The group IV elements are carbon (C), silicon (Si), germanium
(Ge), tin (Sn) and lead (Pb). All have four electrons on the valence
shell. There is a change in nature from non-metallic to metallic
characteristics as we descend the group. Carbon is a non-metal,
silicon and germanium are metalloids, and tin and lead are metals.
Some of the physical properties ofthe elements as well as unique
features of the elements are described below.
PHYSICAL PROPERTIES
The elements in group IV show characteristic trends in physical
properties on descending the group. Table 15.1 below gives some
properties of the group IV elements.
Table 15.1 Some properties of group IV elements
Element Electronic Atomic 1" ionization Structure Density/g Melting Conductivity
configuration radius/ energy /kJ cm3 point/oC
(outer' shell only) nm mol-I
C 2s" 2p" 0.077 1090 Giant 2.25 3730 Non-
molecular (diamond) conductor
3.51 Sublimes Conductor
(graphite)
Si 3s~ 3p" 0.117 786 Giant 2.33 1410 Semi-
molecular conductor
Ge 4s" 4p2 0.122 762 Giant 5.35 937 Semi-
molecular conductor
Sn 5s" 5p2 0.140 707 Giant 7.28 232 Conductor
metallic
Pb 6s" 6p" 0.154 716 Giant 11.30 327 Conductor
metallic
Atomic radius
Atomic radius increases as we descend group IV. This is expected
as a full orbital is added from one successive element to the next
down the group. The screening effect also increases as these full
inner orbitals shield the outer electrons from the increasing nuclear
charge. This results in the outer electrons being further from the
nucleus causing an increase in the size of the atom. Although
the proton number increases, the screening effect outweighs this
-
increase in nuclear charge.
Ionization energy
The ionization energy decreases down the group. Since the atomic
radius increases down the group, the outer electrons get further
away from the nucleus and less energy is required to remove an
outer electron. There is a large difference in ionization energy
from C to Si, after that the difference is relatively small as shown
in Table 15.1. This is a consequence of the d-block elements
within the periodic table. The d orbitals do not screen the nucleus
as efficiently as the sand p orbitals thus the effective nuclear
charge is higher. This results in little difference in the ionization
energy after silicon.
Structure and bonding
The variation in the physical properties of the group IV elements
is related to the change in structure of the elements from giant
molecular to giant metallic. Silicon and germanium show a giant
molecular structure similar to diamond while tin and lead have
metallic structures. As the atom gets larger, the attraction of
the nucleus for the electrons in the covalent bond gets weaker.
This results in electrons becoming delocalized. The de localized
electrons are attracted to the positively charged nucleus hence
bonding changes from covalent to metallic.
The change in bonding gives rise to the variation in the melting
point and conductivity of the elements. Carbon exists mainly as
graphite and diamond. In diamond, each carbon atom is covalently
bonded to four other C atoms in a tetrahedral arrangement. Its
melting point is 3730°C. No free electrons are present and hence
it is a non conductor of electricity. In graphite, each carbon atom
is bonded covalently to three other carbon atoms. The fourth
electron of each carbon atom forms a delocalized electron cloud.
This allows graphite to conduct electricity.
Silicon has a melting point of 1410°C and is referred to as a
semi-conductor. Silicon forms a giant molecular structure having
strong covalent bonds. Germanium has a melting point of 937°C
and is also a semi-conductor. Tin has a melting point of 232°C
and exists in the form of two allotropes, grey and white tin. Grey
tin is a semi-conductor while white tin is a good conductor of
electricity. Lead has a melting point of 237°C and is a good
conductor of electricity.
The decrease in melting points reflects the increasing weakness
of the covalent or metallic bonds as the atoms get bigger and the
bonds get longer.
Bond Bond energy/kJ mol-I Bond length/nm
C-C 347 0.154
Si-Si 226 0.252
Sn-Sn 150 0.280
We know that the larger the bond energy, the stronger the bond.
Also the shorter the bond length, the greater is the strength of the
bond. Since C-C has the greatest bond energy and the shortest
bond length, it has the strongest bond and has a high melting
point.
THE TETRACHLORIDES OF GROUP IV
Carbon, silicon, germanium, tin and lead all form tetrachlorides
with the formula XCI4. They are all simple covalent molecules
with a tetrahedral shape. The group IV element is at the centre
and bonds with four chlorine atoms by four single covalent bonds.
The shape of the silicon tetrachloride is shown below.
Cl
All the tetrachlorides have low melting and boiling points. They are
volatile liquids at room temperature. As the X - Cl bond becomes •
longer down the group, it gets weaker and the tetrachlorides get
less stable.
THE HYDROLYSIS OF THE TETRACHLORIDES
•
OF GROUP IV
(
With the exception oftetrachloromethane, all of the tetrachlorides
readily react with water to produce a precipitate of the hydrated
dioxide and fumes ofHel. For example
SiCI4(1) + 4H20(I) ~ Si02• 2H20(S) + 4HCl(aq)
Silicon, germanium, tin and lead all have empty d orbitals close
enough in energy to the occupied p orbitals. These atoms allow
incoming water molecules to donate a lone pair to their d orbitals
to form a bond. For example in SiCI4, a water molecule can
donate a lone pair into the empty 3d orbitals of silicon to form
a dative covalent bond. As the Si - 0 bonds form, the Si - Cl
bonds weaken and break. The bonds make and break one by one
until all four chlorine atoms are displaced. Thus hydrolysis of the
tetrachloride occurs.
Tetrachloromethane (CC14) is immiscible in water and does not
undergo hydrolysis. The empty 3d orbitals in carbon are too
different in energy for carbon to expand its octet to form dative
bonds with the water molecules. Thus a similar mechanism
for hydrolysis cannot occur and tetrachloromethane shows no
reaction in water.
THE OXIDES OF GROUP IV
Table 15.2 and table 15.3 below give some properties of the
oxides of the group IV elements.
Table 15.2 Properties of the dioxides of group IV elements
The dioxides Boiling Structure Acid-base Thermal
(+4 oxidation state) point/DC nature stability
CO, -78 Simple molecular Acidic Stable at high
temperatures
Si02 2590 Giant molecular Acidic Stable at high
temperatures
Ge02 1200 Intermediate Amphoteric Stable at high
between giant temperatures
molecular and ionic
Sn02 1900 Intermediate Amphoteric Stable at high
between giant temperatures
molecular and ionic
Pb02 Decomposes on Intermediate Amphoteric Decomposes on
heating between giant wanlllng
molecular and ionic
Table 15.3 Properties of the monoxides of group IV elements
The monoxides Structure Acid-base Thermal stability
(+2 oxidation state) nature
CO Simple molecular Neutral Readily oxidize to the dioxide
SiO Simple molecular Neutral Readily oxidize to the dioxide
GeO Predominantly ionic Amphoteric Readily oxidize to the dioxide
SnO Predominantly ionic Amphoteric Readily oxidize to the dioxide
PbO Predominantly ionic Amphoteric Stable
Bonding
All the elements in group IV have four electrons in their valence
shell (ns2 np2). None form the X4+ ion in the solid state due to
the high ionization energies required to remove four successive
electrons from the atom. Consequently, bonding is covalent.
Going down the group, germanium, tin and lead tend to form
ionic compounds in which the group IV element has an oxidation
state of +2. In these compounds, the Ge2+, Sn2+ and Pb2+ ions are
formed when the two p electrons are lost from the valence shell.
The two s electrons remaining on the valence shell is relatively
stable and not easily removed. This is because the effective
nuclear attraction towards them is greater since the d orbitals do
not screen the nucleus as efficiently as the sand p orbitals. This
is called the inert pair effect and it occurs as a result of the two
remaining electrons behaving inertly since the ionization energy
required for their removal is very large.
Oxidation states
Compounds of group IV elements exist with oxidation states +2
and +4. The +4 state is most common in compounds. For example
when the elements are heated in oxygen, with the exception of
lead, they all form oxide with oxidation state +4. It must be noted
however that the relative stabilities ofthe +2 state relative to the +4
state increase down the group as bonding changes from covalent
to ionic. In carbon and silicon, the +4 state is more stable than the
+2 state. CO is readily oxidized to CO2 while SiO is unstable and
does not exist under normal conditions. Germanium, tin and lead
tend to form ionic compounds and form oxides of both +2 and • •
+4 state. GeO is less stable than Ge02 and is oxidized to Ge02.
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 increase
•
••
in stability of the +2 oxidation state on going down the group is
explained in terms of the inert pair effect.
The standard electrode potentials of the X4+( aq ) / X2+(aq ) for
•
germanium, tin and lead can be used to show the relative stabilities
of the +2 and +4 oxidation states of these elements.
Ge4+ + 2 e- ~
~ Ge2+ EO = -1.60 V
~
Sn4+ + 2 e- ~ Sn2+ EO = + 0.15 V
Pb4+ + 2 e- ~
~ Pb2+ EO = + 1.80 V
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 nature of the oxides
The basic character of the oxides increases down the group. The
dioxides are more acidic than the monoxides.
The dioxides
The bonding in CO2 and Si02 is covalent. These oxides show
acidic behaviour. They react with alkalis to form salts.
CO2 + 2NaOH ~ Na2C03 + HzO
sodium carbonate
Si02 + 2NaOH ~ NazSi03 + H20
sodium silicate
The bonding in Ge02, Sn02 and PbOz shows both ionic and
covalent character. These oxides are amphoteric. They show both
acidic and basic properties.
For example tin (IV) oxide reacts with concentrated hydrochloric
acid to give SnCI4.
Sn02 + 4HCI ~ SnCl4 + 2HzO
•• Cone. He1
This dissolves in excess HCI to form the complex [SnCI6]2-.
In the case of lead (IV) oxide, the reaction has to be done at low
temperature because the lead (IV) chloride formed is unstable
and decomposes to give lead (II) chloride and chlorine gas .
• PbOz + 4HCI ~ PbCl2 + Clz + 2HzO
The dioxides also react with alkalis. For example, tin (IV) oxide
reacts with concentrated sodium hydroxide solution to give the
complex [Sn(OH)6P-.
SnOz + 20H- + 2H20 ~ [Sn(OH)6P-(aQ)
In the case of lead (IV) oxide, molten sodium hydroxide is used.
The monoxides
CO and SiO are neutral and react neither with acids or alkalis.
GeO, SnO and PbO are amphoteric. They all react with
concentrated hydrochloric acid. For example, tin (II) oxide reacts
with hydrochloric acid to form tin (II) chloride.
SnO(S) + 2HCI(aq) ~ SnCI2(aq)+ H20(l)
In the reaction with lead (II) oxide, insoluble lead (II) chloride
is formed. This however dissolves in excess concentrated
hydrochloric acid to form the soluble complex [PbCI4]2-.
GeO, SnO and PbO also react with bases. For example
SILICATES
Some geologists estimate that 90% of the Earth's crust is made
up of silicates. The basic chemical unit of silicates is the Si044-
tetrahedron. The central silicon ion has a charge of positive four
while each oxygen atom has a charge of negative two. This
condition leaves each oxygen atom with the option of bonding
to another silicon ion and thus links one Si044- tetrahedron to
another and another. Silicates tetrahedrons can combine to form
chain, sheet and ring structures.
single chain silicate double chain silicate sheet silicate Fig. 15.1
In silicates, some ofthe negatively charged oxygen atoms are able
to interact with positively charges ions like Mg2+, Ca2+and AP+.
•
Asbestos is a single chain silicate which contains magnesium,
calcium or iron ions. It is fire resistant and a poor conductor of
heat. It is used as building material however care must be taken
because exposure to asbestos fibers can cause lung cancer.
Talc is a sheet silicate containing magnesium ions. It is a soft,
slippery material which is used in soaps and talcum powder.
Clays are also sheet silicates but about half of the silicon
atoms are replaced by aluminium atoms. They are also called
aluminosilicates. When clay is wet, water is trapped between
the sheets and the material becomes flexible and can be molded
into different shapes. If the clay is heated at high temperatures,
water is removed and a three dimensional giant structure similar
to quartz is formed.
Ceramics is the name given to materials which are made from clay
and then heated at high temperatures. Ceramic products include
pottery, bricks and tiles. More recently, ceramic production is
geared towards crystalline ceramics which is considered to have
superior properties to those that were produced in years before.
These are designed to have properties such as hardness, strength
and ability to withstand high temperatures for applications such
as heat shields in spacecrafts, and amour protection in military
vehicles .
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1. Explain the variation of the following physical properties of
the group IV elements in terms of structure and bonding.
(a) Melting point
(b) 151 ionization energy
(c) Metallic character
(d) Electrical conductivity
2. Group IV elements show the +2 and +4 oxidation states in
many compounds.
(a) Account for the relative stability of the oxides of the
group IV elements of oxidation states +2 and +4.
(b) What is the trend in the acid-base nature of the oxides
of the group IV elements in the +4 oxidation state?
Illustrate your answer with suitable equations.
(c) Describe the trend in bonding of the oxides ofthe group
IV elements in the +4 oxidation state?
(d) Explain why carbon dioxide is a gas and silicon dioxide
is a high melting point solid.
3. The group IV tetrachlorides are volatile, non-polar liquids.
(a) Draw the molecular shape of carbon tetrachloride.
(b) Explain why carbon tetrachloride is a non-polar
•
off!)
molecule.
(c) Explain the trend in the volatility of the tetrachlorides
of the group IV elements.
4. With the exception oftetrachloromethane, the tetrachlorides
of group IV elements are readily hydrolysed by water.
•
(a) Write an equation for the hydrolysis of one of the
tetrachlorides with water.
(b) Account for the unreactivity oftetrachloromethane with
water.
5. Some properties of ceramics include hardness, strength and
ability to withstand high temperatures. Explain the structure
of silicon IV oxide which makes it suitable as the building
block of ceramics.
