Group 4 Elements

Objective 3.4 Discuss the trends in :

a ) bonding
b ) acid/base character
c ) thermal stability of
the oxides of
oxidation states II
and IV
The Elements 6
C
of Group 4
12
14
28
Si
32
73
Ge
50
119 Sn
82
207 Pb 2
 Bonding
Silicon and germanium shows a giant molecular structure
similar to diamond while tin and lead have metallic structures.

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 Bonding
As the atoms get larger , the attraction of the nucleus for the
electrons in the covalent bonds gets weaker.
This results in delocalized electrons.The delocalized 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.
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 Bonding
Carbon exists mainly as graphite and diamond.In diamond,each
carbon atom is bonded covalently to four other carbon atoms
in a tetrahedral arrangement.Its melting point is 3730 degrees
celsius as it is a non conductor of electricity.
Silicon has a melting point of of 1410 degrees celsius and is
identified as a semi-conductor.Silicon forms a giant molecular
structure having strong covalent bonds.
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 Bonding
Germanium has a melting point of 937 degrees celsius and is a
semi-conductor.
Tin has a melting point of 232 degrees celsius and exists in the
form of two allotropes : grey tin 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 degrees celsius and is a good
conductor of electricity. 6
 Acid- Base Character
The oxides of the elements at the top of Group 4 are
Acid/Base acidic, but acidity of the oxides falls as you go down
the Group. Towards the bottom of the Group, the
Character oxides become more basic - although without ever
losing their acidic character completely.
An oxide which can show both acidic and basic
properties is said to be amphoteric.
The trend is therefore from acidic oxides at the top of
the Group towards amphoteric ones at the bottom.
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 THERMAL STABILITY
Thermal stability is how resistant a molecule is to
decomposition at high temperatures. The thermal stability
decreases down the group as the intramolecular forces
become longer and weaker due to increase in atomic radius.

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 Thermal Stability of Dioxides (oxidation state +4)
Bonding and Thermal Stability
CO2 has simple molecular structure and is thermally stable.
SiO2 and GeO2 have giant molecular structures.
SnO2 and PbO2 have giant molecular structure with little ionic character.
PbO2 is the only oxide which readily decompose:

2PbO2(s) --heat---> PbO(s) + O2(g)

The above trend reflects decreasing stability of +4 oxidation state, since only
lead (IV) oxide (which is at the bottom of the group) decomposes to lead (II)
oxide. 9
Thermal Stability of Dioxides (oxidation state +4)
Acidity
a) CO2 and SiO2 are acidic and react with alkalis to form salts.
CO2(g) + 2NaOH(aq) → Na2CO3(aq) + H2O(l)
2NaOH(aq) + SiO2(s) → Na2SiO3(aq) + H2O(l)
b) GeO, SnO2 and PbO2 are amphoteric and will react with both acids and
alkalis.
SnO2(s) + conc.HCl(l) → SnCl4(l) + 2H2O(l)
SnO2(s) + 2OH-(aq) → SnO32-(aq) + H2O(l)
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Thermal Stability of Monoxides (oxidation state +2)
Bonding and Thermal Stability
CO has simple molecular structure and is thermally stable due to its
strong triple covalent bonds. CO has a lone pair of electrons hence,
can act as a ligand forming complexes with transition metals.

For example: Ni (CO)42+

SiO and GeO have giant molecular structure but the covalent bonds
are relatively weak. So these decompose in a disproportionation
reaction.
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 Thermal Stability of Monoxides (oxidation state +2)
Bonding and Thermal Stability
2GeO(s) ---heat---> GeO2(s) + Ge(s)

2SiO3(s) --heat---> SiO2(s) + Si(s)

SnO and PbO have considerable degree of ionic character and do not
decompose on heating.
When PbO is heated it does not form PbO2 instead it forms Pb3O4, called
red lead oxide. This behaves chemically as a mixture of PbO2.2PbO
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Thermal Stability of Monoxides (oxidation state +2)
Acidity
Carbon monoxide is usually treated as a neutral oxide, but it is slightly

acidic. It does not react with water, but it can react with hot concentrated

sodium hydroxide solution to give a solution of sodium methanoate.

a) CO and SiO are neutral and react neither with acids or alkalis.
b) GeO, SnO, PbO are amphoteric as they react with both acids and
bases:
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Thermal Stability of Monoxides (oxidation state +2)
Acidity

 With acid (Conc. HCl)      

SnO(s) + 2HCl(aq) ----> SnCl2(aq) + H2O(l)

PbO(s) + 2HCl(aq) ----> PbCl2(s) + H2O(l)
GeO(s) + 2HCl(aq) ----> GeCl2 + H2O(l)     

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Thermal Stability of Monoxides (oxidation state +2)
Acidity

With aqueous alkali

SnO(s) + 2NaOH(aq) ----> Na2SnO2(aq) + H2O(l)
                                            Sodium stannate (II)
PbO(s) + 2NaOH(aq) ----> Na2PbO2(aq) + H2O(l) 
             
GeO(s) + 2NaOH(aq) ----> Na2GeO2(aq) + H2O(l)
                                  Sodium Germinate (II)
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Group 4 Elements
Objective 3.5 Discuss the relative
Stabilities of the oxides
and aqueous cations
of the elements in their
higher and lower
oxidation states
The +2 Oxidation
State of Group 4
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 +2
Lead (II) oxide is the
CO
most stable
SiO compound in the +2
GeO oxidation state.
SnO
PbO 18
 +2 Oxidation States
+2
The +2 oxidation state is unstable for C
CO and Si but most stable for Pb.
SiO Compounds of both Pb(II) and Sn(II) are
common in ionic bonding.Compounds
GeO of C(II) , Si(II) , Ge(II) and Sn(II) are easily
SnO oxidized and are therefore strong
reducing agents.
PbO 19
 +2 Oxidation States
+2 CO (carbon monoxide) is a good reducing agent as it loses
electrons readily.

CO A reducing agent loses electrons and is oxidised in a chemical

rxn.

SiO example:At high temperatures,CO,reduces iron(III)oxide to iron.

CO is oxidised to CO2 which is more stable.
GeO Fe2O3(s) + 3CO(g) → 2Fe(l) + 3CO2(g)

SnO Fe2O3- Oxidation number of +3

3CO- Oxidation number of +2

PbO
2Fe- Oxidation number of 0
3CO2- Oxidation number of +4
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The +4 Oxidation
State of Group 4
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 +4 Carbon (IV) oxide is the
CO2 most stable compound
SiO2 in the +4 oxidation
GeO2 state since stability
SnO2 increases up the group.
PbO2 22
 Since the stabilities of the oxides
+4 of the +4 oxidation state increases
CO2 up the group,
SiO2
GeO2
SnO2
PbO2 23
 Going down,
+4 the oxides of the +4 oxidation
CO2 state become better oxidising
SiO2 agents as the tendency to gain
electrons and to be reduced is
GeO2 increased due to the decrease in
SnO2 stability down the group.
PbO2 24
 4 Oxidation States
+4 All elements have four outer atoms which results in

CO2 the oxidation number for most elements to be +4.

Only PbF4 and SnF4 are considered truly ionic.

SiO2 +4 is the most stable state for C ,Si ,Ge and Pb but
the least stable is Pb.
GeO2 Compounds of Pb(IV) are easily reduced to Pb(II)
and are strong oxidising agent.
SnO2 Example: PbO2(s) + 4HCL(aq)→PbCl2(s)
+Cl2(g) + 2H20(g)
PbO2 Lead(II)oxide oxidizes HCL to CL. 25
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 The Electrode Potential
This is the tendency or potential of a chemical
species to undergo reduction(the gain of electrons).
Electrode potential values are measured in volts (V).

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 An Electrode Potential Diagram for Determining the
Feasibility of some Reactions involving Group 4 Cations
E°/V
-0.14V - Sn2+(aq) + 2e- ⇋Sn(s)
+0.15V - Sn4+(aq) + 2e- ⇋Sn2+(aq)
+1.69V - Pb4+(aq) + 2e- ⇋ Pb2+(aq)
-0.60V - Ge4+(aq) + 2e- ⇋ Ge2+(aq)

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 When the electrode potential value increases ,
the tendency of the +4 oxidation to be reduced to
the +2 oxidation is increased.
This shows that the stability of the +4 oxidation
state decreases down Group 4.

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Between these extremes, there is a gradual change in stability of the +2
compared with the +4
This can be interpreted from the E° values of the ions of Group IV elements in aqueous
solutions

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Group 4 Elements
Objective 3.6 Discuss the uses of
ceramics based on
silicon (IV) oxide.

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 Silicon Dioxide (silicon (IV) oxide)

Quartz Crystals Sand

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 The Structure of SiO2
The electronegativity of the elements in group 3 increases as you go
across the period, so by the time you get to silicon, there is not enough
electronegativity difference between the silicon and the oxygen to form
an ionic bond therefore, Silicon dioxide is a giant covalent structure.
There are three different crystal forms of silicon dioxide. The diamond
structure is an example as it is similar to and relates to the structure of
silicon dioxide. Crystalline silicon has the same structure as diamond
but to turn it into silicon dioxide; you need to modify the silicon
structure by including some oxygen atoms.

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 The Structure of SiO2

Diamond Structure Silicon Dioxide Structure

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 Melting and Boiling Point Electrical conductivity

Silicon dioxide has a high melting Silicon dioxide doesn’t have any
point .It varies depending on what mobile electrons or ions – so it
the particular structure is (but they doesn’t conduct electricity
are all around 1700°C. Very strong either as a solid or a liquid.
silicon-oxygen covalent bonds have
to be broken throughout the
structure before melting occurs.
Silicon dioxide boils at 2230°C.
Because silicon dioxides have giant
structures, the melting and boiling
points are all high.
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The uses of ceramics Ceramics is the name given to materials
made from clay and heated at high
based on temperatures ceramics products can include
pottery, bricks and tiles and so on .
silicon dioxide Currently these products are geared
towards crystalline ceramics designed to
have properties such as hardness, strength
and the ability to withstand high
temperatures.

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The uses of ceramics Furnace lining – this is lining consisting of
material with a high melting point; used to line
based on the inside walls of a furnace.So sio2 is used
silicon dioxide because it is a good thermal insulator and has a
very high melting point due to its strong
covalent bonds.

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The uses of ceramics Abrasives - are substances used to smooth out
or machine (to mold or finish by machinery)
based on other softer materials through extensive
silicon dioxide rubbing. They work by scratching away the
surface of materials in order to rid it of
unwanted roughness or substances. examples
are sandpaper, emery, and sand. SIO2 is used to
make this because it is hard has a high melting
point ( heat is also given off when grinding )

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The uses of ceramics
based on
silicon dioxide

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The uses of ceramics Manufacture of glass and porcelain – SIO2 is
used in the manufacture of glass and procelein
based on because it is relatively unreactive and is easily
silicon dioxide molded , the high melting point is useful and
suitable for oven ware.

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The uses of ceramics Food
Using silicon dioxide in food helps in many
based on ways. The main use is the health it renders
silicon dioxide to our bones and joints. Regular intake of
silicon dioxide is helpful in maintaining the
strength and density of bones, thus
reducing the risk of diseases like arthritis
and osteoarthritis.

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RECAP

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Thanks!
Any questions?

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