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Nitrogen

Production of Nitrogen
Nitrogen is obtained when dry ammonia is
passed over heated copper(II) oxide.
2NH3(g) + 3CuO(s) N2(g) + 3H2O(l) +3Cu
At 10 atmosphere pressure dust is removed.
Then CO2 and moisture are removed.
Air is now compressed to 200 atmosphere
pressure and cooled to room temperature.
Sudden expansion cools the gas
Cooled gases recycled many times until liquifies
At -196C nitrogen boils out.

Ammonia
Laboratory preparation of ammonia.
Ca(OH)2(s) +NH4Cl(s) Ca2+(Cl-)2 + 2H2O+
2NH3(g)

Industrial production of ammonia.


N2(g) + 3H2(g) 2NH3(g) H(298K) =
-92kJ.Mol-1
Reaction suggest the production is favored
by high pressure and low temperature.
4 molecules of reagents produce 2
molecules of products and the reaction is

Process condition

Catalyst = finely divided iron


Temperature = 500C
Pressure = 250 atmosphere
High pressure could yield more ammonia,
the cost of production could be high. A
compromise is made to limit the pressure at
250 atmosphere
At very low temperature the rate of reaction
is very low. This brought the reaction
temperature to 500C.

Chemical properties of
ammonia
Ammonium salt resemble the alkali metal
salts. But the decompose when heated
NH4Cl NH3 + HCl
NH4NO2 N2(g) + 2H2O(l)
NH4NO3(s) N2O(g) + 2H2O(l)
With alkali metal it forms amide.
2Na(s) + 2NH3(g) NaNH2(s) + H2(g)
Ammonia reduce chlorine to chloride.

Nitric acid
Nitric acid is made in the laboratory
by dissolving nitrate in sulphuric
acid. Nitric acid boils out at a lower
temperature.
NO3- + H2SO4(l) HSO4-+ HNO3(l)

Industrial production of Nitric acid

Catalyst- Platinum-Rhodium
Temperature 850C
Catalytic oxidation of ammonia produce NO.
4NH3(g)+ 5O2(g) 4NO(g) + 6H2O(g)
Cooled gas is reacted with oxygen to form NO 2.
2NO(g) + O2(g) 2NO2(g)
Then reacted with air and water to form nitric
acid.
4NO2(g) +2H2O(l) +O2(g) 4HNO3(aq)
Any excess NO2 is absorbed in sodium hydoroxide.

dehydrating nitric acid


Nitric acid cannot be evaporated to
remove water. At 120.5C it boils as
68% mixture constant boiling or
azeotropic mixture.
Pure nitric acid can be obtained by
dehydrating it with phosphorus
pentoxide and distilling it.

Chemical properties of nitric


acid.
Concentrated nitric acid decompose
photochemically and gradually
assumes yellow colour due to the
presence of dissolved nitrogen
dioxide.
4HNO3(l) 4NO2(g) +2H2O(l) +O2(g)

Nitration
Benzene and its derivatives are
nitrated by a mixture of nitric acid
and sulphuric acid. The reacting
species being nitronium ion, NO2+.
The purpose of the sulphuric acid is
to increase the NO2+ concentration.
It also prevents presence of nitrate
ion. The two ionisation is as follows

Nitration 2
2HNO3

NO2++ NO3+ H2O

HNO3+ H2SO4 NO2++ HSO4-+ H2O


The ionization equations above first
equation 2 molecules of HNO3 give
one mole of NO2+ ion.
In the second ionization one mole
HNO3 gives one mole of NO2+ion. And
the retarding NO3- ion is absent.

Oxidation of nonmetals
Sulphur and phosphorus are attaked
by nitric acid.
S (s) + 6HNO3 H2SO4(aq) +6NO2(g)
+2H2O(l)
P(s) + 5HNO3 H3PO4 (aq) +
5NO2(g) + H2O(l)

Oxidation of metals
Dilute nitric acid gives NO with
copper.
8HNO3 + 3Cu(s) 3Cu2+(aq) + 6NO3-(aq) +
4H2O(l) + 2NO(g)

Concentrated nitric acid give NO2


with copper.
4HNO3(l) + Cu Cu2+(aq) + 2NO3- (aq)+ 2NO2(g)
+2H2O(l)
Some strange excptions
Zn with very dilute nitric acid.
4Zn (s)+10 HNO3(aq) 4Zn2+ (aq)+ 8NO3-(aq)

Aqua regia
Aqua regia is a mixture of nitric acid
and hydrochloric acid in the ratio 1:3.
it oxidize gold and platinum.
Au(s) +6HNO3 Au3+ (aq) + 3NO3-(aq)+3NO2(g)+
3H2O

Au3+ ion is removed by complex


formed by Cl-ion. The reaction is
catalyzed by NOCl.

Thermal decomposition of
Nitrate
2NO3- NO2(g) + O2-+ O2