Group 14

Vocabulary
• Occurrence, extraction, obtain, ore, refining

• Trend, similarity / dissimilarity

• Inert, brittle, stable / unstable, conductivity

• Ionic / covalent, metal, non-metal, semi-metal, metalloid

• The metallic nature of the elements……as you go

……within the group.
 Learning Objectives
• know the occurrence of, and be able to compare and contrast,
methods of extraction of the elements
• recognise trends in chemical and physical properties down the
group
• be able to explain the shapes of the molecules of the
compounds
• know and understand trends in oxidation states down the
group
• know and be able to explain the properties of the oxides of
oxidation states II and IV
• know and be able to explain the relative stability of the II and
IV oxidation state in aqueous solution
 Introduction
• The Group IV elements carbon, silicon, germanium, tin,
lead, flerovium exhibit a marked change (dissimilarity)
among the elements in the same group.

• The elements vary from non-metal to metals to in 1998

synthesized element Flerovuim (Fl 114).
 Carbon
• Diamond is produced mostly by Russia, Botswana, Congo,
Canada, and South Africa. 80% of all synthetic diamonds are
produced by Russia.

• China produces 70% of the world's graphite. Other graphite-

mining countries are Brazil, Canada, and Mexico.

• Fullerene synthesis methods:

• the arc method

• the combustion method which is preferred for large scale

industrial production.
 Silicon
• The second most abundant element in the Earth’s crust,
about 28% by mass.

• Commonly found as silicon oxide (also known as silica) in

a variety of forms such as sand, quartz and flint. It is also
found as silicates in rocks and clay.
 Preparation of Silicon
1. By reduction of silica with carbon in an electric furnace:

SiO2(s) + 2C(s) → Si(s) + 2CO(g)

2. Extremely pure silicon can be obtained by the reaction of

silicon(IV) chloride with hydrogen:

SiCl4(s) + 2H2(g) → Si(s) + 4HCl(g)

followed by zone refining of the resultant silicon

 Germanium
• Germanium is extracted from the ores of metals such as
zinc. In Russia and China, germanium is also separated
from coal deposits.
• The ores are treated with chlorine to form germanium
tetrachloride, which is mixed with hydrogen gas. Then the
germanium is further refined by zone refining.

• TASK: write the reaction equation for Germanium extraction.

What could be the starting material (Germanium compound)?
 Tin and Lead
• Tin: The tin mineral cassiterite (SnO2) is heated with coke.

• Lead: The most commonly mined lead ore is galena

(PbS). The ores are mixed with coke and limestone and
roasted to produce pure lead. Most lead is recycled from
lead batteries.
The Group 14 elements
• outermost shell electronic configuration ns2np2

Element Electronic configuration

Carbon [He] 2s22p2 2,4
Silicon [Ne] 3s23p2 2,8,4
Germanium [Ar] 3d104s24p2 2,8,18,4
Tin [Kr] 4d 105s25p2 2,8,18,18,4
Lead [Xe] 4f 145d 106s26p2 2,8,18,32,18,4

TASK: What is the electron configuration for Flerovium?

 Structure and Bonding
• Most common structure: giant covalent structure

o Carbon (all allotropes: graphite, diamond, fullerenes)

o Silicon
o Germanium
o Grey tin (an allotrope of tin)

Allotropes are different structures of the same element.

 Structure of diamond
• Extremely hard

• Chemically inert

• All electrons are localized

➔ non-conductor
 Structure of graphite
• The layers slide over each
other easily

➔ brittle and soft

• Electrons between layers are

delocalized

➔ conducts electricity along the

layers
 Fullerene
• A fullerene is an allotrope of carbon in the form of a hollow
sphere, ellipsoid, tube, and many other shapes.

• Spherical fullerenes, also referred to as

Buckminsterfullerenes or buckyballs, resemble the balls used
in football.

• Cylindrical fullerenes are also called carbon nanotubes

(buckytubes).

• Fullerenes are similar in structure to graphite.

• Physical properties: heat resistance and superconductivity.

Silicon and Germanium
• Network lattice: the atoms are covalently bonded to one
another.

http://physicsopenlab.org/wp-content/uploads/2018/01/250px-DiamondCubic.gif
 Tin
• Two allotropes: white tin and grey tin

• White tin: stable form, metallic lattice

structure, atoms are held together by
metallic bonding. Conducts electricity,
shows the properties of a typical
metal.

• Grey tin: network lattice structure

similar to that of diamond.

• White tin expands and crumbles on

cooling
 Lead
• Typical metallic lattice: atoms are held together by metallic
bonding.

• TASK: List the physical properties of metals

 Variation in Melting Point
 on going down the group

C 3527C

Si 1414C

Ge 1211C

Sn 232C

Pb 327C
 Variation in Melting Point
• The very high m.p. of diamond
is due to the strong C – C C 3527C
bonds & the giant covalent
structure. Si 1414C
• Going from C to Ge:
Ge 1211C
• bond length increase

• bond strength decrease Sn 232C

• melting point decrease
Pb 327C
 Variation in Melting Point
• Sn and Pb have exceptionally
low m.p. because C 3527C
1. metallic structures
Si 1414C
➔ extent of bond breaking
on melting is small
Ge 1211C
2. only two of the four
valence electrons are Sn 232C
delocalized (involved in the
sea of electrons)
Pb 327C
(Hox! inert pair)
 Variation in Boiling Point
• The general trend and
explanation similar to those for C 4027C
m.p.
Si 3265C

Ge 2833C

Sn 2602C

Pb 1749C
 Group 14 compounds
• Carbon bonds covalently and the bonds become more and
more ionic in character down the group.

• The most common oxidation state in Group 14 is +4.

• Also oxidation state +2 is observed.

 Group 14 chlorides
• M – Cl bonds are polar with ionic character

• Molecules as a whole are non-polar

d-

d+ d-

d-

d-
 Reactions with water
• CCl4 (l) + H2O (l) → no reaction

• SiCl4 (l) + 2 H2O (l) → SiO2 (s) + 4 HCl (g)

 Chlorides
• Tendency to form dichlorides, MCl2 down
the group -

• All possess covalent character though -

they exist as crystalline solids at room
temperature and pressure. GeCl2

SnCl2

PbCl2
 Chlorides
• On moving down the group: -

Metallic character of elements - -

increase. mainly GeCl2
covalent
Ionic character of MCl2 increase.
SnCl2
mainly
ionic PbCl2
 Metallic character of tin
and lead
• Metals with more than one oxidation state exhibit more
metallic behavior in the lower state. Tin(II) and lead(II)
chlorides are white, crystalline, saltlike solids.

• In contrast, tin(IV) and lead(IV) chlorides are volatile

liquids, indicating the presence of individual molecules.
 Stability
• On moving down the group:

the relative stability of +4 oxidation state decrease

the relative stability of +2 oxidation state increase

 Tin (Sn) Lead (Pb)
[Kr] 4d10 5s25p2 [Xe] 4f145d10 6s26p2

The outermost ns2 electrons are less shielded by

the more diffused inner d and/or f electrons.
→ They are attracted more by the positive
nucleus
→ Less available for forming bonds
→ Form only two bonds using np2
 Oxides
• Two series of oxides formed by the Group 14 elements

the monoxides MO

the dioxides MO2

All Group IV elements form dioxides.

• Carbon dioxide: the only Group 14 dioxide which consists
of simple molecules, exists as a gas at room temperature
and pressure.

• The dioxides of other Group 14 elements: crystalline solids

of high melting points, either giant covalent or giant ionic
structures.
 Monoxides

CO Reducing
agent
Increasing SiO
stability
GeO

SnO Decreasing
ability to
PbO reduce
 Dioxides

Increasing
CO2 ability to
Decreasing oxidise
stability SiO2
GeO2
SnO2
Oxidising
PbO2 agent
 The Relative Stability of the Oxidation
States
❑ CO reduces many hot metal oxides to the metal - a reaction
which is used, for example, in the extraction of iron in a blast
furnace:

• The +4 oxidation state for carbon compounds is more

stable than the +2 state.
 The Relative Stability of the Oxidation
States
❑ Tin(II) will therefore be oxidized fairly easily to Tin(IV) as
shown in the following reactions:

• The +4 oxidation state for tin compounds is more

stable than the +2 state.
 The Relative Stability of the Oxidation
States
• The lead(II) oxidation state is more stable, and there is
a strong tendency for lead(IV) compounds to react to
give lead(II) compounds.
The Acid Base Properties of
the Oxides
+2 Oxidation state

• Carbon monoxide is very, very slightly acidic.

• It doesn't react with water, but it will react with hot
concentrated sodium hydroxide solution to give a
solution of sodium methanoate:

• SiO does not react with acids nor bases.

 The Acid Base Properties of
the Oxides
• GeO, SnO and PbO all react with concentrated HCl as
follows:
XO (s) + 2HCl(aq) ⎯→ XCl2 (aq) + H2O(l)

• GeO, SnO and PbO all react with NaOH as

shown with the GeO example:

GeO(s) + 2OH-(aq) ⎯→ GeO22-(aq) + H2O(l)

 The Acid Base Properties of
the Oxides
+4 Oxidation state

• CO2 is slightly soluble in water forming the weak acid,

carbonic acid:
CO2(aq) + H2O(l) H2CO3(aq) HCO3-(aq) + H+ (aq)

CO32- (aq) + 2H+(aq)

• CO2 also reacts directly with alkali:

CO2(g) + 2OH-(aq) ⎯→ CO32-(aq) + H2O(l)
 The Acid Base Properties of
the Oxides
• SiO2 also reacts with sodium hydroxide solution, but
only if it is hot and concentrated. Sodium silicate
solution is formed:

SiO2(s) + 2NaOH(aq) ⎯→ Na2SiO3(aq) + H2O(l)

• GeO2 , SnO2 and PbO2 are all amphoteric, reacting

with both HCl and NaOH:
GeO2(s) + 4HCl(aq) ⎯→ GeCl4(l) + 2H2O(l)
GeO2(s) + 2OH-(aq) ⎯→ GeO32-(aq) + H2O(l)
Ease of reaction with OH- GeO2 > SnO2 > PbO2
 The acid-base behaviour of
the Group 14 oxides

• The oxides of the elements at the top of Group 4 are

acidic, but acidity of the oxides falls as you go down the
Group.

• Towards the bottom of the Group, the oxides become

more basic - although without ever losing their acidic
character completely => amphoteric.
 The bond type and the relative stability of the monoxides and dioxides formed by
the Group 14 elements

Group IV Oxides Bond type of the

Relative stability
element formed oxide
Unstable
CO Covalent
Carbon (reducing)
CO2 Covalent Stable
SiO Covalent (unstable)
Silicon
SiO2 Covalent Stable
Unstable in the
GeO Predominantly ionic
presence of O2
Germanium
Partly ionic, partly
GeO2 Stable
covalent
 The bond type and the relative stability of the monoxides and dioxides formed by
the Group 14 elements

Group IV Oxides
Bond type of the oxide Relative stability
element formed

Unstable
SnO Predominantly ionic
(reducing)
Tin
Partly ionic, Unstable
SnO2
partly covalent (oxidizing)
PbO Ionic Stable
Lead Unstable
PbO2 Predominantly ionic
(oxidizing)