Group IV Cam 1

GROUP IV

General • occurs in the middle of the periodic table

• contains metals and non-metals
• metallic properties increase down group
• stability of +4 oxidation state decreases down group - the ‘inert pair’ effect
• all have the electronic configuration ... n s2 n p2 .

ELEMENTS

C Si Ge Sn Pb

atomic number 6 14 32
electron config. [He] 2s2 2p2 [Ne] 3s2 3p2 [Ar] 4s2 4p2 [Kr] 5s2 5p2 [Xe] 6s2 6p2
atomic radius / nm 0.077 0.177 0.122 0.140 0.154
electronegativity 2.5 1.8 1.8 1.8 1.8
1st I.E. / kj mol-1 1086 786 760 710 720
description non-metal metalloid metalloid metal metal
bonding gaint covalent giant covalent giant covalent metallic metallic
melting point / °C 3550 (diam) 1410 940 232 328
boiling point / °C 4830 (diam) 2680 2830 2690 1751
electrical graphite - good semiconductor semiconductor good good
conductivity diamond - poor

TRENDS

Melting Point General decrease

down group C Si Ge Sn Pb

Melting point / °C 3550 1410 940 232 328

• change from giant molecular to metallic bonding

• many bonds need to be broken to separate the atoms in giant molecules
• the larger the atoms the weaker the covalent bond

Electrical
conductivity C diamond poor no free electrons - all used for bonding
graphite good one electron per carbon is not used for bonding
and joins delocalised cloud

Si semiconductor

Ge semiconductor

Sn good metallic bonding - delocalised electron cloud

Pb good metallic bonding - delocalised electron cloud

2 Cam Group IV

TETRACHLORIDES

CCl4 SiCl4 GeCl4 SnCl4 PbCl4

boiling point / °C 77 58 87 114 105 (explodes)

bonding covalent covalent covalent covalent covalent
structure molecular molecular molecular molecular molecular
shape tetrahedral tetrahedral tetrahedral tetrahedral tetrahedral
reaction with water none hydrolysed hydrolysed hydrolysed hydrolysed

Bonding Covalency is favoured if the cation is small and has a high charge... therefore
• all should be covalent - in +4 oxidation state
• CCl4 should be the most covalent - small size of carbon
• all will be tetrahedral - repulsion between 4 bond pairs of electrons

Hydrolysis • CCl4 isn’t hydrolysed by water - no available space to accept a lone pair
• remainder are rapidly hydrolysed - not limited to a co-ordination number of 4
- give an acidic solution due to HCl

e.g. SiCl4(l) + 2H2O(l) —> SiO2(s) + 4HCl(aq)

DIOXIDES

CO2 SiO2 GeO2 SnO2 PbO2

melting point / °C -56 1610 1116 1127 decomp 300

thermal stability <——— stable to high temperatures ——–> decomposes
bonding covalent covalent ——— increasingly ionic ———>
structure molecular giant molecule < ———— giant structure ————>
nature acidic acidic amphoteric amphoteric amphoteric
solubility in water slightly insoluble insoluble insoluble insoluble

Stability • All except PbO2 are thermally stable

• The +4 oxidation state gets less stable down the group

Bonding • ionic character increases down the group as atomic size increases
• CO2 is a simple molecule, the rest have giant structures
Group IV Cam 3

Acid-base
character CO2 • acidic (non-metal oxide)
• dissolves in water to give a weak acidic solution

CO2(aq) + H2O (l) H+ (aq) + HCO3¯(aq)

SiO2 • acidic (non-metal oxide)

• insoluble in water
• dissolves in conc alkali
SiO2(s) + 2OH¯(aq) ——> SiO32-(aq) + H2O(l)

GeO2 • amphoteric
• dissolves in acid
GeO2(s) + 4HCl(aq) ——> GeCl4 (aq) + 2H2O(l)

• dissolves in alkali
GeO2(s) + 2OH¯(aq) + 2H2O(l) [Ge(OH)6]2¯ (aq)

SnO2, PbO2 • amphoteric

• similar reactions to germanium
• acidic character decreases down the group

MONOXIDES

Stability • The +2 oxidation state gets more stable down the group
• CO is a powerful reducing agent

Bonding • ionic character increases down the group as atomic size increases
• CO is a simple molecule

Acid-base
character CO • neutral
• insoluble in water

GeO, SnO, PbO • amphoteric

• dissolves in acid
PbO(s) + 2HCl(aq) ——> PbCl2 (aq) + H2O(l)

• dissolves in alkali
PbO(s) + 2OH¯(aq) ——> PbO22- (aq) + H2O(l)
4 Cam Group IV

STABILITY OF OXIDATION STATES

General • +4 oxidation state stability decreases down the group

• +2 oxidation state stability increases down the group
• due to what is called the ‘inert pair’ effect

Examples • CO is a powerful reducing agent CO + ½O2 ——> CO2

3CO + Fe2O3 ——> 2Fe + 3CO2

• PbO2 is a powerful oxidision agent PbO2 + 4HCl ——> PbCl2 + 2H2O + Cl2

• PbCl4 is thermally unstable PbCl4 ——> PbCl2 + Cl2

E° values • the E° value for the reduction of lead(IV) is very positive so it is a favourable reaction
• the value for tin(IV) is much lower so it isn’t as good an oxidising agent

Sn2+(aq) + 2e¯ Sn(s) E° = - 0.4V

Sn4+(aq) + 2e¯ Sn2+(aq) E° = +0.15V

Pb2+(aq) + 2e¯ Pb(s) E° = - 0.13V

4+
Pb (aq) + 2e¯ Pb2+(aq) E° = +1.7V

SILICON(IV) OXIDE - SiO2

Properties Silica based ceramics are • good electrical insulators
• good thermal insulators
• have great rigidity
• are hard

Uses • furnace linings

• glasses for solar panels
• power line insulators
• parts of turbines

Q.1 Why is graphite a better conductor of electricity than diamond or silica?

Q.2 What is the shape of the complex ion [Ge(OH)6]2¯ ?