TETRACHLORIDES

AND OXIDES OF
GROUP 14
ELEMENTS
  Simple molecule with general formula of MCl4
 Colourless liquids at room conditions
 Tetrahedral shape with bond angle od 109.5˚
 Tetrachlorides of silicon, germanium, tin and lead can be
prepared by direct combination, by heating the element
in a stream of dry chlorine gas
TETRACHLO
RIDES  Carbon tetrachloride is prepared by passing dry chlorine
gas into liquid carbon disulphide boiling under reflux in
the presence of a little iodine as catalyst.

 Lead (IV) chloride is prepared by reacting lead dioxide

with concentrated hydrochloric acid at 5˚C.
 BOILING POINT OF THE TETRACHLORIDES

01 02 03
Tetrachlorides of Group Going the group, the size There is no normal
14 elements are simple and the total number of boiling point for lead
covalent compound with electrons in the molecule
increase. The van der Waals
tetrachloride because it
weak van der Waals decomposes on heating
forces get stronger. As a
forces result, the boiling points of • Equation:
the tetrachlorides increase
down the group.
 Going down In contras,
Group 14, the As a result, the SnCl4 undergoes
PbCl4, is so
M-Cl bonds thermal CCl4, SiCl4 and decomposition
unstable that it
GeCl4 are stable on strong
become longer stability of the could undergoes
to heat even at heating to
and weaker as tetrachlorides partial
high produce tin (II)
the atomic decreases down decomposition
temperatures. chloride and
radius of M the group. even at room
chlorine gas.
increases. temperature.

THERMAL STABILITY OF TETRACHLORIDES

 HYDROLYSIS OF TETRACHLORIDES

All tetrachlorides of Group 14 The intermediate then decomposes to

The silicon atom makes use of the
undergoes hydrolysis with water to produce silicon (IV) oxide and
empty 3d orbitals to accept lone pair
produce hydrochloric acid or hydrogen hydrochloric acid.
electrons from two water molecules to
chloride gas depending on the amount • Equation:
form hexa-valency intermediate.
of water used.

On the other hand, there are no empty

Silicon, germanium, tin and lead can
d-orbital in the valence shell of carbon
make use of their empty d orbitals to
in CCl4 to form coordinate bond with
form complexes.
water and is not hydrolysed by water.
 MONOXIDE CO SiO GeO SnO PbO
PHYSICAL
Gas Solid
STATE
STRUCTURE Simple molecule Predominantly ionic
THERMAL
Form dioxide on heating in air Stable
STABILITY
ACID/BASE
THERMAL NATURE
Neutral Amphoteric

STABILITY OF DIOXIDE CO2 SiO2 GeO2 SnO2 PbO2

OXIDES PHYSICAL
Gas Solid
STATE
STRUCTURE Simple Giant Intermediate between giant
molecule covalent covalent and giant ionic
THERMAL
Stable Unstable
STABILITY
ACID/BASE
Acidic Amphoteric
NATURE
 CO SiO GeO SnO PbO

Acid/base
Acid/base Neutral
Neutral Amphoteric
Amphoteric
nature
nature

ACID-BASE Metallic
Metallic character
character increase
increase with
number
number
with increasing
increasing proton
proton

NATURE OF In hot, dilute

In hot, dilute
mineral acid
All monoxide dissolve

THE OXIDES mineral acid

MO(s) + 2H+(aq) M2+(aq) + H2O(l)

In hot, Dissolve
In hot,
concentrated
concentrated
alkali - - MO(s) + 2OH-(aq) + H2O(l)
alkali - - M(OH)42-(aq)
 CO2 SiO2 GeO2 SnO2

Acid/base Acidic Amphoteric

nature
Covalent Intermediate between ionic
and covalent

ACID-BASE
NATURE OF   Carbon dioxide

THE OXIDES Dissolve in cold, dilute alkali

CO2(g) + 2NaOH(aq) Na2CO3(aq) + H2O(l)

 Silicon dioxide
Dissolve slowly in hot, caustic alkali
SiO2(g) + 2NaOH(aq) Na2SiO3(aq) + H2O(l)
   Amphoteric dioxide
 Dissolve in hot, dilute mineral acid
 GeO2(g) + 4HCl (aq) GeCl4(aq) + 2H2O(l)
 SnO2(g) + 4HCl (aq) SnCl4(aq) + 2H2O(l)
(The tetrachloride formed undergoes slight hydrolysis due to the
presence of the common ion Cl-)

ACID-BASE  PbO2(g) + 4HCl (aq) PbCl2(aq) + Cl2(g) + 2H2O(l)

NATURE OF (reaction with hot, concentrated HCl)

 PbO2(g) + 4HCl (aq) PbCl4(aq) + 2H2O(l)
THE OXIDES (reaction with cold, concentrated HCl)

 React with hot, concentrated alkali

 MO2(s) + 2OH-(aq) + 2H2O(l) M(OH)62-(aq)