CHEMICAL PROPERTIES OF GROUP 14

TETRACHLORIDES AND OXIDES OF GROUP 14 ELEMENTS

General Formula: MCl4
- Central atom undergoes sp3 hybridisation to give bond angle of 109.5

By passing dry chlorine gas into liquid carbon disulphide boiling under reflux in the
presence of little iodine as catalyst
3Cl2 (g) + CS2 (l)
CCl4(l) + S2Cl2(l)

Preparation of SiCl4, GeCl4,

SnCl4

Direct combination by heating the element in a steam of dry chlorine gas.

Si(s) + 2Cl2 (g)
SiCl4 (l)

Preparation of PbCl4

Reacting lead hydroxide with conc HCl at 5C

PbO2(s) + 4HCl (aq)
PbCl4 (l) +2H2O

Preparation of CCl4
GENERAL

BOILING POINT
-

THERMAL STABILITY

The bond that hold the atoms together in the tetrachloride

molecules are covalent bonds but intermolecular forces are the
weak Van der Waals forces.
All tetrachloride are colourless.
Going down Group 14, the size and the number of electrons
increases, Van der Waals force getting stronger, boiling point
increases.
*exceptional behavior for CCl4
PbCl4 does not have normal boiling point as it decompose on
heating
PbCl4(l)
PbCl2 (s) + Cl2(g)

The longer the bond length, the weaker the bond and is easier to break
Going down Group 14, M-Cl bonds become longer and weaker as the atomic radius of M increases
Thermal stability decreases down the group.
CCl4, SiCl4 and GeCl4 are stable to heat even at high temperature
SnCl4 decomposes on strong heating ;
SnCl4(l)
SnCl2(s) + Cl2(g)
PbCl4 is so unstable that it undergoes partial decomposition even at low temperature;
PbCl4(l)
PbCl2 (s) + Cl2(g)

HYDROLYSIS

XCl4 +2H2O
XO2 + 4HCl
All Group 14 tetrachloride undergoes hydrolysis to produce hydrochloric acid or hydrogen chloride
gas depends on the amount of water used. [Except carbon tetrachloride]
Exp: SiCl4(l) + 2H2O (l)
SiO2(s) + 4HCl (aq)
During hydrolysis, silicon, germanium, tin and lead make use of their empty d- orbitals in their
valence shell to form coordinate bond with water molecules.

Exception for carbon tetrachloride

- There are no empty d-orbital in its valence shell to form coordinate bond with water and is not
hydrolysed by water.

THERMAL STABILITY OF THE OXIDES

-

Group 14 form two series of oxides with oxygen. Monoxide with the general formula MO and dioxide with the general formula of MO2.
The oxidation state of the element in the monoxide is +2 while in dioxide is +4

Monoxide
(+2)

CO

SiO

GeO

SnO

PbO

Dioxide

CO2

Physical
state

Gas

Solid

Physical
state

Gas

Structure

Simple molecule

Predominantly ionic

Structure

Simple
covalent

Thermal
Stability

Acid-base
nature
-

Form dioxide on heating in air

Neutral

Stable

Amphoteric

Monoxides of C, Si, Ge and Sn are converted to the dioxides on heating in

air.
2CO (g) + O2(g)
2CO2(g)
2GeO (g) + O2(g)
2GeO2(g)
2SnO (g) + O2(g)
2SnO2(g)
Lead monoxide is stable to heat
ACID BASE NATURE OF OXIDES

SiO2

SnO2

Giant
covalent

Intermediate between giant covalent and

giant ionic

Stable

Acid

Unstable

Amphoteric

Dioxides of C, Si, Ge and Sn stable to heat.

Brown lead dioxide decomposes to yellow monoxide on heating
2PbO2(s)

PbO2

Solid

Thermal
Stability

Acid-base
nature

GeO2

2PbO(s) + O2(g)

MONOXIDES
-

CO and SiO are neutral oxides, monoxide of germanium, tin and lead are

amphoteric
This is because the metallic character increases with increasing proton

DIOXIDES
-

number
-

Monoxides of germanium, tin and lead dissolve in hot, dilute mineral

acids
MO(s) + 2H+ (aq)
M2+ + H2O(l)
+
Exp: GeO(s) + 2H (aq)
Ge2+ + H2O(l)
Monoxides of germanium, tin and lead dissolve in hot concentrated
alkali to form salts.

MO(s) + 2OH-(aq) +H2O(l)

Exp: GeO(s) + 2OH-(aq) +H2O(l)

M(OH)42-(aq)
Ge(OH)42-(aq)

CO2 and SiO2 are acidic dioxides, covalent dioxides.

CO2 dissolve in cold, dilute alkali to form carbonates.
CO2(g) + 2NaOH(aq)
Na2CO3(aq) + H2O(l)
SiO2 dissolve in hot, caustic alkali to form silicates.
SiO2(g) + 2NaOH(aq)
Na2SiO3(aq) + H2O(l)
Dioxides of germanium, tin and lead are amphoteric
a) GeO2 and SnO2 react with hot concentrated hydrochloric acid to form
tetrachloride.
GeO2(s) + 4HCl(aq)

GeCl4 (l) + 2H2O(l)

SnO2(s) + 4HCl(aq)
SnCl4 (l) + 2H2O(l)
b) Lead dioxide react with hot concentrated hydrochloric acid to
produce lead (II) chloride with the liberation of chlorine gas due to
the decomposition of unstable lead tetrachloride.
PbO2(s) + 4HCl(aq)
PbCl2 (s) + Cl2(g) +H2O(l)
c) Lead dioxide react with cold, concentrated hydrochloric acid to
produce lead tetrachloride.
PbO2(s) + 4HCl(aq)

RELATIVE STABILITY OF +2 AND +4 OXIDATION STATES OF GROUP 14 ELEMENTS

PbCl4 (s) + 2H2O(l)

Valence shell configuration :ns2 np2

Can exhibit two oxidation states : +2 and +4
+2 oxidation state involve only s2 electrons, while +4 oxidation state involve s2 and p2 electrons.
Going down the group, the atomic radius increases and the strength of the covalent bond formed gets weaker and less energy is released.
As a result, +4 oxidation state becomes less stable and +2 oxidation state become more stable.

C, Si and Ge - +4 oxidation state is more stable than +2 oxidation state .

Sn - +4 oxidation state is slightly stable than the +2 oxidation state.
Pb- +2 oxidation state is more stable than +4 oxidation state.

Inert pair effect- The inert pair arises from the non-involment of a pair of valence s electron in bond formation.
The inert pair effect is caused by the 5d and 4f orbital that exist between 6s and 6p orbitals causing the removal of 2 electrons from
6p is easier.
The more positive the E value, the more stable is the +2 oxidation state.