CHAPTER 24: Group IV

24.1 Physical Properties of Group IV Elements

24.2 Group IV Chlorides
24.3 Group IV Oxides
24.3 Relative Stability of +2 and +4 Oxidation States

Learning outcomes:

(a) outline the variation in melting point and in electrical conductivity of the elements and
interpret them in terms of structure and bonding.
(b) describe and explain the bonding in, molecular shape and volatility of the tetrachlorides.
(c) describe and explain the reactions of the tetrachlorides with water in terms of structure and
bonding.
(d) describe and explain the bonding, acid-base nature and thermal stability of the oxides of
oxidation states II and IV.
(e) describe and explain the relative stability of higher and lower oxidation states of the elements
in their oxides and aqueous cations including, where relevant, E values.
24.1 Physical Properties of Group IV Elements
Introduction to Group IV elements

1) Group IV elements are p-block elements with a characteristic outer shell

configuration of ns²np².

2) Group IV elements exist in two different oxidation states, +2 and +4 states.

The +2 state compounds become more stable going down the Group while the
+4 state compounds become less stable going down the Group. The reasons will
be explained later.

Variation in structure

1) Going down the Group, there is a trend of non-metal to semi-metal to metal.

2) Carbon exists in two different allotropes, diamond and graphite(for the structures,
refer to Chapter 5), they are both giant covalent compounds.

3) Silicon and germanium have the same type of structure as diamond. They
are both giant covalent compounds.

4) There are two types of tin:

i. Grey tin or alpha-tin has a giant covalent structure, same as the one diamond
has.
ii. White tin or beta-tin(the more common one) has a distorted 12-co-ordinated
metallic structure with metallic bonds.

5) Lead is a metal and it has a simple 12-co-ordinated metallic structure.

Variation in melting and boiling point

1) From carbon to germanium, the melting

point decreases. This is because going down
the Group, the covalent bond length
increases. Longer bonds have lower bond
energies. Less energy is required to overcome
the covalent bonds, therefore melting point is
lower.

2) i. Tin has a lower melting point than lead. This is because in the solid state,
metallic tin has a distorted structure, resulting the metallic bonds being
less effective. This factor outweighs the larger atomic size of lead.
Therefore, less energy is required to overcome the metallic bond in tin.
ii. Tin has a higher boiling point than lead, this is because in the liquid state,
there is no ordered arrangement between the atoms. The larger atomic
size of lead resulting the metallic bond being longer and weaker.
Therefore, less energy is required to overcome the metallic bond in lead.

Variation in electrical conductivity

1) The electrical conductivity increases down the Group as the nature of the
elements changes from non-metal to semi-metal to metal.

2) i. Carbon(diamond form) does not conduct electricity. This is because

all the outer electrons are used in covalent bonding. Therefore there are no
free and moving electrons to conduct the electricity.
ii. However, carbon(graphite form) conducts electricity. This is because in
the graphite structure each atom donates one electron to a delocalised system
of electrons(for more details, refer to Chapter 5). Therefore there are free electrons
present to conduct the electricity.

3) Silicon and germanium are semi-conductors, whose conductivity is

between that of metals and non-metals.

4) Tin and lead are metals, hence they are good conductors of electricity.
This is because each atom involved in metallic bonding donates electrons into
the sea of delocalised electrons. Therefore free electrons are present to conduct
electricity.
24.2 Group IV Chlorides
Introduction to Group IV chlorides

1) All Group IV chlorides are simple covalent molecules which exist as liquid at
room temperature with the general formula of XCl4, where
X = A Group IV element.

2) All of them have a tetrahedral shape with a bond

angle of 109.5°. A typical example is carbon
tetrachloride:

3) The boiling point of Group IV tetrachlorides increases

down the Group. This is because as the number of
electrons increases, more temporary dipoles can be set up
between the molecules. Hence the van der Waals' forces
of attraction are stronger.

Note: Carbon tetrachloride, CCl4 is an exception.

Reaction with water, H2O(Hydrolysis)

1) i. Carbon tetrachloride does not react with water. If carbon tetrachloride is

added to water, two immiscible layers are formed.
ii. There are two reasons for this:
- Carbon is a small atom cluttered with big chlorine atoms. This
causes the water molecule to have difficulty approaching
the bulky molecule. Even if the water molecule successfully
gets in, the transition state is very cluttered and unstable, the
activation energy is very high.
- Also, there isn't any convenient orbital on the carbon that the lone pair
of the water molecule can attaches itself to.

2) i. Silicon, germanium and tin tetrachlorides(also called silicon(IV)

chloride, germanium(IV) chloride and tin(IV) chloride) hydrolyses in water to
form an oxide and steamy fumes of hydrogen chloride.
XCl4 + 2H2O → XO2 + 4HCl ; where X = Si/Ge/Sn/Pb
ii. Unlike carbon tetrachloride, this is possible because the Group IV atoms are
bigger, the molecules are less bulky.
3) Lead(IV) chloride behaves similarly as silicon, germanium and tin
tetrachlorides. However, the heat released during the reaction would tend to
decompose lead(IV) chloride, PbCl4 to lead(II) chloride, PbCl2.
PbCl4 → PbCl2 + Cl2

4) The hydrolysis reactions become more vigorous going down the Group. This
is because going down the Group, the X-Cl bond becomes longer. A longer
bond has a lower bond energy and it is more easy to be broken.

Relative stability of the oxidation states of Group IV chlorides

1) A fact about Group IV elements is as such:

i. Going down the Group, compounds with a +2
oxidation state Group IV element become more stable.
ii. Going up the Group, compounds with a +4 oxidation
state Group IV element become more stable.

2) This means that the +4 oxidation is less favourable down the Group while the
+2 oxidation state is more favourable down the Group.

3) From carbon to tin, the +4 oxidation state is more stable than +2 oxidation
state. However, for lead, the +2 oxidation is more stable. This is why lead(IV)
chloride decomposes to lead(II) chloride on heating.

24.3 Group IV Oxides

Introduction to Group IV oxides

1) Group IV elements form two types of oxides: monoxide and dioxide. This is
because the elements have two possible oxidation states, +2 and +4.

2) Monoxides include:
i. carbon monoxide, CO
ii. silicon monoxide/silicon(II) oxide, SiO
iii. germanium monoxide, GeO
 iv. tin(II) oxide, SnO
v. lead(II) oxide, PbO

3) Dioxides include:
i. carbon dioxide, CO2
ii. silicon dioxide/silicon(IV) oxide, SiO2
iii. germanium dioxide, GeO2
iv. tin(IV) oxide, SnO2
v. lead(IV) oxide, PbO2

4) i. Carbon monoxide and carbon dioxide is a simple covalent

molecule which exists as a gas at room temperature.

5) i. Silicon monoxide and silicon dioxide has a giant covalent structure(for

more details, refer to Chapter 5).
ii. The difference in structure between carbon dioxide and silicon dioxide is due
to silicon atom being larger. When the atom is larger, the overlapping of p
orbitals to form a π bond is less complete and a π bond as such is very
unstable. So, silicon bonded with the oxygen atoms in such a way that π bonds
are not formed.

6) Germanium monoxide and germanium dioxide have the same structure

as silicon monoxide and silicon dioxide respectively.

7) Tin(II) oxide and tin(IV) oxide have a giant ionic lattice structure with ionic
bonds between the Sn²⁺/Sn⁴⁺ and O²⁻.

8) Lead(II) oxide and lead(IV) oxide have a giant ionic lattice structure with
ionic bonds between the Pb²⁺/Pb⁴⁺ and O²⁻.

Group IV monoxides

1) Carbon monoxide is a slightly acidic oxide which is only slightly soluble in

water. It reacts with hot and concentrated sodium hydroxide, NaOH to give a
solution of sodium methanoate.
CO + NaOH → HCOONa

2) i. Germanium, tin and lead monoxides are amphoteric oxides. They

can act as an acid as well as a base.
 ii. As a base : XO + 2HCl → XCl2 + H2O ; where X = Ge/Sn/Pb
iii. As an acid : XO + 2NaOH → Na2XO2 + H2O ; where X = Ge/Sn/Pb

Group IV dioxides

1) Carbon dioxide is a slight acidic oxide which is only slightly soluble in

water. It reacts with cold sodium hydroxide, NaOH to give either sodium
carbonate or sodium hydrogencarbonate solution, depending on the proportion.
CO2 + 2NaOH → Na2CO3 + H2O or
CO2 + NaOH → NaHCO3

2) Silicon dioxide is weakly acidic. It reacts with hot and concentrated sodium
hydroxide to give sodium silicate. However, it does not react with water due to
the strong covalent bonds need to be broken.
SiO2 + 2NaOH → Na2SiO3 + H2O

3) i. Germanium, tin and lead dioxides are amphoteric oxides. They can
act as an acid as well as a base.
ii. As a base : XO2 + 4HCl → XCl4 + 2H2O ; where X = Ge/Sn/Pb
For germanium and tin dioxides, hot and concentrated hydrochloric acid is
used. However, for lead dioxide, cold hydrochloric acid is used. This is
because lead dioxide will decompose if the temperature increases.
iii. As an acid : XO2 + 2NaOH → Na2XO3 + H2O ; where X = Ge/Sn/Pb
For all reactions, hot and concentrated sodium hydroxide is used.

Thermal stability of Group IV oxides

1) Carbon, silicon and germanium oxides will disproportionate on

heating.
2XO → X + XO2 ; where X = C/Si/Ge

2) Tin and lead monoxide are stable on heating.

3) This reflects the stability of +2 oxidation state of Group IV elements increases

down the Group.

4) All dioxides are stable on heating except lead dioxide(lead(IV) oxide). This
decomposes on heating to give lead(II) oxide and oxygen.
2PbO2 → 2PbO + O2
5) This shows the stability of +4 oxidation state of Group IV elements decreases
down the Group.

24.3 Relative Stability of +2 and +4 Oxidation

States
The stability of +2 and +4 oxidation states

1) i. +4 compounds at the top of the Group is more stable than at the bottom.
ii. +2 compounds at the bottom of the Group is more stable than at the top.

2) For carbon, carbon dioxide(+4) is more stable than carbon monoxide(+2).

Therefore, carbon monoxide is readily oxidised to carbon dioxide, it is a
good reducing agent. For example, it reduces iron(III) ions to iron.
Fe2O3 + 3CO → 2Fe + 3CO2

3) For lead, lead(II) oxide(+2) is more stable than lead(IV) oxide(+4). Therefore,
lead(IV) oxide is readily reduced to lead(II) oxide, it is a good oxidising
agent. For example, lead(II) oxide oxidises hydrochloric acid to chlorine.
PbO2 + 4HCl → PbCl2 + Cl2 + 2H2O

4) Between these extremes, there is a gradual change in stability of the +2

compared with the +4 state.
i. The +4 state of germanium compounds is more stable than the +2 state.
Therefore, germanium(II) compounds are good reducing agents.
ii. The +4 state of tin compounds is slightly more stable than the +2 state.
Therefore, tin(II) compounds are weak reducing agents.

5) This can be interpreted from the E° values of the ions of Group IV elements in
aqueous solutions.
6) i. The more positive the value of E°, the easier it is to reduce the species on the
left of the half-equation.
ii. The less positive the value of E°, the easier it is to oxidise the species on the
right of the half-equation.