CHEMISTR

Y
OF
NITROGEN
•Nitrogen occurs chiefly as a free
element in the air, making up about
78% by volume of the atmosphere.
Free nitrogen in air is important
because it dilutes the oxygen where
combustion,respiration and oxidation of
metals are reasonably slow.
 Laboratory
Preparation of
Nitrogen
•Since nitrogen makes up a large
percentage of air, it can be
obtained from air by removing
the other constituents.
•For example,carbon(iv)oxide and
oxygen can be removed by
passing air through caustic soda
and heated copper turnings
respectively.
•However,the nitrogen obtained
this way contains about 1% by
volume of rare gases as
impurities, and is denser than
pure nitrogen.
•Nitrogen can also be produced by
the following chemical methods:
•1. From ammonium dioxonitrate(iii)
• NaNO3 + NH4Cl --› NH4NO2 + NaCl
• NH4NO2 --› N2 + 2H2O
•2. From ammonium
heptaoxodichromate(vi)
• (NH4)2Cr2O7 --› N2 + Cr2O3 + 4H2O
•3. From ammonia
• 2NH3 + 3CuO --› 3Cu + 3H2O + N2
•4. From dinitrogen(i)
• N2O + Cu --› CuO + N2
 INDUSTRIAL
PREPARATION
•Industrially, nitrogen is prepared by
the fractional distillation of liquid air.
Air,from which carbon(iv)oxide has
been removed, is liquefied by
subjecting it to successive compression
and cooling processes.
•Upon distillation, nitrogen is
evolved first at -196°C and is
separated from oxygen which
boils at -183°C.
 Physical
Properties
•1. Nitrogen is a colourless, odourless
and tasteless gas.
•2. Pure nitrogen is slightly soluble in
water.
•3. The melting point is -210°C and it’s
boiling point is -196°C.
 Chemical
Properties
•1. With metals: Nitrogen
combines directly with very
electropositive metals.
•3Mg + N2 --› Mg3N2
•2. With non-metals: Nitrogen
combines reversibly with
hydrogen to produce ammonia.
•N2 + 3H2 --› 2NH3
 Uses of Nitrogen
•1. Nitrogen is used in the industrial
manufacture of ammonia, cyanide,
cyanamide an carbamide.
•2. Liquid nitrogen is used as a
cooling agent.
• 3. Due to its inert nature, nitrogen is used
• - as a carrier gas in gas chromatography.
• - in providing an inert atmosphere for certain
industrial processes.
• - as a preservative to prevent rancidity(
oxidation of fatty acid)
 AMMONIA
•Ammonia is a hydride of nitrogen.
It is a very important chemical in
industries. In nature, ammonia is
produced when nitrogenous matter
decays in the absence of air.
 Laboratory
Preparation
•Ammonia is prepared in the laboratory
by heating any ammonium salt with a
non-volatile base. Usually, ammonium
chloride and calcium hydroxide are
used. Calcium hydroxide is used
because it is not deliquescent.
• Ca(OH)2 + 2NH4Cl --› CaCl2 + 2H2O + 2NH3
• The usual drying agents like concentrated
tetraoxosulphate(vi) acid and fused calcium
chloride are not suitable for drying ammonia
because they react with the gas.
 Industrial
Preparation
•Ammonia is manufactured from
nitrogen and hydrogen by the
Haber Process. Basically, the
process involves mixing nitrogen and
hydrogen in the volume ratio of 1:3
and passing the mixture
•- over finely divided iron catalyst.
•- at a temperature of about 450°
C.
•- a pressure of about 200
atmospheres.
•N2 + 3H2 ---› 2NH3
 Physical
Properties
•1. Ammonia is a colourless gas with
a characteristic choking smell.
•2. In large quantities, it is
poisonous because of its effect on
the respiratory muscles.
•3. It is an alkaline gas, changing
red moist litmus paper blue.
•4. It is about 1.7 times less dense
than air.
•5. It changes into liquid at -34.4°
C.
•6. Ammonia has a boiling point
of -77.7°C.
•7. Ammonia is a very soluble
gas.
 Chemical
Properties
•1. Ammonia burns readily in
oxygen with a greenish yellow
flame.
•4NH3 + 3O2 --› 6H2O + 2N2
•2. As a reducing agent:
•3CuO + 2NH3 --› 3Cu + 3H2O + N2
•3. Reaction with carbon(iv)oxide
•2NH3 + CO2 --› (NH2)2CO H2O
•4. Ammonia is decomposed at
temperatures above 500°C or by
prolonged sparking to yield nitrogen
and hydrogen.
•5. As a weak base
•2NH3 + H2SO4 --› (NH4)2SO4
 Test For
Ammonia
•Ammonia has a characteristic
choking smell which is easily
recognizable. Its presence can
be confirmed by doing the
following tests:
•1. Action on litmus paper: Hold a
damp red litmus paper into the jar
containing the unknown gas. If the
litmus paper turns blue, then the
gas is probably ammonia.
•2. Action with hydrochloric acid:
•Dip a glass rod in conc.
Hydrochloric acid and then insert it
in the gas jar containing the
unknown gas. White fumes are
formed if the gas is ammonia.
 Uses of
Ammonia
•1. Aqueous ammonia is used in
softening temporary hard water.
•2. Aqueous ammonia is also used in
laundries as a solvent for removing
grease and oil stains.
•3. Liquid ammonia is used as a
refrigerant, although it is now
being replaced by less toxic and
unreactive fluorocarbons.
•4. Ammonia is used in the
manufacture of
•- trioxonitrate(v)
•- sodium trioxocarbonate(iv) by the
Solvay process.
• 5. The most important use of ammonia is in
the manufacture of nitrogenous fertilizers like
• - ammonium tetraoxosulphate(vi)
• - ammonium trioxonitrate(v)
• - carbamide
• - ammonium tetraoxophosphate(v)
 Oxides of
Nitrogen
•1. Nitrogen(i)oxide (N2O)
•Nitrogen(i)oxide, the first oxide of
nitrogen identified, was discovered by
Priestley. It is known as laughing gas
because it causes uncontrollable fits of
laughter when inhaled.
 Laboratory
Preparation
• KNO3 + NH4Cl --› KCl + NH4NO3
• NH4NO3 ---› 2H2O + N2O
 Physical
Properties
• 1. Nitrogen(i)oxide is a colourless gas with
a faint, pleasant but sickly smell, and a
sweetish taste.
• 2. It is fairly soluble in cold water.
• 3. It is 1.5 times denser than air.
• 4. It is neutral to moist litmus paper.
 Chemical
Properties
•1. Nitrogen(i)oxide does not burn in
air. However, it decomposes rapidly
at red heat into its component
elements.
•2N2O --› 2N2 + O2
•2. Reduction by metals:
•Nitrogen(i)oxide is reduced to
nitrogen when it passes over heated
copper or iron.
•Cu + N2O --› N2 + CuO
 Uses
•Nitrogen(i)oxide is used as a mild
anaesthetic for minor surgical
operations e.g in dental surgery. It
is usually administered with about
20% oxygen, which is required to
keep the patient alive.
Nitrogen(iv)Oxi
de
•Nitrogen(iv)oxide is a reddish
brown gas given off when the
trioxonitrates(v) of heavy metals
are heated.
 Laboratory
Preparation
•The most suitable trioxonitrate(v) for
the preparation of nitrogen(iv)oxide is
lead(ii)trioconitrate(v). This is because
it’s crystals do not contain any water
of crystallization which could interfere
with the preparation.
•On heating strongly, lead(ii)
trioxonitrate(v) crystals crackle,
melt and decompose to yield
lead(ii)oxide, oxygen and
nitrogen(iv)oxide.
•The gases formed are passed through
a U-tube immersed in a freezing
mixture. The nitrogen(iv)oxide becomes
liquefied in the u-tube as a green
liquid (yellow if pure), while the oxygen
escapes from the u-tube as a gas.
•The residue of lead(ii)oxide left
behind in the boiling tube is
reddish-brown when hot, but turns
yellow on cooling.
•2Pb(NO3)2 --› 2PbO + O2 + 4NO2
 Physical
Properties
•1. Nitrogen(iv)oxide is a reddish
brown gas.
•2. It turns damp blue litmus paper
red and dissolves in water to form
an acidic solution.
•3. It is easily liquefied into a yellow
liquid at 21°C.
•4. It has an irritating smell and is
poisonous.
•5. It is much heavier than air and can
be poured downwards.
 Chemical
Properties
• Nitrogen(iv)oxide can exist in molecular forms.
At low temperatures, it exists mainly as
dinitrogen(iv)oxide.
• Above 140°C, nitrogen(iv)oxide dissociates into
nitrogen(ii)oxide and oxygen.
• N2O4 ‹--› 2NO2 ‹--› 2NO + O2
• Pale Yellow Reddish brown Colourless
•2. Nitrogen(iv)oxide does not burn
in air, but it will support the
combustion of any burning
substance.
•2NO2 --› N2 + 2O2
•3. Nitrogen(iv)oxide dissolves in
water to form a mixture of
Dioxonitrate(iii) and trioxonitrate(v)
•2NO2 + H2O --› HNO2 + HNO3
 Trioxonitrate(v)
Acid
•Trioxonitrate(v) acid, HNO3, is
an important acid which is used
extensively in the laboratory and
in the industry. It was first
prepared by Glauber in 1658.
•Early alchemists used the acid for
separating gold from silver. Due to
its corrosive action on metals, it
was previously known as aqua
fortis, meaning strong water.
 Laboratory
Preparation
• Trioxonitrate(v) acid can be displaced from any
trioxonitrate(v) by conc.tetraoxosulphate(vi). The
trioxonitrate(v) of potassium and sodium are usually
used because they are cheap.
• KNO3 + H2SO4 --› KHSO4 + HNO3
• An all glass apparatus is used for the preparation
because the hydrogentrioxonitrate(v) acid vapour will
attack cork or rubber.
 Physical
Properties
•1. Trioxonitrate(v) is a fuming
liquid with a sharp choking smell.
Although, it is colourless when
pure, it tends to turn yellowish
after some time.
•2. The pure acid is very
corrosive and readily destroys
organic matter such as skin,
rubber, cork and clothing.
•3. The dilute acid turns blue litmus
red.
•4. Pure trioxonitrate(v) is miscible
with water in all proportions.
•5. The density of the pure acid is
1.52g/cm³. It boils at 86°C and melts
at -47°C.
 CHEMICAL
PROPERTIES
•1. As an acid:
• HNO3 + NaOH --› NaNO3 + H2O
• 2HNO3 + CaCO3 --› Ca(NO3)2 + H2O + CO2
•2. With metals: It oxidises metals:
• 4HNO3 + Cu --› Cu(NO3)2 + 2H2O + 2NO2
• 3. With non-metals: It oxidises non-metals to
their highest oxides.
• 4HNO3 + C --› CO2 + 2H2O + 4NO2
•4. With reducing agents: As a strong
reducing agent, HNO3 also undergoes
redox reactions with common reducing
agents like hydrogen sulphide.
•H2S + 2HNO3 --› S + 2H2O + 2NO2
•5. Decomposition: HNO3
decomposes at room temperature
(especially in the presence of light)
and rapidly when heated to yield
nitrogen(iv)oxide and oxygen.
•4HNO3 --› 2H2O + 4NO2 + O2
•6. Nitration reactions: In the
presence of concentrated H2SO4,
HNO3 dissociates to form the nitryl
-
cation, NO2 , which can replace the
hydrogen ions from many organic
compounds.
•This process is known as nitration
and is of great industrial
importance.
•C6H6 + HNO3 --› C6H5NO2 + H2O
 Uses of HNO3
•1. It is used as an acid, an
oxidizing agent and a nitrating
agent in the laboratory.
•2. It is used as rocket fuel.
•3. It is used as an oxidizing
agent in the production of
important polymers like nylon and
terylene.
•4. A mixture of three parts of
hydrochloric acid and one part of
trioxonitrate(v) acid known as
aqua regia, is used as a solvent
for gold and platinum.
•5. It is used as an important
starting material in the
manufacture of
fertilizers(nitrochalk), dyes,
drugs and explosives.