FIGURE 3.1 - Elements in Group Four (IV)

Chemistry of the Elements
GROUP FOUR ELEMENTS
Si
Ge
Sn
Pb
FIGURE 3.1 Elements In Group Four (IV)
Metals are good conductors of electricity with atomic conductance (atomic electrical
conductivity) greater than 10-3 ohm-1 cm-1. Their conductivity slowly falls as the temperature rises.
Metalloids are poor conductors of electricity with some atomic conductance usually less than 10 -3
but greater than 10-5 ohm-1 cm-1. The conductivity of the metalloids increase as the temperature
rises. It is also considerably affected by the presence of impurities.
Non metals are usually or virtually non conductors. Their atomic conductance is usually less than
10-10 ohm-1 cm-1.
The element carbon exists in the form of allotropes. Graphite is a poor conductor of electricity
and would be classified as a metalloid. Diamond, however, is an insulator and is therefore
classified as a non metal.
Copyright Pooran Appadu
3.1
PHYSICAL PROPERTIES OF GROUP IV

Carbon
(C)
Silicon
(Si)
Electronic Structure
Atomic Radius
Electronegativity
M.P / oC
B.P / oC
Density / g cm-3
2s22p2
0.077
2.5
3730 d
4830 d
2.26 gr, 3.51
3s23p2
0.117
1.8
1410
2680
2.33
Germaniu
m
(Ge)
4s24p2
0.122
1.8
937
2830
5.32
Conductivity
Fairly Good
Semiconduc
tor
gr
Electrical
Conductivity / Ohm-1
m-1
Thermal Conductivity /
J cm-1 s-1 K-1
Enthalpy Change
Hoat / KJ mol-1
1st I.E / KJ mol-1
Principal Ox. No.
Type Of Structure
Non Cond
1 X 10-7
0.24
gr
+716
gr
1086
+4
Giant
Molecules
Tin
(Sn)
Lead
(Pb)
5s25p2
0.141
1.8
232
2270
7.3
6s26p2
0.154
1.8
327
1730
11.44
Semiconduc
tor
Good
Good
1 X 106
2 X 106
8 X 106
5 X 106
0.84
0.59
0.63
0.35
+456
+376
+302
+195
787
+4
Giant
Molecular,
Similar To
Diamond
760
+2, +4
Giant
Molecular,
Similar To
Diamond
707
+2, +4
Giant
Metallic
715
+2, +4
Giant
Metallic
TABLE 3.1 Physical Properities Of Group IV
Carbon and silicon are non metals and give acidic oxides. Those of germanium, tin and lead are
amphoteric. Although some lead oxides are definitely basic, covalency dominates with carbon
and silicon and then ionic with tin and lead.
The most striking feature of the compounds of the group IV elements is the existence of two
oxidation states, +2 and +4. The relative stabilities of the +2 and +4 oxidation states vary. In
carbon and silicon compounds, the +4 is very stable relative to +2. Germanium forms oxides in
both +4 and +2 states. However, GeO 2 is rather more stable than GeO. GeO 2 does not act as an
oxidizing agent and GeO is readily converted to GeO 2.
In tin compounds, the +4 is only slight more stable than the +2 state. Thus aqueous tin (II) ions
are mild reducing agents. They will convert Mercury (II) ions to mercury and iodine to iodide.
Sn2+ (aq)
+ Hg2+ (aq)
Sn4+ (aq)
+ Hg (l)
Sn2+ (aq)
+ I2 (aq)
Sn4+ (aq)
+ 2I- (aq)
In lead compounds, however, +2 is unquestionably more stable, PbO 2 is a strong oxidizing agent,
whilst PbO is relatively stable. Thus PbO 2 can oxidise hydrochloric acid to chlorine and
hydrogensulphide to sulphur.

PbO2 (s)
+ 4HCl (aq)
PbCl2 (aq) + Cl2 (g) + 2H2O (l)
There is a steady increase in the stability of the lower oxidation state relative to the higher
oxidation state on moving down the graph from Carbon to Lead.
Relative Stability Falls
+4 State
+2 State
C
Relative Stability Rises

Si
Ge
Sn
Pb
FIGURE 3.1 Relative Stability Of The +4 And +2 Oxidation States Of Group IV
The greater stability of the +4 and +2 oxidation state with respect to +4 state as the atomic
number rise is well illustrated by the standard electrode potentials of the M 4+(aq) /M2+(aq) system for
germanium, tin and lead.
Ge4+ + 2e-
Ge2+ ; Eo = -1.6V
Sn4+ + 2e-
Sn2+ ; Eo = +0.15 V
Pb4+ + 2e-
Pb2+ ; Eo = +1..8 V
As the electrode potential gets more positive from Ge 4+ to Pb4+, the oxidized form is more readily
reduced to the +2 state.
All group IV elements have four electrons in their outermost shell and therefore show an
oxidation state of +4 but more forms cation of +4, M4+ ion in the solid state. This is due to the
high ionization energy involved in removing the four electrons. Consequently the bonding in the
tetravalent compounds is predominantly covalent. Compounds of tin and lead in which the group
IV element has an oxidation number of +2 (e.g. PbF 2, PbCl2, PbO) are normally regarded as ionic.
In these compounds, the Sn2+ and Pb2+ ions are formed by the loss of the two p electrons from
the 5p2 and 6p2 subshell. The two s electrons remain relatively stable and unreactive on the field
subshell. This is referred to as the inner pair effect.
3.2
REACTIONS OF TETRACHLORIDES WITH WATER

All the chlorides (except CCl4) are readily hydrolyzed. Tetrachloromethane will not react with
water but SiCl4 is immediately converted to silica.
SiO2 (s) + 4H+ (aq)
SiCl4 (l) + 2H2O (l)
+ 4Cl- (aq)
The difference is explained by assuming that one of the lone pairs on a water molecule can
overlap with one of the empty 3d orbitals or the silicon atoms. The 3d orbitals are much higher in
carbon, so bonding cannot occur between them and water molecules. Once electron density is fed
into the silicon atom, the chlorine atoms can detach themselves by inverting into chloride ions
and the SiCl4 is destroyed.
Very
Large
Gap
Small
Gap
2p
3p
4p
Very
Small
Gap
5p
FIGURE 3.2 Differences Between The 2p and 3d Energy Of Carbon
The diagram illustrates the large difference between the 2p and 3d energy of carbon. The carbon
3d orbitals are so high in energy that they cannot be used in bonding. The 3p and 3d for silicon is
relatively small, so silicon can use the 3d orbital in bonding.
Element
Carbon
Silicon
Germanium
Tin
Lead
Typical Halides
CCl4
SiCl4
GeCl4, GeCl2
SnCl4, SnCl2
PbCl4, PbCl2
Complex Halides
None, d orbitals needed.
SiF62GeFe22-, GeCl62SnF62-, SnCl42-, SnCl62PbCl42-, PbCl62-
TABLE 3.2 Typical & Complex Halides Of Group IV
Similar compounds are given with fluorine, chlorine, bromine and iodine. PbBr4, PbI4, do not
exist.

GeCl4 + 4H2O
Ge(OH)4 + 4HCl
SnCl4
+ 4H2O
Sn(OH)4 + 4HCl
PbCl4 + 4H2O
Pb(OH)4 + 4HCl
*PbCl4 must be kept below 5 oC or it dissociates.

PbCl4
PbCl2 + Cl2
Cl
Cl
Si +
Cl
Si
Cl
Cl
Cl
H
..
O:
Cl
Cl
OH2
Cl
Cl
Si +
Cl
Si
Cl
Cl
Cl
H
..
O:
Cl
OH
OH2
Cl
Cl
Si +
OH
Si
Cl
Cl
Cl
H
..
O:
Cl
OH
OH2
Cl
OH
Si +
OH
Si
Cl
Cl
Cl
H
..
O:
Cl
OH
OH2
Cl
OH
Si +
OH
Si
Cl
Cl
H
..
O:
Cl
H
FIGURE 3.3 Reaction Mechanism For SiCl4 And H2O
OH
OH

THE
DIOXIDES
Oxides
Boling Point
(oC)
Structure
Nature
GROUP IV ELEMENTS WITH +4 OXIDATION STATE

CO2
SiO2
GeO2
SnO2
PbO2
-78
2590
1200
1900
Decompose
s On
Heating
Simple
Molecular
Giant
Molecular
Intermediate Between
Giant And Ionic
ACIDIC
AMPHOTERIC
Reaction with Alkalis

giving XO32- salts.
React with fused alkalis giving XO32salts.
CO2 + 2OH- CO32- +

H2O
SnO2 + 2OH SnO32- + H2O
SiO2 + 2OH SiO3 +

H2O
-
PbO2 + 2OH SnO32- + H2O

React with concentrated acid forming
+4 salts.
SnO2 + 4H+ Sn4+
(aq)
+ H 2O
PbO2 + 4HCl PbCl4 + 2H2O
TABLE 3.3 Reaction Mechanism For SiCl4 And H2O

THE
MONOXIDES
GROUP IV ELEMENTS WITH +2 OXIDATION STATE
Oxides
CO
Boling Point (oC)
-191
SiO
GeO
SnO
PbO
1470
Structure
Simple Molecular
Neutral Oxides
Predominantly Ionic
Amphoteric Oxides
Nature
Reacts with neither

acids nor alkalis.
Reacts with acids to form salts:

PbO + 2H+ Pb2+ + H2O
SnO + 2H+ Sn2+ + 2H2O
Reacts with alkalis to forms salts:
PbO + OH- Pb(OH)3-+ H2O
Trihyrdroxyplumbate (II)
SnO + OH- + H2O Sn(OH)3Trihydroxystannate (II)
TABLE 3.3 Reaction Mechanism For SiCl4 And H2O
3.5
CERAMICS
The word ceramics literally means heat resistant and traditional ceramic materials are ones such
as porcelain which are fired during manufacture. Hardened by heat are the best known ceramics
and are based on clay, such as pottery.
Clays are found naturally and contain a number of minerals such as kaolinite, Al 2Si2O5(OH)4, an
alumino silicate. Clay contains crystals. When water is added it acts as a lubricant, allowing the
crystals to slide over one another. This makes the clay easy to shape. If the water is gently dried,
the shaped articles become hard, but if more water is added the clay becomes moldable again. If
the dry clay is then heated to a temperature of around 1000 oC (fired), chemical changes occur
and a glass is formed, which glues the clay crystals together. These chemical changes are not
reversible and the fired ceramic article can never be remolded. It will neither melt nor will it react
with oxygen in air, as it is already an oxide.
Ceramics are good insulators of both heat and electricity and are brittle. This last property is
because they have giant structures which are either covalently or ionically bonded.
Brittleness is the result of tiny cracks present on the surface.
Under load these cracks increase in size and lead to failure of the material.
No Crack. Each chain of atoms shares the load.
A small crack if found. Each load is

placed on the next chain
which breaks.
More load. Eventually the

structure breaks.
FIGURE 3.4 The Effect Of A Load On A Crack Within A Ceramic Structure
A small surface crack (Griffith crackio) can dramatically reduce the strength of a material under
tension.
FIGURE 3.5 Structure Of Kaolinite

FIGURE 3.1 - Elements in Group Four (IV)

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FIGURE 3.1 - Elements in Group Four (IV)

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Chemistry of the Elements

GROUP FOUR ELEMENTS