GROUP 15 (AS)

NITROGEN
 1.Nitrogen undergoes few reactions
and is unreactive due to
 Very strong N N bond
 Requires a lot of energy* to break
 Or Ea is very high
 N N bond energy : + 994 kJmol-1
 Most reactions tends to be
endothermic and do not occur at rtp
 However nitrogen does react under
the following conditions :
 1) presence of catalyst to lower Ea
 2) high temperature to overcome
the high Ea
 2.Reactions of nitrogen

 a. Formation of nitrogen oxides

(NOx)
 Conditions : occurs under high
temperature and high pressure
 in car engines and during lightning
flashes
 Eg : N2 (g) + O2(g)  2NO (g)

From air
 Other possible oxides formed :
 N2O , dinitrogen oxide and NO2
 Enthalpies of formation of NOx are
positive due to the high bond
energy of N2 molecule
 Note : However nitrogen and
oxygen do not react at room
temperature.
 Reasons :
 1) reaction is endothermic
 2) nitrogen has a high bond energy
 3) a high Ea is required
 b. Haber process
 Equation :N2(g) +3H2(g)  2NH3(g)
 Conditions : High pressure and high
temperature , catalyst
 c. Formation of nitrides ( N3- )
 Eg : 3Mg + N2  Mg3N2
 magnesium
nitride
 Conditions : High temperature and

burning Mg
 AMMONIA
 1. Shape : trigonal pyramidal
 3 bond pairs and one lone pair of electrons
 Bond angle : 107.30
 2.Presence of lone pair or non-
bonding pair of electrons on
nitrogen,
 therefore are proton acceptors (
acts as a weak base )
 a. aqueous ammonia :
 NH3 + H2O  NH4+ + OH-
 base acid
 b. neutralises acids  ammonium
salts
 Eg : NH3 + HCl  NH4Cl
 Note :Other rxns/changes involving
lone pair of electrons on nitrogen :
 (1)AgCl (s) dissolves in aq NH3
 Due to complex formation,
[Ag(NH3)2]+
 H3N Ag+ NH3
 lone pair on N forms dative bond
with Ag+
 (2)Hydrogen bonds between NH3
molecules
 H3N H-NH2
H bond
 (3)Formation of NH4+
 H3N H+

 (4)Formation of dative bonds

 Eg : NH3 + BF3  H3N BF3
 3. Manufactured by Haber process
 N2 (g) + 3H2 (g)  2NH3 (g)
 Conditions :
 Fe (s) , 450 – 5500 C , 250 atm
 N2 from liquified air and H2 from
natural gas ( CH4 )
Diagram
Nitrogen &
hydrogen Hot gases
Heat converter
exchanger

Nitrogen &
hydrogen Nitrogen,hydrogen,
recycled
& ammonia

condenser

Condensed
ammonia

Note : Heat exchanger warm gas

mixture & speed up reaction
 4.Heat NH4+ compounds with an
alkali
 NH3 gas evolved
 NH4+ + OH-  NH3 (g) + H2O
 Notes:
 a)NH4+ is acidic/ a proton donor
 b)Test for NH4+ ions
 5. Uses of ammonia :
 a. manufacture of HNO3(Ostwald Process)

Pt/Rh
 4NH3 + 5O2  4NO + 6H2O , H=neg
9000 C
6 atm

 2NO + O2  2NO2
 4NO2 + O2 + 2H2O  4HNO3
 Uses of HNO3 : manufacture of
 1)explosives eg TNT
 2)organic dyes
 3)AgNO3 (used in photography)
 b. manufacture of nitrate fertilisers
 Eg N2 + H2 Add directly to soil ammonia
CO2
urea
 NH3
H2SO4 Ammonium

oxidation sulphate
H3PO4 Ammonium
phosphate
 HNO3 Ammonium
nitrate
 i)Major nutrients required by plants
: N , P (K)
 Nutrients added to soil by use of
fertilisers: Eg
 1)Nitrogenous fertilisers ( nitrates
or ammonium salts ) supplies N
 2)Phosphate fertilisers supplies P
 ii) Nitrogeneous fertilisers has to be
added from time to time as
presence of denitrifying bacteria in
soil makes the soil poorer in
nitrogen
 NO3- / NH4+ nitrogen in air
 However the bacteria has no effect
on phosphates
Environmental problems
 1. Uncontrolled use of nitrate fertilisers
:
 If excess fertiliser is added to soil,
 Excess nitrates leach out of soil into
streams or lakes
 Excessive growth of algae/aquatic plants
 When plants/algae die, oxygen is used
up
 Fish/aquatic life unable to live
 Process called eutrophication
 Note : also causes general
poisoning of water supplies
( NO3- poisonous )
 To reduce pollution effects :
 a) Use less fertiliser or use natural
fertiliser
 b) Use other methods of increasing
yield
 Eg : use more productive strains of
wheat / grain etc
 2. Nitrogen oxides (NOx) pollution
from car engines :
 Under high temperature :
 N2 + O2  2NO NOx
Nitrogen oxides
 2NO + O2  2NO2
 NOx damages the environment in
the following ways :
 a. + H2O + O2 to form HNO3 ( acid
rain )
 2NO2 + H2O + ½O2  2HNO3

 b. + other air pollutants to form

ozone ( irritates eyes )
 c. NO2 can react with SO2 ( from burning
of fossil fuel) in the presence of water
vapour in the atmosphere :
 1) NO2 + SO2 + H2O  H2SO4 + NO
 2) 2NO + O2  2NO2
 Overall equation:
 2SO2(g)+2H2O(g)+O2(g)  2H2SO4
 NO2 (g) functions as homogenous
catalyst
 OR
 1) SO2 + NO2  SO3 + NO
 +4 oxd agent +6
 2) 2NO + O2  2NO2

 Overall equation:
 2SO2 (g) + O2 (g)  2SO3
 NO2 (g) functions as homogenous catalyst
and oxidising agent
 Note : NO2 can also be a reducing agent
 To prevent NOx pollution :
 Use catalytic converter to reduce
pollutants in car exhaust
Catalytic converters for car exhaust

 1.Air pollutants from motor vehicles /

car exhaust fumes :
 a) from incomplete combustion of
hydrocarbon fuel :
 CO
 Unburnt hydrocarbons
 Carbon soot
 b) from reaction between O2 and N2
in air under the high temperature in
car engines:
 Nitrogen oxides, NOx (NO and NO2)
 Equations: for formation of NOx
 i) N2 + O2  2NO
 ii)2NO + O2  2NO2
 c) from anti knock additives:
 Lead oxides
 Note :no lead oxide present if
unleaded petrol is used
 2.Effect of pollutants on humans :
 a.Hydrocarbons – breathing
problems
 b.CO – react with haemoglobin /
reduces absorption of oxygen
 c.NOx – acid rain* / breathing
problems / photochemical smog
 * main hazard
 3.Use of catalytic converter :
 To convert gases which are
environmentally harmful into
harmless or less harmful gases
 4.The catalytic converter contains a
filter of fine meshed aluminium
alloy coated with platinum* or
platinum and rhodium mixture
 Fine meshed : greater surface area
therefore faster reaction
 5. Converter speeds up the
following reactions :
 a. to remove CO :
 CO + nitrogen oxides  CO2 + N2
 Eg : 2NO + 2CO  N2 + 2CO2
 b. to remove NOx :
 Eg :Hydrocarbons + nitrogen oxides
 CO2 + N2 + H2O (qualitative eqn)
 NO + H2  H2O + ½N2
 2NO + 2CO  N2 + 2CO2
 c. to remove hydrocarbons :
 Eg :Hydrocarbons + nitrogen oxides
 CO2 + N2 + H2O (qualitative eqn)
6.Diagram
 7.Drawbacks of usage:
 a. high cost (*)
 b. car must run on lead-free petrol
or the catalyst will be poisoned by
lead or lead may be trapped in the
converter
 c. catalyst system only effective at
sufficiently high temperature
 With stop start usage , converter
would be inactive for much of the
time as it would not reach the
operating temp
 8.However exhaust fumes are still
hazardous :Reasons
 a. toxic gases not removed until
converter has warmed up
 b. too much CO to be completely
removed
 c. converter may be less efficient
over a period of time / gets clogged
up
 d. CO2 passes through , causes
global warming
 e. SO2 passes through , causes acid
rain
GROUP 16 (AS)

SULFUR
( eg SO2 )
Sources of SO2

 1. From human activity : egs

 a. combustion of fossil fuel/petroleum
 Proteins in plants and animals consist of
amino acids. Certain amino acids contains S
 Eg : cystine and methionine
 Plants & animals decay compressed by
high pressure & temp  forms fossil fuel
 Petroleum burned in air  S oxidised to SO2
 b. Contact process
 c. manufacture of cement or bricks
 d. coal power stations
 FeS present in coal is oxidised to SO2
 CaO is used to absorb and prevent the SO2
from being released into the atmosphere
 2. From natural sources: egs
 a. volcanoes
 b. rotting vegetation and plankton
Acid Rain

 1. Role of SO2 :
 a. Acid rain: rain having pH less than 5.6
 b. One of the chief culprit in formation of acid
rain is SO2 released into the atmosphere
 c. SO2 + moisture + O2 forms H2SO4
 Eqn : 2SO2 + 2H2O + O2  2H2SO4
2. Effects of acid rain :

 a. kills fishes in lakes :

 SO42- in acid rain combines with aluminium
in complex compounds (eg clay) to form
soluble Al2(SO4)3
 This washes into streams where it interferes with
the operation of fish gills which becomes clogged
with mucus.
 Fishes die from lack of oxygen
 b. damage to trees and crops :
 i) Al3+ poisons trees
 ii) essential nutrients are washed from soil.
Trees starve to death.
 c. corrodes or damages
 i) buildings ( contains limestone or marble
CaCO3 )
 ii) metallic structures eg bridges , ships and
motor vehicles
Uses of SO2

 1. Manufacture of H2SO4 (Contact Process)

 a. sulfur is burned in air
 S + O2  SO2 , H = exothermic
 b. further oxidation :
 2SO2 + O2  2SO3 , H = exothermic
 Conditions :
 catalyst – V2O5 , vanadium (V) oxide
 4500 C , 1 - 2 atm
 c. SO3 absorbed in 98% H2SO4
 SO3 (g) + H2SO4 (l)  H2S2O7
 oleum
 H2S2O7 (l) + H2O (l)  2H2SO4 (l)
 Note : SO3 is not absorbed in water
 Equation : SO3 (g) + H2O (l)  H2SO4 (l)
 Reason :
 Reaction is intensely exothermic as to
vaporise H2SO4 formed(fumes are corrosive )
 Industrial importance of H2SO4 :
 Manufacture of fertilisers , detergents ,
pigments , synthetic fibres and organic
chemicals ( eg dyestuff and explosives )
 2. As a preservative :
 a. SO2 is an inorganic food additive
 Eg : soft drinks . wine , soups , preserved
vegetables or fruits ( apricots , raisins )
 Function of SO2 :
 To kill or inhibit growth of yeast / fungi /
micro-organisms/bacteria
 b. cooked and processed food contains carbonyl
compounds
 SO2 is a reducing agent ( anti oxidant ) therefore
retard oxidation of food
 Eg : Prevents alcohols and carbonyl compound (
aldehydes ) in food from being oxidised and
forming sour-tasting acids
 Note : SO32- (sulfites) are also used in food
preservation