONDING OF THE TETRACHLORIDES
The tetrachlorides all contain the Group (IV) elements with oxidation number +4. They are all
simple covalent molecules with a tetrahedral shape.

The tetrachlorides are volatile liquids at room temperature with low melting and boiling points.
Stability of the tetrachlorides decreases going down the group with lead (IV) chloride
dissociating at room temperature to form lead (II) chloride and chlorine.
PbCl4 (s)

PbCl2 (s)

Cl2 (g).

HYDROLYSIS OF THE TETRACHLORIDES

Tetrachloromethane, CCl4, is immiscible with water and does not react with it. The reaction,
given enough time (many years) may actually happen as it proceeds at an extraordinarily slow
rate.

The other tetrachlorides react readily with water. Example, silicon tetrachloride, SiCl4, contains a
longer and weaker X------Cl bond than the carbon, and reacts with water to produce a white
precipitate of hydrated silicon dioxide and hydrogen chloride fumes. It gives of fumes in moist
air.
SiCl4 (l) + 2H2O(l) SiO2 (s)

+ 4HCl(l) .

SiCl4 (l) + 4H2O(l) SiO22H2O (s)

+ 4HCl(l).

All the elements except carbon have empty d orbitals close enough in energy to the occupied
p orbitals. These atoms allow the incoming water molecules to donate a lone pair to their d
orbitals to form a dative covalent bond. As the bond forms between the group (IV) element and
the oxygen of water, Si -----O, the bond between the group (IV) element and chlorine, Si -----Cl,
weakens and breaks. This continues until all the chlorine atoms have been displaced.
Tetrachloromethane is unable to react in this way as the empty 3d orbitals are too different in
energy for the carbon to expand its octet to form dative covalent bonds with water molecules.
The ease of hydrolysis decreases in the order Si < Ge < Sn < Pb as metallic character increases
down the group.

THE OXIDES OF GROUP (IV) ELEMENTS

Bonding between group (IV) elements and oxygen is covalent but changes to ionic going down
the group as the oxidation state changes to +2. When the elements are heated in oxygen they all,
with the exception of lead, form oxides of oxidation number +4. In carbon and silicon the +4
state is more stable than the +2 state. Carbon monoxide, CO, is readily oxidized to give CO2,
while silicon monoxide, SiO, is unstable and does not exist under normal conditions.
Germanium, tin and lead form oxides of both +2 and +4 state. GeO is less stable than GeO2 and
is oxidized to GeO2. The +4 state in tin is slightly more stable than the +2 state while the +2 state
in lead is more stable than the +4 state.
The standard electrode potentials of the X4+(aq) / X2+(aq) for germanium, tin and lead can be used to
show the relative stabilities if the +2 and +4 oxidation states of these elements.
Ge4+ +

2e-

Ge2+

E = - 1. 60V

Sn4+ +

2e-

Sn2+

E = + 0. 15V

Pb4+ +

2e-

Pb2+

E = + 1. 80V

As the standard electrode potentials get more positive from Ge4+ to Pb4+, aqueous ions in the +4
state is more easily reduced to the +2 state.

ACID/ BASE CHARACTER OF THE OXIDES

Group (IV) elements trend from non-metals to metals down the group and as such the basic
character of the oxides increases going down the group. However, the dioxides are more acidic
than the monoxides.
Carbon dioxide, CO2, is an acidic gas. It dissolves in water to give an acidic solution of pH 5.
CO2 (g) + H2O(l)
H2CO3 (aq)

+ H2O(l)

H2CO3 (aq).
H3O+(aq) + HCO32-(aq).

It neutralizes bases to give carbonates

CO2 (g) + 2NaOH(aq) Na2CO3 (aq) + H2O(l).
Silicon dioxide, SiO2, is also acidic but it is a solid with a high melting point, 1610OC. it reacts
with molten bases to give silicates.
SiO2 (g)

+ 2NaOH(aq) Na2SiO3 (aq) + H2O(g).

GeO2, SnO2 and PbO2 are amphoteric oxides.

Example, tin (IV) oxide reacts with concentrated hydrochloric acid to give tin (IV) chloride.
SnO2(s)

+ 4HCl(aq)

SnCl4

+ 2H2O(l).

Tin (IV) chloride dissolves in excess hydrochloric acid to form the complex [SnCl6]2-.
Lead (IV) oxide will also react with concentrated hydrochloric acid to form lead (IV) chloride.
This reaction must occur at low temperatures as the lead (IV) chloride will decompose to lead
(II) chloride and chlorine gas.
PbO2(s)

+ 4HCl(aq)

PbCl2

+ Cl2 (g) + 2H2O(l).

Tin (IV) oxide reacts with concentrated sodium hydroxide to form a complex [Sn(OH)6]2-.
SnO2 (s) + 2OH-(aq) + 2H2O (l)

[Sn(OH)6]2-(aq).

Lead (IV) oxide reacts with molten sodium hydroxide.

PbO2 (s) + 2NaOH (aq)

Na2PbO2

H2O.

The monoxides of carbon and silicon are neutral and do not react with neither acids nor alkalis.
The monoxides of the other elements of the group, GeO, SnO and PbO are amphoteric.
Tin (II) oxide reacts with hydrochloric acid to form tin (II) chloride.
SnO(s) + 2HCl(aq)

SnCl2 (aq)

+ H2O(l).

In the reaction with lead (II) oxide, insoluble lead (II) chloride is formed. This can then be
dissolved in concentrated hydrochloric acid to form the soluble complex [PbCl4]2-.
Lead (II) oxide reacts with nitric acid to give salt and water.
PbO (s) +

HNO3 (aq)

Pb(NO3)2 (aq) + H2O(l).

GeO, SnO and PbO also react with alkalis.

SnO (s) + 2OH-(aq)

SnO22-(aq) + H2O(l).

RELATIVE STABILITY OF AQUEOUS CATIONS OF GROUP (IV)

ELEMENTS
The elements carbon to germanium do not form cations in aqueous solutions since they are
covalent. However, tin and lead do. This is supported by the E values for the equation

M4+(aq)

+ 2e- M2+(aq) of the elements.

USES OF CERAMICS
Ceramics are objects made from clay hardened by heat.
Ceramic products include pottery, bricks and tiles. They can also be used to make gas turbine
engines, synthetic bones, dental implants among other things.

PRACTISE QUESTION