Group IV Elements

Non-Metal to Metal
R.Wint
Cape Chemistry

Objectives
Relate variations in physical properties-MP, BP,
Conductivity- to structure and bonding
Describe bonding in tetrachlorides
Reactions of tetrachloride with water
Discuss Trends in:
Bonding
Acid/base nature
Thermal stability of +2 and +4 oxides

Compare relative stabilities of +2 and +4 oxides

Compare relative stabilities of aqueous cations in
lower and higher Ox. States
Discus use of silicon in ceramics

General Atomic Trend Down

Any Group

Increase in atomic radius

Decrease in effective nuclear charge (Zeff) due

maximum shielding
Decrease in electronegativity (thus tendency to
lose electrons rather than sharing)
Decrease in first ionisation energy

42.1 Introduction (SB p.106)

Introduction

The Group IV elements

reveals a marked change among the
elements
exhibit considerable change in
character (or dissimilarity)

42.1 Introduction (SB p.106)

Introduction

The Group IV elements

carbon
silicon
germanium
tin
lead

Non-Metal to Metal
Descending the group:
Moves from Giant Covalent Molecular (CarbonGermanium) to Metallic (Tin and Lead)
Explain: Decrease in electronegativity, owing to
decrease in Zeff, thus bottom elements tend to lose
their electrons to become delocalised resulting in
metallic bonding

COVALENT BONDS ARE STRONGER

THAN METALLIC BONDS!!
In a covalent bond, an electron is shared/held between two nuclei,
whereas electrons in metallic bond are free and delocalised

42.1 Introduction (SB p.106)

Carbon
dull black in the form of graphite

Appearances of the Group IV elements

at room temperature and pressure:
carbon (graphite)

42.1 Introduction (SB p.106)

Introduction

Carbon
hard and transparent in the form of
diamond

42.1 Introduction (SB p.106)

Introduction

Silicon and germanium

dull grey or black
Germanium

Silicon

42.1 Introduction (SB p.106)

Introduction

Tin and lead

shiny grey
Tin

Lead

42.1 Introduction (SB p.106)

Introduction

The Group IV elements

outermost shell electronic configuration
of ns2np2
Element

Electronic configuration

Carbon

[He] 2s22p2

Silicon

[Ne] 3s23p2

Germanium

[Ar] 3d104s24p2

Tin

[Kr] 4d 105s25p2

Lead

[Xe] 4f 145d 106s26p2

42.2 Characteristic Properties of the Group IV Elements (SB p.107)

Structure and Bonding

Moving down the group

change from non-metal to metal

42.2 Characteristic Properties of the Group IV Elements (SB p.107)

Structure and Bonding

Carbon
non-metal: Giant Molecular

Silicon and germanium

metalloids: Giant Molecular

Tin and lead

typical metals

42.2 Characteristic Properties of the Group IV Elements (SB p.107)

Structure and Bonding

The most common structure in Group IV

elements
giant covalent structure

42.2 Characteristic Properties of the Group IV Elements (SB p.107)

Structure and Bonding

Example of giant covalent structure

carbon
silicon
germanium
grey tin (an allotrope of tin)

42.2 Characteristic Properties of the Group IV Elements (SB p.107)

1. Carbon

Carbon
two important allotropic forms
diamond and graphite

42.2 Characteristic Properties of the Group IV Elements (SB p.107)

1. Carbon

Diamond
extended covalently-bonded structure
each carbon atom is bonded to four
other carbon atoms

42.2 Characteristic Properties of the Group IV Elements (SB p.107)

1. Carbon

This compact and rigid arrangement of

carbon atoms
extremely hard and chemically inert

42.2 Characteristic Properties of the Group IV Elements (SB p.108)

Structures of the two allotropic forms

of carbon: diamond

42.2 Characteristic Properties of the Group IV Elements (SB p.107)

1. Carbon

Graphite
layered structure
layers of covalently-bonded carbon
atoms are held together by weak van
der Waals forces

42.2 Characteristic Properties of the Group IV Elements (SB p.107)

1. Carbon

These layers slide over each other easily

brittle and soft

42.2 Characteristic Properties of the Group IV Elements (SB p.108)

Structures of the two allotropic forms

of carbon: graphite

42.2 Characteristic Properties of the Group IV Elements (SB p.108)

2. Silicon and Germanium

Silicon and germanium

network lattice
the atoms are covalently bonded to
one another

42.2 Characteristic Properties of the Group IV Elements (SB p.108)

3. Tin and Lead

Tin
two allotropes
white tin and grey tin

42.2 Characteristic Properties of the Group IV Elements (SB p.108)

3. Tin and Lead

White tin
stable form
metallic lattice structure
atoms are held together by metallic
bonding

42.2 Characteristic Properties of the Group IV Elements (SB p.108)

3. Tin and Lead

White tin
conducts electricity
shows the properties of a typical
metal

42.2 Characteristic Properties of the Group IV Elements (SB p.108)

3. Tin and Lead

Grey tin
network lattice structure
similar to that of diamond

42.2 Characteristic Properties of the Group IV Elements (SB p.108)

3. Tin and Lead

Lead
typical metallic lattice
atoms are held together by metallic
bonding

42.2 Characteristic Properties of the Group IV Elements (SB p.108)

Some physical properties of the Group IV elements

Carbon (C)
Electronegativity value

Silicon (Si) Germanium (Ge)

2.5

1.74

2.0

1s22s22p2

[Ne] 3s23p2

[Ar] 4s24p2

0.077

0.117

0.122

Bond enthalpy (kJ mol1)

347

226

188

Melting point (C)

3550

1410

937

Boiling point (C)

4287

2355

2830

Enthalpy change of
atomization (kJ mol1)

716

456

376

Electronic configuration
Atomic radius (nm)

42.2 Characteristic Properties of the Group IV Elements (SB p.108)

Some physical properties of the Group IV elements

Tin (Sn)

Lead (Pb)

1.7

1.55

[Kr] 5s25p2

[Xe] 6s26p2

0.140

0.154

Bond enthalpy (kJ mol1)

150

Melting point (C)

230

327

Boiling point (C)

2270

1740

Enthalpy change of
atomization (kJ mol1)

302

195

Electronegativity value
Electronic configuration
Atomic radius (nm)

42.2 Characteristic Properties of the Group IV Elements (SB p.109)

Variation in Melting Point

The variation
in melting point
of the Group
IV elements

42.2 Characteristic Properties of the Group IV Elements (SB p.109)

Variation in Melting Point

The melting points

general decrease on going down the
group

42.2 Characteristic Properties of the Group IV Elements (SB p.109)

Variation in Melting Point

To melt or boil, interatomic forces must be
overcome. Decreases down the Group
Carbon- Germanium: atoms are covalently
bonded, with C-C being shortest and
strongest
Tin and lead: metallic bonding, electrons are
already delocalised thus easier to separate

42.2 Characteristic Properties of the Group IV Elements (SB p.109)

Variation in Melting Point

Going from carbon to germanium

the bond lengths increase
the bond strengths decrease
the lower melting points

42.2 Characteristic Properties of the Group IV Elements (SB p.109)

Variation in Melting Point

A further and bigger fall to tin

a slight rise to lead

42.2 Characteristic Properties of the Group IV Elements (SB p.109)

Variation in Melting Point

Tin and lead

metallic structures
no need to break strong metallic
bonds to bring about melting

42.2 Characteristic Properties of the Group IV Elements (SB p.109)

Variation in Melting Point

Tin and lead

only two of the four valence
electrons are delocalized to form
metallic bonds
unusually low melting points

42.2 Characteristic Properties of the Group IV Elements (SB p.110)

Variation in Boiling Point

Variation in boiling
point of the Group
IV elements

42.2 Characteristic Properties of the Group IV Elements (SB p.110)

Variation in Boiling Point

The general trend and explanation

similar to those for melting point

Electrical Conductivity

Increases down the group

Descending the group, elements become more

metallic with free delocalised electrons that
can carry current.
Carbon(Non-Conductor)Si and Ge (Semiconductor) Sn and Pb (good conductors)

Semiconductor: substance that can conduct

electricity under some conditions but not others,
depending on the presence of impurities

Stability of Oxidation States

Group IV elements exists in +2 and +4
oxidation states
Trend: Steady increase in the stability of
toward the lower ox. state(+2), down the
group
Carbon: +4 is much more stable, (hence why
CO is quickly oxidised to CO2)
Silicon: + 4 much more stable, than +2 rare
and readily oxidise
Germanium: +4 more stable
Tin: +4 is slightly more stable than +2
Lead: +2 is certainly more stable than +4

Relate Oxidation Stability to Eo

Recall: more positive E o = reaction will likely

occur
Note the Reduction Potentials Trend:
Ge4+ + 2e- Ge2+ EO = -1.6V
Sn

4+

+ 2e- Sn2+ EO = +0.15V

Pb4+ + 2e- Pb2+ EO = +1.8V

The reduction Eo become more positive means

that the +2 state is becoming more stable

Trend in Bonding
Covalent compounds becomes less stable
down the group
Tendency to form ionic bonds down the
group (why? Decrease in electronegatvity=
easier to transfer electrons)

42.3 Composition of Chlorides and Oxides of the Group IV Elements

characteristic (SB p.110)

Chlorides

Two series of chlorides formed by the

Group IV elements
the dichlorides (MCl2)
the tetrachlorides (MCl4)

Going down the group

an increasing tendency to form
dichlorides

42.3 Composition of Chlorides and Oxides of the Group IV Elements

characteristic (SB p.111)

Chlorides

All Group IV elements

form covalent tetrachlorides
liquids at room temperature and
pressure (volatility decreases down
the group)
all simple covalent molecules with a
tetrahedral shape

42.3 Composition of Chlorides and Oxides of the Group IV Elements

characteristic (SB p.111)

All tetrachlorides of the Group IV

elements have a tetrahedral shape

42.3 Composition of Chlorides and Oxides of the Group IV Elements

characteristic (SB p.111)

Chlorides

The bonds formed by the Group IV

elements and chlorine (M Cl bonds)
covalent:
Not ionic because high ionisation energies
to remove 4 electrons
substantial amount of ionic character

42.3 Composition of Chlorides and Oxides of the Group IV Elements

characteristic (SB p.111)

Chlorides
Group IV tetrachlorides are hydrolysed by water (except CCl4)
to form the hydroxide (or hydrated oxide) and
hydrochloride gas.
MCl4(l) + 2H2O(l) M(OH)4(s) or MO2.xH2O(s) + HCl(g)

*carbon lacks a vacant 3d subshell so it cannot increase its

valency

42.3 Composition of Chlorides and Oxides of the Group IV Elements

characteristic (SB p.111)

Chlorides

Each M Cl bond
polar
molecule as a whole
no dipole moments
symmetrical shape

42.3 Composition of Chlorides and Oxides of the Group IV Elements

characteristic (SB p.111)

Chlorides

Going down the group, the relative

stability
the +4 oxidation state decreases
the +2 oxidation state becomes more
stable

42.3 Composition of Chlorides and Oxides of the Group IV Elements

characteristic (SB p.111)

Chlorides

Lead(II) chloride
more stable than lead(IV) chloride

42.3 Composition of Chlorides and Oxides of the Group IV Elements

characteristic (SB p.111)

Oxides

Two series of oxides formed by the

Group IV elements
the monoxides (MO)
the dioxides (MO2)

42.3 Composition of Chlorides and Oxides of the Group IV Elements

characteristic (SB p.111)

Oxides

Monoxides
oxidation state of +2

Dioxides
oxidation state of +4

42.3 Composition of Chlorides and Oxides of the Group IV Elements

characteristic (SB p.111)

Oxides

All Group IV elements

form the dioxides

Carbon dioxide
only one which consists of simple
molecules
exists as a gas at room temperature
and pressure

42.3 Composition of Chlorides and Oxides of the Group IV Elements

characteristic (SB p.111)

Oxides

The dioxides of other Group IV elements

crystalline solids of high melting
points
either giant covalent or giant ionic
structures

Oxides

All Group IV elements (except silicon)

form the monoxides at normal

conditions
Carbon monoxide (CO)
molecular compound

Germanium monoxide (GeO)

black solid
formed by the reduction of
germanium dioxide (GeO2)

42.3 Composition of Chlorides and Oxides of the Group IV Elements

characteristic (SB p.112)

Oxides

Tin monoxide (SnO) and lead monoxide

(PbO)
predominantly ionic solids

42.3 Composition of Chlorides and Oxides of the Group IV Elements

characteristic (SB p.112)

Oxides

Going down the group

a general increase in stability of the
monoxides relative to the dioxides

42.3 Composition of Chlorides and Oxides of the Group IV Elements

characteristic (SB p.112)

The bond type and the relative stability of the monoxides

and dioxides formed by the Group IV elements
Group IV
element
Carbon

Silicon

Germanium

Oxides
formed

Bond type of the oxide

Relative stability

CO

Covalent

Unstable (reducing)

CO2

Covalent

Stable

(SiO)

Very unstable

SiO2

Covalent

Stable

GeO

Predominantly ionic

Unstable in the
presence of oxygen

GeO2

Partly ionic, partly covalent Stable

42.3 Composition of Chlorides and Oxides of the Group IV Elements

characteristic (SB p.112)

The bond type and the relative stability of the monoxides

and dioxides formed by the Group IV elements
Group IV
element
Tin

Lead

Oxides
formed

Bond type of the oxide

Relative stability

SnO

Predominantly ionic

Unstable (reducing)

SnO2

Partly ionic, partly covalent Unstable (oxidizing)

PbO

Ionic

Stable

PbO2

Predominantly ionic

Unstable (oxidizing)

Check Point 42-3

42.4 Silicon and Silicates (SB p.113)

Silicon

Silicon
the second most abundant element in
the Earths crust
about 28% by mass

Silicon
commonly found as silicon oxide
(also known as silica)

42.4 Silicon and Silicates (SB p.113)

Silicon

Example:
in a variety of forms such as sand,
quartz and flint
also found as silicates in rocks and
clay
can be obtained from silica
by reduction with carbon in an
electric furnace
SiO2(s) + 2C(s)

Si(s) + 2CO(g)

42.4 Silicon and Silicates (SB p.113)

Silicon

Extremely pure silicon

can be obtained by the reaction of
silicon(IV) chloride with hydrogen
followed by zone refining of the
resultant silicon
SiCl4(s) + 2H2(g)

Si(s) + 4HCl(l)

42.4 Silicon and Silicates (SB p.113)

Silicon

Silicon is the basic material

for making semi-conductors used in
the construction of transistors and
rectifiers
for making steel and aluminium
alloys

Silicon and Ceramics

These are materials which are fashioned at room
temperature from clays or other natural earths and then
permanently hardened by heat.
Feldspar + carbon dioxide + water clay + silica +
potassium carbonate
When silica is reacted with other oxides in the process of
glazing (the final stage in making ceramics), the important
silicate ion (SiO32-) is formed.
Silicon carbide, Silicon nitride, zirconium dioxide

Ceramics
Hard and brittle
(unidirectional bonds)
Non-corrosive and
insulating to heat and
electricity (no mobile
electrons)
Resistant to high and low
voltages and high melting
point (because of the high
strength of the SiO

Uses

Utensils
Artificial bone
Dental implants
Valve component in
car engine
Ball bearing

42.4 Silicon and Silicates (SB p.113)

Silicon

The chemistry of silicon

dominated by its strong tendency to
form Si O single bond
reflected by its formation of silica and
a variety of silicates

42.4 Silicon and Silicates (SB p.113)

Structures and Bonding of Silicates

1. SiO44 as the Basic Chemical Unit of Silicates

Silicates
compounds of silicon, oxygen and
one or more metals

42.4 Silicon and Silicates (SB p.113)

The basic chemical unit of silicates: the

SiO44 anion

42.4 Silicon and Silicates (SB p.114)

1. SiO44 as the Basic Chemical Unit of Silicates

Each oxygen atom

located at the corner of the
tetrahedron
forms only one single bond
gain an extra electron in order to
achieve the stable octet electronic
configuration

42.4 Silicon and Silicates (SB p.114)

1. SiO44 as the Basic Chemical Unit of Silicates

Zircon (ZrSiO4)
brilliant appearance
high refractive index
used as a diamond-like gem

Sidenote: Preparing Insoluble

Lead Compounds
Pb(OH)2 white precipitate
Pb(NO3)2 + small amount of NaOH(aq)

PbCl2 white precipitate

Pb(NO3)2 + KCl

PbI2 yellow precipitate

Pb(NO3)2 + KI

The END

42.3 Composition of Chlorides and Oxides of the Group IV Elements

characteristic (SB p.112)

What is/are the oxidation state(s) of lead in Pb3O4?

Answer

Pb3O4 is a mixed oxide (PbO2 and 2PbO). The oxidation states

of lead are +4 and +2 in the mixed oxide Pb3O4.

Back

42.3 Composition of Chlorides and Oxides of the Group IV Elements

characteristic (SB p.112)

Why does carbon dioxide exist as a gas while

the dioxides of the other Group IV elements
exist as solids of high melting points at room
Answer
temperature and pressure?

Carbon dioxide is a molecular compound. The carbon dioxide

molecules are only held together by weak van der Waals forces. This
results in its low melting point. In contrast, the dioxides of other Group
IV elements have either giant covalent structure or giant ionic structure.
As a result, strong covalent bonds or ionic bonds have to be broken in
the process of melting of these compounds. Therefore, they have
relatively high melting points.

Back

42.4 Silicon and Silicates (SB p.116)

What is the chemical formula of the sheet silicate

anion?

Answer

Si4O104

Back