INORGANIC CHEMISTRY

CHAPTER 4 :
NITROGEN AND ITS
COMPOUND
4.1 Introduction to nitrogen
Name and symbol Nitrogen ; N (naturally exist as N2)
Electronic configuration 1s2 2s2 2p3
Position in Periodic Table Group 15 : Period 2
Melting point –210oC
Boiling point –196 oC
Electronegativity 3.0
1st ionisation energy 1s2 2s2 2p3
Type of bonding Covalent bond

Nitrogen exists naturally as diatoms and held by short strong triple bond

It is inert as triple bond of nitrogen is short and strong. This can be

supported by the ∆Hatom where;
½ N2 (g)  N (g) ∆Hatom = + 472 kJ / mol

Nitrogen can be obtained by air fractional distillation, as the major
constituent of air is nitrogen (78%)

In laboratory, nitrogen can be prepared using the following methods

Thermal decomposition of solid ammonium dichromate (VI)
(NH4)2Cr2O7 (s)  Cr2O3 (s) + 4 H2O (g) + N2 (g)
Mixing solid sodium nitrate, NaNO3, with ammonium chloride, NH4Cl
NaNO2 (s) + NH4Cl (s)  NaCl (s) + N2 (g) + 2 H2O (g)
4.2 Chemical properties of nitrogen

Nitrogen gas itself is an inert gas as the short bond of nitrogen gas (shown
above) which causes a lot of energy is required to break the bond.

Under high temperature, nitrogen can react easily with other elements to
form new compound.

It can react easily with substance which is very exothermic o react with air,
for example like reacting with magnesium and aluminium to form nitride
(N3-) based compound
3 Mg (s) + N2 (g)  Mg3N2 (s) 2 Al (s) + N2 (g)  2 AlN

The nitride formed will be hydrolysed and ammonia gas is released
Mg3N2 (s) + H2O (l)  3 Mg(OH)2 + 2 NH3
AlN (s) + H2O (l)  Al(OH)3 + NH3

Other than in the form of nitride, N3-, nitrogen can exist in compound with
different oxidation state
Nitrogen NH3 ; NH2O HNO2 NO2 ; HNO3
N2H4 N2 N2O NO
compound N3- H ; NO2- N2O4 N2O5
Oxidation
–3 –2 –1 0 +1 +2 +3 +4 +5
state
4.3 Ammonia and its salt
4.3.1 Production of ammonia


Haber Process
Ammonia is produced in industries using …………………………………

It is formed from combustion of nitrogen and hydrogen under iron as
catalyst

The pressure and temperature is high to achieve high yield of ammonia

production. (The yield of ammonia can be deduce using Le Chatelier’s
Principle)
Ammonia is used widely in industrial in the following application :

manufacturing fertiliser such as ammonium sulphate, ammonium phosphate
and ammonium nitrateproducing nitric acid

use in refrigeration when liquefied

use as a “smelling salt” to prevent fainting, in the form of hydroxide.

Ammonia is prepared in laboratory by using ammonium salt with strong
base
NH4Cl (s) + NaOH (aq)  NaCl + NH3 (g) + H2O (l)

4.3.2 Physical properties of ammonia

Ammonia is a colourless gas with pungent smell.

It is a polar molecule with pyramidal shape

It is easily dissolve in water and form hydrogen bond

Liquid formed of ammonia undergoes autoionisation to produce opposite
charge ion. Hence ammonia is a weak conductor of electricity
2 NH3 NH4+ + NH2–
4.3.2 Chemical properties of ammonia

Ammonia is a weak base. When dissolve in water, ammonia dissociate
to form hydroxide ion
NH3 (g) + H2O (l) NH4+ (aq) + OH-(aq) Kb = 1.8 x 10-5 mol dm-3

In this case, ammonia act as a Bronsted Lowry base (a proton
acceptor). Since it has a low Kb, it indicates the dissociation of
ammonia in water is only partially.

Ammonia react with acid to form ammonium salt

NH3 (aq) + HCl (aq)  NH4Cl

NH3 (aq) + H2SO4 (aq)  (NH4)2SO4

Aqueous ammonia solution is also used in the identification of cation.
For example, when dissolve ammonia in 3 different cation solutions;
Copper (II) ion ; Nickel (II) ion and lead (II) ion
 In small amount of NH3 (aq)
Cation In excess NH3 (aq) solution
solution
The blue precipitate of copper
(II) hydroxide dissolve in
A blue precipitate of copper
Cu2+ excess to form deep blue
(II) hydroxide is first formed.
Copper (II) ion solution.
Cu2+ + 2 NH3 + 2 H2O 
Cu(OH)2 + 4 NH3 
Cu(OH)2 + 2 NH4+
Cu(NH3)42+ + 2 OH–

The white precipitate of zinc

A white precipitate of zinc hydroxide dissolved in excess
Zn2+ hydroxide is first formed. to form colourless solution.
Zinc ion Zn2+ + 2 NH3 + 2 H2O  Zn(OH)2 + 4 NH3 
Zn(OH)2 + 2 NH4+ Zn(NH3)42+ + 2 OH–

A white precipitate of lead (II) The white precipitate does not

Pb2+ hydroxide is first formed. soluble in excess as lead
Lead (II) ion Pb2+ + 2 NH3 + 2 H2O  does not form complex
Pb(OH)2 + 2 NH4+ solution with ammonia

Ammonia molecule attached to metal ion using the lone pair electron
of ammonia. At this point, ammonia act as a Lewis base, where it
donate the lone pair electrons to the metal ion and become ligand.

a) tetraamminecopper (II) ion b) hexaamminechromium (III) ion

H3N 2+

Cu
H3N NH3
NH3

Other than becoming a ligand, ammonia can also donate the lone
pair electron to electron deficient molecules such as boron trifluoride,
aluminium trichloride or beryllium dichloride

a) boron trifluoride + ammonia b) beryllium dichloride + ammonia


Ammonia can also behave as a reducing agent. When ammonia is
oxidised to nitrogen :
2 NH3  N2 + 6 H+ + 6 e-

Whenever ammonia gas react with chlorine gas, the following
reaction occur
8 NH3 (g) + 3 Cl2 (g)  N2 (g) + 6 NH4Cl (s)

If excess chlorine gas is passed through ammonia gas, nitrogen
trichloride can be produced with white fume released.
NH3 (g) + 3 Cl2 (g)  NCl3 (l) + 3 HCl (g)

Ammonium compound when heated can be decomposed. Though, all
the reaction can be explosive.
NH4NO2  N2 + 2 H2O
(NH4)2Cr2O7  Cr2O3 (s) + 4 H2O (g) + N2 (g)
NH4NO3  N2O + 2 H2O
4.4 Manufacture of Nitric Acid (Ostwald Process)

Nitric acid mainly manufactured by catalytic oxidation of ammonia which
produced by Haber Process. The ammonia & air are passed over platinum
gauze at temperature around 8500C. It is oxidised to nitric oxide
4 NH3 (g) + 5 O2 (g)  4 NO (g) + 6 H2O (l)

The hot nitric oxide gas is cooled & then oxidised by more air to nitrogen
dioxide
2 NO (g) + O2 (g)  2 NO2 (g) ∆H = – 114 kJ / mol

The nitrogen dioxide & excess air are then passed up the towers filled wit
broken bricks to flows water slowly. The nitrogen dioxide dissolved in
water to form nitric acid. The temperature needed is at 80oC & pressure
of 8 atm.

Under the presence of air

4 NO2 (g) + 2 H2O (l) + O2 (g)  4 HNO3 (aq) ∆H = –950 kJ / mol

 Under the absence of air (anaerobic)

3 NO2 (g) + H2O (l)  2 HNO3 (aq) + NO (g) [Nitrogen monoxide

can be recycle back to chamber, reproducing nitric acid]
• The percentage of purity of nitric acid produced at this stage is approximately 68%.A
higher concentration of nitric acid can be obtained by distillation with concentrated
sulphuric acid whereby the purity of nitric acid can be increased as high as 98%

N2 + + O2 (g) NO
3 H2 NH3 8500C /1 (nitrogen + O2 (g) NO2 (g)
atm + Pt
monoxide)
+ H2O (l)
NO is recycle

Fractional 68% HNO3 (aq) Extract

98% HNO3 distillation (in azeotropic from
mixture with water) vessel
4.4.1 The uses of nitric acid

Manufacture of ammonium nitrate & sodium nitrate for fertiliser

Produce chemical explosive for mining & quarrying such as

trinitroglycerine (from nitric acid & glycerin) & TNT (trinitrotoluene)

which from toluene & nitric acid and were misused in war.

Use as a strong oxidising agent

Use as acid. However, only very dilute nitric acid will give off

hydrogen gas with electropositive metal

4.4.2 Physical / Chemical properties of nitric acid

Pure nitric (V) acid is a colourless, viscous liquid. Concentrated nitric (V) acid
always looks yellowish due to the decomposition of nitric acid to nitrogen
dioxide (which makes the solution look yellow) and oxygen gas
4 HNO3 (aq)  4 NO2 (g) + O2 (g) + 2 H2O (l)

Light and heat will accelerate the decomposition. This is why nitric acid is
always kept in dark bottle.

Pure nitric (V) acid is actually a weak electrolyte because of the
autoionisation.
2 HNO3  NO3– + NO2+ + H2O

Hence, pure nitric (V) acid not a strong acid. (pure nitric acid has high
covalent characteristic)

Still, nitric (V) acid dissolves in water easily and formed diluted nitric (V)
acid. Diluted nitric acid is a strong acid and dissociate completely in water.

Dissociation equation :
HNO3 + H2O  NO3– + H3O+

Since it is an acid, it can react with base to form salt and water.
Example : NaOH (aq) + HNO3 (aq)  NaNO3 (aq) + H2O (l)
PbO (s) + 2 HNO3 (aq)  Pb(NO3)2 (aq) + H2O (l)

When react with carbonate, it also liberates carbon dioxide.

Example : K2CO3 (aq) + 2 HNO3 (aq) 

2 KNO3 (aq) + CO2 (g) + H2O (l)

However, unlike any acid, dilute nitric acid does not liberate
hydrogen gas when react with metal. Nitric acid is a strong oxidising
agent. Conditions of the reaction with acid also determine the product
that might be formed.

When react with a less electropositive metal like copper and lead :

Cu (s) + 4 HNO3 (aq) Hot concentrated Cu(NO3)2 (aq) + 2 NO2 (g) + 2 H2O (l)
3 Cu (s) + 8 HNO3 (aq) Warm diluted 3 Cu(NO3)2(aq) + 2 NO (g) + 2 H2O (l)

When react with a more electropositive metal such as zinc
10 HNO3 (aq) + 4 Zn (s)  4 Zn(NO3)2 + NH4NO3 (aq) + 3 H2O (l)

Some metal does not actually react with nitric acid (discussed in aluminium
once) as nitric acid will increase the oxide layer of the metal causing the
metal become more passive.

When hot concentrated nitric (V) acid react with non metal, it will form the
non-metal acid at the highest oxidation state. Nitrogen dioxide and water
are formed as side product.

If phosphorous, P :
2 P + 10 HNO3  P2O5 + 10 NO2 + 5 H2O

If sulphur, S:
S + 6 HNO3  SO3 + 6 NO2 + 3 H2O

If carbon, C:
C + 4 HNO3  CO2 + 2 NO2 + 2 H2O
4.5 Oxide of nitrogen

Table below shows the many type of nitrogen oxide compounds
Oxide of nitrogen N2 O NO N2O3 NO2 N2O4 N2O5
Oxidation state of N +1 +2 +3 +4 +4 +5
Boiling point (oC) -88 -152 3 - 21 32

1. Nitrogen monoxide (NO)

Nitrogen monoxide is colourless, toxic and insoluble in water.

The Lewis structure of nitrogen monoxide

Nitrogen monoxide can be produced naturally when

Nitrogen and oxygen in the atmosphere combined at high temperature
(given when there’s lightning).

Nitrogen and oxygen in the hot vehicle engine reacted

N2 (g) + O2 (g)  2 NO (g)


Nitrogen monoxide can also be produced in laboratory when reacting
copper to warm diluted nitric acid
3 Cu (s) + 8 HNO3 (aq) Warm diluted 3 Cu(NO3)2(aq) + 2 NO (g) + 2 H2O (l)

Due to the odd number of electron in nitrogen monoxide, it is easily oxidised

to form nitrogen dioxide.

2 NO (g) + O2 (g)  2 NO2 (g)

2. Nitrogen dioxide (NO2) and Dinitrogen tetraoxide (N2O4)

Nitrogen dioxide is a brown and toxic gas. Under room temperature, the
Lewis structure ;

Nitrogen dioxide produce naturally when nitrogen monoxide is oxidised to

nitrogen dioxide (as above)

In laboratory, when heating nitrate salt, nitrogen dioxide can be produced
through decomposition.
2 M(NO3)2  2 MO (s) + 4 NO2 (g) + O2 (g)

When nitrogen dioxide dissolve in water, disproportionation occur where
nitrous acid and nitric acid is produced
2 NO2 + H2O  HNO3 + HNO2

Same things occur when dissolve in sodium / potassium hydroxide

2 NaOH + 2 NO2  NaNO3 + NaNO2 + H2O


Like nitrogen monoxide, nitrogen dioxide, NO2, also have a single electron
which makes NO2 unstable hence toxic. Since it is unstable, nitrogen dioxide
tend to form a dimer of dinitrogen tetraoxide, N2O4, a colourless gas.
Under room condition, nitrogen dioxide exist in equilibrium with its dimer.
N2O4 (g) 2 NO2 (g) ∆H = + 58.2 kJ / mol

As a conclusion, from nitrogen and oxygen to dinitrogen tetraoxide, the
following can be deduced :

N2 At r.t.p.
1. Engine
+
2.Lightning
NO +O2 NO2 N2O4
O2 heat
Environmental Problem caused by nitrogen oxide

1. Acid rain – one of the 3 main components in acid rain is
produced from nitrogen dioxide

3 main components are

CO2 + H2O  H2CO3

NO2 + H2O  HNO3 + HNO2
SO2 + H2O  H2SO3

pH of the acid rain is between 4.1 – 5.6.

Acid rain causes damages to marbles and limestone of building and
statues. Its also harmful to vegetation and aquatic life
2. Nitric oxide is the product of the reaction between atmospheric oxygen
& nitrogen in an internal combustion engine or at very high temperatures
N2 (g) + O2 (g) 2 NO (g) + O2 (g) 2 NO2 (g)

Once released into atmosphere, nitric oxide quickly oxidised to nitrogen
dioxide

With sunlight, photochemical decomposition of nitrogen dioxide occurs
forming oxygen radical
NO2 (g) + hv NO (g) + O• (g)

Oxygen radical is highly reactive, combine with oxygen mol in air to
form ozone
O2 (g) + O• (g) O3 (g)

Ozone attacks the C=C linkage in hydrocarbons to form ozonide ,then
the ozonide is hydrolised & forms cleavage products like ketones

This reaction is called ozonolysis, where it cause rubber tyre cracks &
harmful to health (damage lung).

Concentration of NO2 in air is low in morning, but when sun rises, NO +
O2 reaction will be enhance + air release by the automotive vehicles. It
will causes smoky vision, which is known as haze
3. Automobile exhaust

Used in cars to minimise air pollution problem

Petrol burns in engines released a lot of heat at high temperature At this
temperature, nitrogen and oxygen combined and form nitric oxide
N2 (g) + O2 (g) 2 NO (g)

Spontaneous burning results incomplete combustion of petrol producing
carbon monoxide and released to atmosphere as smoke that contains
nitric oxide,carbon monoxide & residual hydrocarbons and pollute the
air.So,catalytic converters reduce the pollution.

The catalytic converters consists of two chambers

In the 1st chambers, hot exhaust gases passed over catalyst. Air is
injected to help accelerate the complete burning of carbon monoxide
& hydrocarbons

In 2nd chamber, different catalyst CuO or Cr2O3 used to dissociate
nitric oxide to form harmless nitrogen & oxygen gases
CO + NO  CO2 + ½ N2
4.7 Nitrogen cycle

Lightning causes nitrogen & oxygen gases in the air to form nitric
oxide, which then oxidised to nitrogen dioxide,NO2.The gas then
washed out by rain as nitric acid

The acid form nitrates in soil which is absorb by plants from the soil

through the roots as protein. The nitrogen then passed to herbivores

& carnivores in the food chain.

When plants and animals died, nitrogen compounds are returned
back to soil as aluminium compounds. These compounds may be
converted to free nitrogen through denitrification & back to the
atmosphere