Chemistry R&D 2010

4. Group 15: Nitrogen and its Compound

1) Nitrogen
2) Ammonia
3) Oxides of nitrogen

Name: Ng Siang Bing (6AH1)

Sharon Low Kit Wah (6AH1)

Teacher’s name: Puan Jaya Mary

1
The Inert Nature of Nitrogen
• Form covalent bond to achieves stable octet electron arrangement
• Consists of simple diatomic molecules with a covalent triple bond
•Very stable & relatively inert
o Short bond length and high bond energy
(bond energy increase, energy to dissociate the molecules increase)
o Linear and non-polar
(distribution of electrons is symmetrical, no polarity)

Extraction of Nitrogen from Air

Stage 1: Liquefaction of air
 Clean air is cooled and passed through the compressor under high temperature
 Cooled air is then passed through the expansion nozzle with lowered temperature
 Liquefied air is produced and thus passed through the filter to filter off solid
CO2 & hydrocarbons
 The process of compression and expansion is repeated
Stage 2: Fractional Distillation
 Liquefied air contains nitrogen and oxygen
o Nitrogen has the lower boiling point which will vaporise first
 Liquefied air is passed through the fractionating column
 Nitrogen gas will be the first vaporise and realease at the top of the fractionating
column
 The nitrogen gas is then distilled off to produced 40% of oxygen
 Liquid oxygen is condensed at the bottom of the fractionating column
 Fractional distillation produce nitrogen, argon and liquid oxygen

Ammonia
Formation of ammonia from ammonium salts
 Ammonia gas is prepared by heating a mixture of ammonium salt and a base( NaOH,
KOH, CaO, Ca(OH)2, CaCO3)

NH4 + + OH - NH3 + H2O

 For example, when ammonium chloride(ammonium salt) is heated with calcium
hydroxide(a base), ammonia gas is given out.

2NH4Cl + Ca(OH)2(s) CaCl2 + 2H2O + 2NH3 (g)

(s) (s) (l)

2
 Ammonia gas is dried by passing it through anhydrous calcium oxide and is collected
by upward delivery. The other common dehydrating agents such as concentrated
sulphuric acid and anhydrous calcium chloride cannot be used because they react with
ammonia.

Properties of Ammonia
• Ammonia is a compound of nitrogen and hydrogen with the formula NH3. It is a
colourless gas with a characteristic pungent odour.
• Ammonia molecule is pyramidal in shape wih a lone pair of electrons. The bond
angle of H-N-H-N is 107.8°.

• In terms of Lewis theory, ammonia is a Lewis base because it acts as an electron-pair

donor. Ammonia can form dative bond by donating a pair of unpaired electrons on
the nitrogen atom to any Lewis acid.
• In terms of Bronsted-Lowry theory, ammonia is a base because it is a proton acceptor.
Ammonia accepts a proton to form an ammonium ion.
NH3(g) + H2O(l) NH+4 (aq) + OH− (aq)
(proton (proton donor) (conjugate (conjugate
acceptor) acid) bae)
• Ammonia is a highly soluble in water producing a weak base solution with a low base
dissociation constant (Kb=1.81x10-5 mol dm-3). Its high solubility is due to hydrogen
bonding between ammonia molecules and water molecules.
NH3(g) + H2O(l) N3N.H2O(or H3N…H-OH)

3
• A solution of ammonia in water is sometimes known as ammonium hydroxide even
though NH4OH molecue does not exist. Actually a solution of aqueous ammonia
contains NH3.H2O species that is partially ionised to form ammonium ions and
hydroxide ions:
H3N…H-OH NH+4 (aq) + OH− (aq)
• Ammonia can react with aqueous acid to form ammonium salts. The unpaired
electrons on the nitrogen atom can bond with a proton to form tetrahedron ammonium
ion.
NH3(g) + H3O+(aq) → NH+4 (aq) + OH− (aq)
(base) (acid) (salt) (water)
• Gaseous ammonia can react as a base towards acidic gases. For example, when
ammonia is allowed to mix with gaseous hydrogen chloride, white fumes of
ammonium chloride are formed. This is also used as a test for the presence of
ammonia gas.
NH3(g) + HCl(g) → NH4Cl(g)
A daive bond is formed between the nitrogen in ammonia with the hydrogen in
hydrogen chloride.

• Aqueous ammonia is used as a reagent to identify in qualitative analysis. All cations

produce metal hydroxides as precipitates except Na+, K+ and NH+4.
• Some metal hydroxides dissolve in excess ammonia to produce complexes that are
soluble in water. Ammonia acts as ligands in the formation of complexes by donating
the lone pair of electrons to the empty orbitals of metal ions.
• Ammonia can acts as a reducing agent in redox reactions. In the process, ammonia
will be oxidised to nitrogen.
2NH3 + 3Cl2 → N2 + 2HCl
2NH3 + 3CuO → 3Cu + N2 + 2H2O

Uses of Ammonia
• About 80% of the ammonia produced by industry is used in agriculture as fertilizer.
Ammonia is also used as a refrigerant gas, for purification of water supplies, and in
the manufacture of plastics, explosives, textiles, pesticides, dyes and other chemicals.
It is found in many household and industrial-strength cleaning solutions. Household
ammonia cleaning solutions are manufactured by adding ammonia gas to water and
can be between 5 and 10% ammonia.Ammonia solutions for industrial use may be
concentrations of 25% or higher and are corrosive.

NH3 + HNO3 → NH4NO3 (ammonium nitrate)

2NH3 + H2SO4 → (NH4)2SO4 (ammonium sulphate)
2NH3 + CO2 → (NH2)2CO(area) + H2O

4
• Ammonia is used in the manufacture of nitric acid; certain alkalies such as soda ash;
dyes; pharmaceuticals such as sulfa drugs, vitamins and cosmetics; synthetic textile
fibers such as nylon, rayon and acrylics; and for the manufacture of certain plastics
such as phenolics and polyurethanes.
• Nitric acid is produced commercially by the Ostwald process.

Stage 1: Catalytic oxidation of ammonia

Ammonia is oxidised by air to nitrogen monoxide at 850-900°c in the presence of
platinum as a catalyst.
4 NH3(g) + 5 O2(g) 4 NO(g) + 6 H2O(g)

Stage 2: Oxidation of nitrogen monoxide to nitrogen dioxide. Nitrogen monoxide,

NO is further oxidised by air yo nitogen dioxide, NO2.
2 NO(g) + O2(g) 2 NO2(g)

Stage 3: Formation of nitric acid from nitrogen dioxide. Nitrogen dioxide gas
dissolves in water to form nitric acid (50-60%) and nitrous acid.
3 NO2(g) + H2O(l) 2 HNO3(aq) + NO(g)

Nitrogen monoxide is then recycled to produce more nitrogen dioxide.

2 NO(g) + O2(g) 2 NO2(g)

Overall equation:
4 NO2 (g) + O2 (g) + 2 H2O (l) → 4 HNO3 (aq)
The resulting solution is fractionally distilled to produce an azeotropic mixture consisting
68% HNO3.

• Others uses of ammonia:

a) Ammonia is used by the ammonia-soda industry for producing soda ash.
b) Ammonia is used in the manufacture of certain dyes and applied in the dyeing and
scouring of cotton,wool and silk.
c) The pharmaceutical industry uses ammonia in the manufacture of certain products
such as sulfa drugs, vitamins and cosmetics.
d) The petroleum industry utilizes ammonia to neutralize acid constituents of crude
oil and to protect equipment from corrosion.
e) The mining industry uses ammonia to extract certain metals such as copper,
nickel and molybdenum from their ores.
f) The rubber industry uses ammonia to prevent premature coagulation by
stabilizing natural and synthetic latex during transportation from plantation to
factory.
g) The pulp and paper industry use ammonia for pulping wood and as a casein
dispersant in the coating of paper.

5
 h) The food and beverage industry use ammonia as a nitrogen source needed by
yeast and microorganisms.
i) The textile industry uses ammonia in the manufacture of synthetic fibers such as
nylon and rayon.
j) The plastics industry uses ammonia in the manufacture of phenolics and
polyurethanes.
k) Ammonia is used by the leather industry as a curing agent, as a slime and mold
preventative in tanning liquors and as a protective agent for leathers and furs in
storage.
l) Weak ammonia solutions are also widely used as commercial and household
cleaners and detergents.

Oxides of Nitrogen
 Nitrogen monoxide (NO)
 Nitrogen dioxide (NO2)
 Dinitrogen tetroxide (N2O4)

 Insoluble in water
 Colourless neutral gas
 Reducing agent
 Unstable & easily oxidised by oxygen
 Resonance of two structure
 Unpaired electron of NO – paramagnetic & weakly attracted by magnetic field

Resonance structure of NO

x O•
xN O • N
•

Properties of NO2
 Brown acidic gas
 Pungent smell

Molecular geometry = V-shaped

Exists as resonance hybrid structure (doubled bond & dative bond btw N and O are
delocalised)

6
 Hybrid resonance structure of NO2
• •

O O O O
Properties of N2O4
 Colourless gas
 Structure = planar
 Formed by dimerisation of NO2
-reversible process
-depends on temperature
 Dissociation process = endothermic reaction

21-140°C
N2O4(g) 2NO2(g)

Hybrid resonance structure of N2O4

O O
N N N N
O O O
Changes of the composition of the oxides of nitrogen

N2O4 2NO2 2NO + O2 heat N2+2O2

cooled cooled
(colourless) (brown) (colourless) (colourless)

 When temperature decrease, the position of equilibrium shift to the left. The
concentraion of NO2 decrease, thus the intensity of brown colour decrease.
 When temperature increase, the position of equilibrium shift to the right. The
concentraion of NO2 increase, thus the intensity of brown colour increase.

Formation of Oxides of Nitrogen in the Environment

•Lightning cause the dissociation of N molecules then react with O2 to form NO

7
 N2 (g) + O2 (g) 2NO(g)
• NO combines with O2 to form NO2
2NO (g) + O2 (g) 2NO2 (g)

Formation of Oxides of Nitrogen in the Internal Combustion

Engine
•Combustion of fuel in the engine cylinder – fast
o Temperature rises rapidly (2800°C)
• N2(g) + O2 (g) 2NO(g)

converted
• NO NO2
• Oxides emitted with other exhaust pollutants
o e.g. Carbon monoxide, unburnt hydrocarbon, sulphur dioxide, lead bromide
(leaded petrol)

Effects of Oxides of Nitrogen on Air Pollution

 Formation of acid rain

 Formation of photochemical smog



Formation of Acid Rain

Dissolved in rain water

Oxides of nitrogen Nitrous acid & nitric acid

2NO2 + H2O HNO2 + HNO3

4NO2 + 2H2O + O2 4HNO3

NO2 catalyses the oxidation of SO2 to SO3

NO2 + SO2 NO + SO3 (1)

NO + ½ O2 NO2 (2)

Overall: SO2 + ½ O2 SO3

Dissolved in rain water

SO2 Sulphurous acid
8
 Dissolved in rain water
SO3 + H2O Sulphuric acid

Primary pollutants:
 Suplhur dioxide
 Oxides of nitrogen

Propertis of Acid Rain

 Secondary pollutant
 pH < 5

 Corrode metal structure, marble & concrete building
 Depletes nutrients of soil when it react with minerals
o Produce salts which leached out of topsoil
o

Photochemical Smog

NO2 + hydrocarbons from vehicles photochemical smog

Stage 1 UV light cause the formation of oxygen

radicals from NO2

NO2 (g) uv NO (g) + O (g)

Stage 2 Oxygen radicals + O2 molecules ozone molecules

O (g) + O2 (g) O3(g)

9
 Photochemical smog affect:
 eyes and lungs
 cause repiration problems

Ozone:
 secondary pollutants
 harmful to animals and plants
 combined with unsaturated hydrocarbon (from incomplete combustion of fuels) to
form organic radicals which then combine with NO. The final product is the
component of smog.
 Oxidise unsaturated hydrocarbon to produce less volatile organic products such as
alcohol, carboxylic acids, aldehydes and ketones.Smog is formed when the vapour of
organic products condese on dust particles in air.

Catalytic Converters to Reduce Air Pollution

Reduce oxides of nitrogen & CO emission

Catalytic
converters
Consists of 2 compartments

O2 added
First compartment Thermal reactor
Heat at high
temperature

Unburnt hydrocarbons oxidised CO2 + H2O

oxidised
CO CO2
10
 Catalyst : platinum or palladium
2CO + O2 2CO2

Second Mixture of exhaust gases & air

compartments Catalytic reactor
Solid/ catalyst
Catalyst: alumina layered with CuO Cr2O3

At low temperature,
reduced
oxides of nitrogen N2 + O2

2NO N2 + O2

Overall equation of catalytic converters:

2CO + 2NO 2CO2 + N2

The use of catalytic converter needs to be followed by the usage of lead-free fuel.
Why?
 The additives, tetramethyl lead and tetraethyl lead from leaded petrol can “poison”
the catalyst.
o These additives will adsorp on the catalyst and hinder the reactivity of the
catalyst on the active sites.

11