Oxides of Group 14

Oxides of Group 14
Group 14 elements form oxides of the type MO and MO2. The acidic nature decreases with
increases of atomic number. CO2 and SiO2 are acidic while GeO2, SnO2 and PbO2 are
amphoteric. All these dissolve in alkalies giving carbonates, silicates, germinates,stannets and
plumbates, respectively.
MO2 + 2NaOH→Na2MO3 + H2O

The dioxides of Ge, Sn and Pb also

dissolve in acids.
GeO2 + 4HCl→GeCl4 + 2 H2O
SnO2 + 4HCl→ SnCl4 + 2H2O
PbO2 + 4HCl → PbCl2 + Cl2 + 2H2O
Among the monoxides, CO is neutral,
GeO is basic, and SnO and PbO are
amphoteric.

Lead forms mixed oxide Pb3O4. This is called red lead and may be represented as 2PbO.PbO2:
clearly it contains Pb(II) and Pb(IV). Pb3O4 is used in paint to prevent the rusting of iron and
steel. It is also used to colour and vulcanize plastic and artificial rubber. PbO2 is used as a strong
oxidizing agent and is produced in situ in lead storage batteries.
 Oxides of Carbon
• Carbon form more oxides
than the other elements and
these oxides differ from
those of the elements
because they contain pπ-pπ
multiple bonds between C
and O.
• Two of these oxides, CO and
CO2 are extremely stable and
important.
• Three are less stable: C3O2,
C 5 O 2 and C 12 O 9 . Others
which are even less stable
include graphite oxide, C2O
and C2O3.
 Carbon monoxide
CO is a colourless, poisonous gas. It is formed
when C is burned in a limited amount of air. In the
laboratory it is prepared by dehydrating formic acid
with concentrated H2SO4.
HCOOH + H2SO4 → CO + H2O

CO is toxic because it forms a complex with

haemoglobin in the blood and this complex is
more stable than oxy-hemoglobin. This prevents
the hemoglobin in the red blood corpuscles from
carrying oxygen round the body. This causes an
oxygen deficiency, leading to unconsciousness
and then death.

CO is sparingly soluble in water and is a

neutral oxide. CO is an important fuel,
because it evolves a considerable amount of
heat when it burns in air.
2CO + O2→ 2CO2 ∆Ho = -565 kJ mol-1
 Carbon monoxide containing fuel
Water gas
It is an equimolar mixture of CO and
H2. Water gas is made by blowing
steam through red or hot coke.
C + H2O →CO + H2 (water gas)

Producer gas
It is the mixture of CO and N2.
Producer gas is made by blowing air through
red hot coke.
2C+ O2 + 4N2 →2CO + N2 (Producer gas)

Coal gas
It is the mixture of CO, H2, CH4 and CO2.
Producer gas is a less efficient fuel than water
gas i.e. it has lower calorific value.
 Reaction of Carbon monoxide
CO is a good reducing agent and can reduce
many metal oxides to the metal.
Fe2O3 + 3CO → 2Fe + 3CO2
Cu + CO → Cu + CO2
CO combines with O, S and the halogens.
CO + S → COS (Carbonyl sulphide)
CO + Cl2 → COCl2 (Carbonyl chloride/ phosgene)
The carbonyl halides are readily hydrolysed by water, and
react with ammonia to form urea.
COCl2 + 2NH3→CO(NH2)2 + 2HCl
Carbonyl chloride is extremely toxic, and was used as a
poisonous gas in World War I where it was responsible
for 85,000 deaths. It is a highly potent pulmonary irritant.
Phosgene was first synthesized in 1812 by British chemist John Davy. It became
known as "phosgene" because Davy created it by reacting carbon monoxide and
chlorine in the presence of sunlight, using the Greek words for "light" and "to give
birth" German chemist Fritz Haber later developed and implemented phosgene as a
weapon during World War I.
CO is an important ligand. In the Mond Process for purifying nickel, nickel carbonyl Ni(CO)4
was made from Ni and CO at 50oC. Separated Ni(CO)4 gas then decomposed at 230oC to get
pure Ni.
 Carbon dioxide (CO2)
CO2 is a colourless and odourless gas. It is recovered from
fermentation processes in breweries, from the gases evolved
from calcining limestone in lime kilns and from the flue
gases from coal-burning electric power stations.
C6H12O6 → 2C2H5OH + CO2
(yeast under anaerobic conditions)
CaCO3 → CaO + CO2 (Strong heat)

The CO2 is recovered by absorbing it in either Na2CO3 or ethanolamine.

NaCO3 + CO2 + H2O → 2NaHCO3
2HOCH2CH2NH2 + CO2 + H2O → (HOCH2CH2NH3)2CO3

Dry ice
CO2 gas can be liquefied under pressure at
-57oC to +31oC. The solid is produced as
white snow by expanding the gas from
cylinder (Expansion causes cooling) is called
dry ice or cardice. Dry ice has an extremely
low temperature of -78.5 °C (-109.3 °F)at
standard atmospheric pressure. It is used to
freeze meat, frozen foods and ice cream and
in the laboratory as the coolant.
 Properties of Carbon dioxide (CO2)
CO2 gas is detected by the action on lime
water Ca(OH)2 or baryta water Ba(OH)2, as a
white insoluble precipitate of CaCO3 or BaCO3
is formed. If more CO2 is passed through the
mixture, the cloudiness disappears as the
soluble bicarbonate formed.
Ca(OH)2 + CO2→ CaCO3 (white ppt) + H2O
CaCO3 + CO2 + H2O → Ca(HCO3)2 (soluble)

CO2 is an acidic oxide, and reacts with base,

forming salts. It dissolves in water but it is only
slightly hydrated to carbonic acid H2CO3, and the
solution contains few carbonate or bicarbonate ions. A
hydrated CO2.8H2O can be crystallized at 0oC under a
pressure of 50 atmospheres CO2.
CO2 + H2O → H2CO3
Carbonic acid has never been isolated, but it gives rise
to two series of salts, bicarbonates (acid salt) and
carbonates (normal salt).
 Carbon suboxide (C3O2)
Carbon suboxide(O=C=C=C=O) is a foul-smelling gas, boiling point 6oC.
It is made by dehydrating malonic acid with P4O10.
[Link]
 Oxides of Silicon
Two oxides of silicon, SiO and SiO2, have been reported. Silicon monoxide is
thought to be formed by high temperature reduction of SiO2.
 Silicon dioxide (SiO2)
Silicon dioxide SiO2 is commonly called silica and it is widely found as sand and quartz,
which comprises more than 10% by mass of the Earth's crust. Quartz is the only polymorph of
silica stable at the Earth's surface. In chemistry and mineralogy, polymorphs are different
crystal structures of the same compound with distinct physical properties like solubility,
stability, and dissolution rate.

• Pure SiO 2is colourless, but traces of

other metals may colour it, giving
semi-precious gemstones such as
amethyst (violet), rose quartz (pink),
smoky quartz (brown), citrine
(yellow) and non-precious material

• SiO 2 exists in at least 12 different

forms. The main ones are quartz,
tridymite and cristobalite, each of
which has different structures at high
and low temperatures.
• Alpha-quartz is by far the most
common and is a major constituent of
granite and sandstone.
 Structure of Silicon dioxide (SiO2)
• In all of these forms each Si is tetrahedrally
surrounded by O atoms.
• Each corner is shared with another tetrahedron,
thus giving an infinite array.
• The difference between these structures is the way in
which the tetrahedral SiO4 units are arranged.
Heating any solid form of SiO2 to its softening
temperature or slow cooling of molten SiO2, gives a
glass like solid. This is amorphous, and contains a
disordered mixture of rings, chains and three-
dimensional [Link] of these distinct crystalline
forms always have the same local structure around Si
and O.
• In α-quartz the Si–O bond length is 161 pm, Typical subunit for low pressure
whereas in α-tridymite it is in the range 154–171 silicon dioxide
pm.
• The Si–O–Si angle also varies between a low
value of 140° in α-tridymite, up to 180° in β-
tridymite. In α-quartz, the Si–O–Si angle is 144°.
 Reactions of Silicon dioxide (SiO2)
• Silica in any form is unreactive.
• It is an acidic oxide and so does not react
with acids.

• However, it does react with with HF,

forming silicon tetrafluoride SiF4. When
the SiF4 comes into contact with a drop
of water it is hydrolysed to silicic acid.
This can be seen as a white solid
forming on the surface of a drop of
water.
H2SO4 + CaF2 →HF
HF+ SiO2→SiF4
SiF4 + H2O→HF + Si(OH)4 or SiO2.2H2O
This is the test for fluoride ion.
 Reactions of Silicon dioxide (SiO2)
Why NaOH is not kept in glass container?

SiO2 is an acidic oxide it dissolves

slowly in aqueous alkali and more
rapidly in fused alkalis MOH and
fused carbonates M2CO3, forming
silicates.
SiO2 + NaOH→ (Na2SiO3)n and
Na4SiO4
This reaction accounts for ground
glass stoppers sticking in reagent
bottles containing NaOH.
 Why CO2 is gas and SiO2 is a solid?
CO2 has a linear structure. Carbon atom is linked to two
oxygen atoms by double covalent bonds. Carbon is sp
hybridized. These hybrid orbitals overlap with the p-
orbital of each oxygen atom. The remaining 2p-orbitals
of each oxygen atom form π-bonds with p-orbitals of
carbon atom. So, CO2 molecules are held together by
weak van der Waals' forces hence, it exists as a gas at
ordinary temperatures.

Silica (SiO2) has a three dimensional

infinite structure (sp3 hybridized) in which
silicon is tetrahedrally bonded to four
oxygen atoms and each oxygen atom is
bonded to two silicon atoms by covalent
bonds. Hence, silica has high melting
point and is a solid. Silica is insoluble in
water and acts as a very weak acid.