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Nitrogen and its compounds

NITROGEN AND ITS COMPOUNDS


Introduction :
Nitrogen was discovered in 1772 by Daniel Ruther ford, a Scottish physician and chemist.
Others who made important contributions towards its discovery are Priestley, Cavendish,
Scheele and Lavoisier who proved its elementary nature and called it azote ( = without life). The
present name was derived from nitre a well known nitrogen compound.
Occurrence :
It occurs in the free state as well as in the combined state.
In the free state, it is present in air nearly 75% by mass and 80% by volume. It also occurs in
certain natural gases coming out in volcanic regions.
In the combined state, it occurs in
a) Minerals such as nitre (KNO3) and Chile salt petre (NaNO3).
b) Animal products e.g. white of an egg.
c) Certain gases like ammonia, nitrogen oxides.
d) Nitrogen is an essential constituent of all proteins found in animals and plants.

Methods of preparation of nitrogen :


I) Nitrogen is prepared in the laboratory by heating a mixture of sodium nitrite and ammonium
chloride.
Reaction:
NH Cl + NaNO NaCl + [NH4NO2 ]
4 2
unstable

NH4NO2 2H2O + N2(g)


(or)
NaNO2 + NH4Cl NaCl + 2H2O + N2
Collection:
Nitrogen is collected by the downward displacement water.
i) It is slightly soluble in water.
ii) It is almost as heavy as air, so it is not collected over air.
Note:
1. N2 is not obtained directly from NH4NO2 as it is an unstable compound, so cannot be stored.
2. The mixture is taken in the aqueous state as solid ammonium chloride which sublimes on
heating before it react with Sodium Nitrite.
II) From air
Air is an important source of nitrogen where it is present in mixture with oxygen and carbon
dioxide. The CO2 can be removed by passing air through caustic potash while oxygen can be
removed by either of the following methods :
a) By burning phosphorous in it over water when oxygen combines with phosphorus to from
phosphorus pentoxide which dissolves in water leaving behind nitrogen.
P4 + 5O2 P4O10
P4O10 + 6H2O 4H3PO4
b) By passing air over heated copper gauze when oxygen present in air combines with copper
forms copper oxide leaving behind nitrogen.

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Nitrogen and its compounds
III) Manufacture Of Nitrogen Gas From Liquid Air
Nitrogen required for industrial purposes is manufactured by fractional evaporation of liquid air.
Liquid air is a mixture of mostly liquid nitrogen and liquid oxygen and the difference in their
boiling points is 12.8 K. The two are, thus, easily separated by fractional evaporation when
nitrogen being more volatile escapes first.
IV) Other Methods Of Preparation
a) By the oxidation of ammonia.
When ammonia is heated with oxidizing agents like oxygen, chlorine, copper oxide, lead
monoxide or bleaching powder, it yields free nitrogen.
1. Red hot copper oxide
2NH3 + 3CuO 3Cu + 3H2O + N2
2. Lead oxide
2NH3 + 3PbO 3Pb + 3H2O + N2
3. Chlorine
8NH3 + 3Cl2 6NH4Cl + N2
Cu

4. Air
4NH3 + 3O2
Burning
2N2 + 6H2O
5. Bleaching powder
3CaOCl2 + 2NH3 3CaCl2 + 3H2O + N2(g)
b) By heating ammonium dichromate
When orange crystals of ammonium dichromate are heated, they yield nitrogen
The residue is green in colour due to the formation of chromic oxide.
Cr2 O3
(NH4)2Cr2O7
chromic + 4H2O + N2.
oxide

Note:
Atmospheric nitrogen is denser and less reactive than nitrogen prepared in laboratory because
it contains trace amounts of inert gases.

PHYSICAL PROPERTIES OF NITROGEN


1) Nitrogen is a colourless, odourless and tasteless gas
2) It is slightly lighter than air
3) It is slightly soluble in water
4) It is not poisonous. But animals die in an atmosphere of N 2 for lack of oxygen i.e., due to
suffocation
5) It liquefies to a colourless liquid which boils at 195.8 0C. It solidifies to a colourless solid at
210.50C
6) Nitrogen puts off burning candle because it is neither combustible nor a supporter of combustion
7) It is less reactive due to high N N bond dissociation energy.

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Nitrogen and its compounds
CHEMICAL PROPERTIES OF NITROGEN
I) Combination with non-metals: It is less reactive gas. It combines with some non-metals under
special conditions.
a) Combination with oxygen
Nitrogen combines with oxygen to form nitric oxide. This reaction is used for the manufacture of
HNO3
N2 + O2 2NO Heat
Condition:
During lightning discharge or on passage through electric arc the reaction is reversible and is
highly endothermic.
b) Combination with hydrogen
Nitrogen combines with hydrogen to give ammonia gas by Habers process.
N2 + 3H2 2NH3 + Heat

Condition:
The two gases are compressed to a pressure of 200 to 900 atmospheres and then passed over
finely divided iron catalyst mixed with molybdenum heated to 450 0C.
The reaction is reversible and exothermic.
II) Reaction with metals:
Condition:
Only red-hot metals like magnesium, calcium and aluminium form their corresponding nitrides.
3Mg + N2 Mg3N2 (Magnesium nitride)
3Ca + N2 Ca3N2 (Calcium nitride)
2Al + N2 2AlN (Aluminium nitride)
All nitrides react with water to form ammonia, and with acids to form salts
Mg3N2 + 8HCl 3MgCl2 + 2NH4Cl
Mg3N2 + 6H2O 3Mg(OH)2 + 2NH3
AlN + 3H2O Al(OH)3+ NH3
III) Reaction with compounds:
Combination with calcium carbide
On heating calcium carbide at about 8000C to 10000C in a current of nitrogen, an important
fertilizer NITROLIM(CaCN2 + C) is formed.

0

800 C to
CaCN2 C
CaC2 + N2 10000 C Calcium Carbon
cyanamide

Since calcium cyanamide is hydrolysed in the soil to urea and ammonia, it is used as a fertilizer
CaCN2 + 2H2O + CO2 CaCO3 + NH2CONH2
H2NCONH2 + H2O 2NH3 + CO2
TESTS FOR NITROGEN GAS
Nitrogen is chemically inert and there is no positive chemical test for the gas.
i) If a gas extinguishes burning paper, candle or sulphur; if it is neutral to litmus, and does not turn
lime water milky, it is most probably nitrogen.

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Nitrogen and its compounds
ii) When a burning magnesium ribbon is introduced in a jar of nitrogen, it continues burning,
forming a very pale yellow powder. This powder on treating with water gives a very strong smell
of ammonia gas. This gas gives dense white fumes when a glass rod dipped in HCl solution is
brought near it.
Reaction:
3Mg + N2 Mg3N2
Mg3N2 + 6H2O 3Mg(OH)2 + 2NH3
NH + HCl NH4 Cl
3 Dense white fumes

USES OF NITROGEN :
1) In high temperature thermometers
The space above mercury is filled with nitrogen to reduce its evaporation. Such thermometers
can measure upto 5000C.
2) In canning foodstuffs
Coffee, vegetable ghee etc. retain their flavour and colour better if the air space in the can is
filled with nitrogen. A layer of inactive nitrogen prevents the oxidation of food and retards
bacterial growth.
3) In Industries
Being inert, nitrogen is flushed in laboratory and industrial reactions (such as extraction of
metals, manufacture of transistors, and nylon) to remove oxygen of the air and to provide an
inert atmosphere.
4) Due to its inertness only, it is also used in filling electric bulbs. (Argon is now preferred due to its
better heat conductivity)
5) When electric welding is carried out in air, metals tend to get oxidized and hence the welded
part can break. To avoid oxidation, an atmosphere of nitrogen is provided.
6) Liquid nitrogen is used to provide low temperature in the laboratory i.e., as a refrigerant and to
store the eye, blood at low temperatures in hospitals.
7) Nitrogen serves to dilute the action of oxygen in air and this makes combustion much less rapid.
8) It is used in the manufacture of NH3, HNO3, CaCN2 and other nitrogen compounds.

COMPOUNDS OF NITROGEN
AMMONIA
PREPARATION OF AMMONIA
A) In general, ammonia can be produced by heating ammonium salts with alkalies.
e.g., (NH4)2SO4 + Ca(OH)2 2NH3 + 2H2O + CaSO4
NH4Cl + NaOH NH3 + H2O + NaCl
2NH4Cl + Ca(OH)2 2NH3 + CaCl2 + 2H2O
Drying of ammonia Ammonia is best dried by passing it through quicklime, which absorbs the
vapours of water present in the gas. It cannot be dried by means of anhydrous CaCl 2, P2O5 or
conc. H2SO4 because even though these chemicals absorb water, they also react with
ammonia.
B) By Habers Process: Large quantities of ammonia are manufactured by direct union of the
elements by the Habers process.

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Nitrogen and its compounds
Nitrogen and hydrogen combine according to the equation
N2 + 3H2 2NH3;
The reaction is reversible and exothermic.
C) Cyanamide Process: Hydrolysis of calcium cyanamide with superheated steam at 450 K is
another important method for the manufacture of ammonia.
CaCN2 + 3H O CaCO + 2NH .
Calcium cyanamide 2 3 3

D) From urea: Ammonia is also produced when urea is heated with soda lime.
NH2 CONH2 2NaOH Na2CO3 2NH3
urea

PHYSICAL PROPERTIES OF AMMONIA


1) Ammonia is a colourless gas having pungent and irritating smell.
2) It is lighter than air and is collected, therefore, by the downward displacement of air
3) It is extremely soluble in water
4) It liquefies when cooled under pressure to a colourless liquid. Liquid ammonia freezes to white
snowy crystals.

CHEMICAL PROPERTIES OF AMMONIA


1) Combustion: Ammonia is neither combustible nor a supporter of combustion. A jet of ammonia
can however, be made to burn in an atmosphere of oxygen.
4NH3 + 3O2 2N2 + 6H2O
2) Dissociation: Ammonia decomposes into nitrogen and hydrogen on strong heating or when
electric sparks are passed through it.
2NH3 N2 + 3H2
3) Oxidation: We have already seen that a jet of ammonia burns in oxygen when it is oxidized to
nitrogen. It is also oxidized when passed over heated copper oxide.
3CuO + 2NH3 3Cu + N2 + 3H2O
4) It is oxidized to nitric oxide when a mixture of ammonia and air is passed over heated platinum
gauze (catalyst) at 1075 K(Excess of oxygen).
4NH3 + 5O2 4NO + 6H2O
5) Action of Halogens: Both chlorine and bromine oxidize ammonia and liberate nitrogen.
2NH3 + 3Cl2 N2 + 6HCl
6NH3 6HCl 6NH4 Cl
8NH3 3Cl2 N2 6NH4 Cl
With excess of chlorine, an explosive substance, nitrogen trichloride(NCl 3), is formed.
6) Action of metals: Heated metals such as sodium and potassium combine with ammonia to
form amides of the metals, e.g.,
2NH + 2Na 2NaNH2 + H
3 sodium amide 2

7) Reaction with acids: It reacts with acids to produce salts.


NH + HCl NH4 Cl
3 ammonium chloride

2NH3 + H2SO4 ammonium


NH4 SO 4
sulphate

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Nitrogen and its compounds
8) Action of water: It dissolves in water to form ammonium hydroxide, which ionizes to produce
hydroxide ions.
NH3 + H2O NH4OH(aq) NH4 (aq) + OH-(aq).

IMPORTANT AMMONIUM SALTS


Ammonium hydroxide is alkaline in nature. So it reacts with acids like HCl, HNO 3, H2SO4, H3PO4
to form corresponding slats.

AMMONIUM CHLORIDE
PREPARATION
Ammonium chloride is prepared by neutralizing ammonium hydroxide with Hydrochloric acid,
ammonium chloride is formed in solution. Crystaline NH 4Cl separates on concentrating this
solution by evaporation.
NH4OH + HCl NH4Cl + H2O
USES
1) Ammonium chloride is used in soldering.
2) It is used in medicine and as a reagent in the laboratory.

AMMONIUM SULPHATE
PREPARATION
1) Ammonium sulphate is manufactured by passing ammonia vapour into 60% concentrated
sulphuric acid. On cooling ammonium sulphate crystals separate out.
2NH3 + H2SO4 (NH4)2SO4
2) Ammonia manufactured by Habers process is passed into water containing carbon dioxide to
form ammonium carbonate. Gypsum is added to this which form ammonium sulphate and
calcium carbonate. Calcium carbonate being a precipitate is filtered off. The filtrate is
concentrated to get crystals of ammonium sulphate.
2NH3 + H2O + CO2 (NH4)2CO3
(NH ) CO + CaSO4 CaCO + (NH ) SO
4 2 3 (gypsum)
3 4 2 4

USES
1) Ammonium sulphate is used as a fertilizer.
2) It is used to prepare other ammonium salts like ammonium nitrate.
AMMONIUM NITRATE
PREPARATION
1) Ammonium hydroxide is reacted with nitric acid to produce ammonium nitrate in solution.
Concentration of this solution and cooling gives crystals of ammonium nitrate.
NH4OH + HNO3 NH4NO3 + H2O
2) Ammonium nitrate is also prepared by double decomposition of ammonium sulphate and
sodium nitrate.
(NH4)2SO4 + 2NaNO3 Na2SO4 + 2NH4NO3
Sodium sulphate crystallizes first on cooling and is filtered. Evaporation of the filtrate gives
Ammonium nitrate.

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Nitrogen and its compounds

USES Ammonium nitrate is used


1) As fertilizer
2) In making explosives like amatol [80% NH4NO3 + 20% TNT (trinitro toluene)] and ammonal
(NH4NO3 + Al powder).
3) In the manufacture of Nitrous Oxide.

AMMONIUM PHOSPHATES
PREPARATION
Ammonium reacts with phosphoric acid and produces three different types of phosphates viz.,
Mono ammonium phosphate (MAP), diammonium phosphate (DAP) and ammonium phosphate.
NH3 + H3PO4 NH4H2PO4 (MAP)
2NH3 + H3PO4 (NH4)2HPO4 (DAP)
3NH3 + H3PO4 (NH4)3PO4
Calculated amounts of Ammonia and phosphoric acid are used to manufacture MAP and DAP.
Solution of DAP when supersaturated with ammonia deposits crystals of ammonium phosphate.
USES
All the ammonium phosphates are used as fertilizers.

CALCIUM AMMONIUM NITRATE


Calcium Ammonium nitrate is a mixture of calcium carbonate and ammonium nitrate. Powdered
calcium carbonate is mixed with ammonium nitrate and ground well to get intimate mixture. The
mixture is dried as pellets, which are brown in colour. This mixture is used as a fertilizer.
NOTE:
Substance to be used as a fertilizer must have the following characteristics. It should (a) be
soluble in water. (b) be fairly stable (c) be easily assimilated by plants. d) Not be injurious to
plants e) be cheap
Important functions of nitrogen fertilizers are: Nitrogen is very essential for plants as it
i) causes rapid growth
ii) increases protein content
iii) imparts green colour to plants

TESTS FOR AMMONIA


1) It has a characteristic pungent odour
2) It turns moist red litmus paper blue.
3) With a drop of concentrated hydrochloric acid, it gives thick white fumes of ammonium chloride
NH3 + HCl NH4Cl (White fumes)
4) With Nesslers reagent (alkaline K2[HgI4](aq)), it gives a reddish brown precipitate
[H2N.HgO.HgI(iodide of Millons base)].
USES OF AMMONIA
1) As a refrigerant in ice-plants.
2) In the manufacture of nitric acid by Ostwalds process.

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Nitrogen and its compounds
3) In the manufacture of manures, e.g., ammonium sulphate and other ammonium salts which
have important uses of their own.
4) As a cleansing agent for removing grease in dry-cleaning.
5) In the manufacture of urea.

NITRIC ACID
Nitric acid is also called aquafortis, meaning strong water, because it attacks nearly all the
metals.
PREPARATION OF NITRIC ACID
i) Nitric acid is prepared in the laboratory by heating a nitrate (sodium nitrate or potassium nitrate)
with concentrated sulphuric acid.
NaNO3 + H2SO4 NaHSO4 + HNO3
ii) From Air (Birkland and Process): The process is based on the following chemical reactions :
N2 + O2 2NO;
2NO + O2 2NO2
4NO2 + 2H2O + O2 4HNO3
iii) From Ammonia (Ostwalds Process): Large quantities of ammonia manufactured by Habers
Process are converted into nitric acid by Ostwalds process.
The process is based on the following chemical reactions
4NH3 + 5O2 Catalyst
4NO + 6H2O
2NO + O2 2NO2
4NO2 + 2H2O + O2 4HNO3

PHYSICAL PROPERTIES OF NITRIC ACID


1) It is a colourless liquid when pure, but may be coloured yellow by its dissociation products
mainly nitrogen dioxide(NO2).
2) It has an extremely corrosive action on the skin and causes painful blisters.
NOTE:
Fuming nitric acid contains dissolved NO 2 in concentrated nitric acid. It is obtained by distilling
conc. HNO3 with a little starch. Nitric acid is reduced by starch into NO 2 which dissolves in the
remaining acid to form fuming nitric acid.
CHEMICAL PROPERTIES OF NITRIC ACID
It acts as acid, oxidizing agent, Nitrating agent

Acidic properties: Nitric acid is a strong acid. It reacts with basic oxides, hydroxides and carbonates
to form the corresponding nitrates.
CuO + 2HNO3 CuNO3 + H2O
KOH + HNO3 KNO3 + H2O
CaCO3 + 2HNO3 Ca(NO3)2 + H2O + CO2
Oxidation reactions: Since nitric acid decomposed very easily to give nascent oxygen, it acts as a
powerful oxidizing agent.
Oxidation of compounds
i) Hydrogen sulphide to sulphur

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Nitrogen and its compounds
H2S + 2HNO3 S + 2H2O + 2NO2
ii) Sulphur dioxide to sulphuric acid
SO2 + 2HNO3 H2SO4 + 2NO2
iii) Acidified ferrous salts to ferric salts
2FeSO4 + H2SO4 + 2HNO3 Fe2(SO4)3 + 2H2O + 2NO2
iv) Potassium iodide to iodine
6KI + 8HNO3 6KNO3 + 3I2 + 4H2O + 2NO
v) Halogen acids to halogens
2HBr + 2HNO3 Br2 + 2H2O + 2NO2
Oxidation of non-metals
i) S + 6HNO3 H2SO4 + 2H2O + 6NO2
ii) C + 4HNO3 CO2 + 2H2O + 4NO2
iii) I2 + 10HNO3 2HIO3 + 4H2O + 10NO2
iv) B + 3HNO3 H3BO3 + 3NO2
v) P4 + 20HNO3 4H3PO4 + 4H2O + 20NO2
Reaction with Metals: Metals like, Fe, Co, Ni, Cr, Al becomes passive with conc. HNO 3.
The inertness exhibited by metals under conditions in which chemical activity is expected is
known as passivity
The passivity is due to formation of a thin film oxide on the surface of the metal which prevents
further reaction.
When reacts with metals it acts as acid and also as oxidizing agent
More active metals liberates [H] from HNO 3 which reduces nitric acid to give different products.
Nature of products formed depends on
a) Nature of metals b) concentration of HNO3 c) Temperature
The reactions are :
Metal + HNO3 Nitrate + [H]
2HNO3 + 2[H] 2NO2 + 2H2O
2HNO3 + 6[H] 2NO + 4H2O
2HNO3 + 10[H] N2 + 6H2O
2HNO3 + 16[H] 2NH3 + 6H2O
NOTE: Only Mg and Mn liberate H2 from dil.HNO3.
Action on less active metals: With metals like Cu, Ag, Pb and Hg dilute nitric acid forms nitrate and
nitric oxide, while concentrated nitric acid forms nitrate and nitrogen dioxide.
3Cu + 8HNO3(dil.) 3Cu(NO3)2 + 4H2O + 2NO
Cu + 4HNO3(conc.) Cu(NO3)2 + 2H2O + 2NO2
2Ag + 4HNO3(dil.) 2AgNO3 + 2H2O + 2NO2
Ag + 2HNO3(conc). AgNO3 + H2O + NO2
Action on organic compounds (As a nitrating agent):
i) C6H6 HNO3 (conc.) C6H5NO2 H2O
conc.

Benzene H2 SO4 Nitrobenzene

H5 CH3 3HNO3 (conc.) C6H2 (NO2 )3 CH3 3H2O .


ii) C6Toluene
conc.
H SO22,4,6 Trinitrophenol(T.N.T )
4

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Nitrogen and its compounds
TESTS FOR NITRATES:
Brown ring test: This test is useful to test the presence of nitrates. Take aqueous solution of
potassium nitrate and add freshly prepared ferrous sulphate solution. Pour concentrated
sulphuric acid slowly along the sides of inclined test-tube. A brown ring is observed at the
junction of two liquids due to the formation of FeSO 4NO.

USES OF NITRIC ACID


1) In the manufacture of
i) Fertilizers, e.g., Basic calcium nitrate [CaO.Ca(NO 3)2] is prepared by the action of dilute nitric
acid on lime stone.
ii) Explosives, e.g., nitroglycerine, dynamite, TNT, and smokeless powder.
iii) Perfumes, dyes and medicines from coal-tar products.
2) As an important reagent in the laboratory.

ATMOSPHERIC NITROGEN
Nitrogen is an essential constituent of all living cells, animals and human beings. It is present
there as proteins. Animals and human beings depend on plants for their food, containing
proteins, and plants in turn depend on solids for their nitrogenous compounds which have to be
in the assimilating form, like nitrates. The increasing demand of cereal products like wheat and
rice, results in nitrogen deficiency in the soil. Hence, there is a need to supply assimilating
nitrogen to the soil regularly. Since atmospheric air is an inexhaustible source of nitrogen gas, it
is converted into assimilating nitrogen compounds. This conversion is called Fixation of
atmospheric nitrogen.

FIXATION OF NITROGEN
Fixation of nitrogen is defined as the process of converting atmospheric nitrogen into useful
nitrogenous compounds by natural or artificial means which can be assimilated by plants.
NATURAL FIXATION OF NITROGEN
This is done in two ways.
1) Leguminous Plants : Leguminous plants (such as peas and beans) which have nodules in
their roots are able to fix atmospheric nitrogen through Symbiotic bacteria(rhizobium) and
convert it into soluble nitrates. The soluble nitrates are directly absorbed by plants.
2) Lightning Discharge: During thunder storms, electrical discharges cause combination of
atmospheric nitrogen and oxygen to form nitric oxide (NO).
N2 + O2 2NO
This oxide on cooling further reacts with oxygen of the air to give nitrogen dioxide.
2NO + O2 2NO2
Nitrogen dioxide dissolves in rain water to form nitric acid and comes down to the soil.
4NO2 + 2H2O + O2 4HNO3
Nitric acid reacts with compounds like limestone present in the soil to produce calcium nitrate
which can be assimilated by plants.
CaCO3 + 2HNO3 Ca(NO3)2 + H2O + CO2
MgCO3 + 2HNO3 Mg(NO3)2 + H2O + CO2

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Nitrogen and its compounds

ARTIFICIAL FIXATION OF NITROGEN


1) Habers Process : Atmospheric nitrogen is made to combine with hydrogen in the ratio
1 : 3 under a pressure of approximately 200 900 atmospheres and then passed over a
catalyst ferric oxide and a promotor molybdenum at a temperature ranging from 450 0C to 5000C
to form ammonia.
N2 + 3H2 2NH3
Ammonia is directly converted into urea or ammonium sulphate both of which are nitrogenous
fertilizers.
Ammonia is oxidized catalytically by the Ostwalds process to give nitric acid
Nitric acid combines with limestone and converts it into a soluble nitrate or is used for preparing
fertilizers like ammonium nitrate, sodium nitrate, potassium nitrate and calcium nitrate.
CaCO3 2HNO3 Ca(NO3 )2 H2 O CO2
2) Cyanamide Process: In this method atmospheric nitrogen is made to react with heated calcium
carbide at 10000C to form calcium cyanamide, which yields ammonia on heating it with water
under pressure
0
CaC2 + N2
800 to 1000 C
CaCN2 + C
NITROGEN CYCLE:
Nitrogen cycle is one of the major cycles of chemical elements in the environment. Nitrates in
the soil are taken up by plant roots and may them pass along food chains into animals.
Decomposing bacteria convert nitrogen-containing compounds (especially ammonia) in plant
and animal wastes and dead remains back into nitrates, which are released into the soil and can
again be taken up by plants. Though nitrogen is essential to all forms of life, the huge amount
present in the atmosphere is not directly available to most organisms. It can, however, be
assimilated by some specialized bacteria and is thus made available to other organisms
indirectly. Lightning flashes also make some nitrogen available to plants by causing the
combination of atmospheric nitrogen and oxygen to form oxides of nitrogen, which enter the soil
and form nitrates. Some nitrogen is returned from the soil to the atmosphere by denitrifying
bacteria.
N it r o g e n in t h e
a tm o s p h e r e
N it r o g e n f ix a t io n N it r o g e n f ix a t io n
b y lig h t n in g b y b a c te r ia

O x id e s o f n it r o g e n D e n itr if ic a t io n N it r o g e n in
in t h e a tm o s p h e r e b a c t e r ia

N it r if ic a t io n
N it r a t e s in t h e
s o il

N it r if ic a t io n U p ta k e b y
ro o ts
( N it r if y in g b a c r e r ia )

P r o te in in F e e d in g P r o te in in
p la n ts a n im a ls
N it r it e s
D e a th D e a th

A m m o n ia in
dead
( A m m o n ify in g b a c te r ia )
o r g a n ic
m a tte r
N it r if ic a t io n
( N it r o s o f y in g b a c te r ia )

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Nitrogen and its compounds

Nitrification: a chemical process in which nitrogen (mostly in the form of ammonia) in plant and
animal wastes and dead remains is oxidized at first to nitrites and then to nitrates. These
reactions are effected mainly by the bacteria Nitrosomonas and Nitrobacter respectively. Unlike
ammonia, nitrates are readily taken up by plant roots; nitrification is therefore a crucial part of
nitrogen cycle.
WORKED EXAMPLES
1. Explain the following
i) Burning magnesium continues to burn in nitric oxide, while burning sulphur is extinguished.
ii) It is advisable to grow a leguminous crop on a soil every three or four years.
Ans: i) Heat evolved during burning of magnesium is enough to decompose NO into N 2 and O2: while
the heat of burning of sulphur is less.
ii) Leguminous plants have nodules in their roots. Nodules have nitrogen fixing bacteria and
thus convert N2 of soil to nitrates which thus become nitrogen deficient after one or two years.
2. What will be the maximum decrease in volume when 5ml of nitrogen is sparked with
15 ml of hydrogen.
Ans: N2 + 3H2 2NH3
1 vol 3 vol 2 vol
From the above reaction, we know that 1 volume of N 2 reacts with 3 volumes of H2 to form 2
volumes of NH3
Thus decrease in volume for 1 vol of N2 = (1 + 3) 2 = 2 vol
Decrease in volume for 5 ml of N2 = 2 x 5 = 10 ml.
3. Magnesium is burnt in the air and water is added to the product. The smell of ammonia gas is
detected. Write the equation for the reaction which produces ammonia gas in this situation
(magnesium nitride is an expensive and unstable compound. Thus, preparation of ammonium
from magnesium nitride is seldom followed) .
Ans: When Mg burns in air
3Mg + N2 Mg3N2
When water is added to Mg3N2 (Magnesium nitrate)
Mg3N2 + 6H2O 3Mg (OH)2 + 2NH3
4. Conc. H2SO4, phosphorus pentoxide (P2O5) and anhydrous calcium chloride are generally used
in laboratory as drying agents but these are not useful for drying ammonia gas Explain why ?
Ans: Because ammonia gas reacts with these compounds
2NH3 + H2SO4(conc) (NH4)2SO4
with phosphorus pentoxide
6NH3 + P2O5 + 3H2O 2(NH4)3PO4
with anhydrous calcium chloride
8NH3 + CaCl2 CaCl2 . 8 NH3 (Addition compound)
5. Why is conc. Sulphuric acid and not conc. Hydrochloric acid used in the laboratory preparation
of nitric acid ?
Ans: Concentrated sulphuric acid is a non-volatile acid having a boiling point of 338 0C. Thus, when
reaction mixture of potassium nitrate and conc. Sulphuric acid is heated to around 200 0C, the
sulphuric acid does not volatilise, and hence, only pure nitric acid distills over.

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Nitrogen and its compounds
Concentrated hydrochloric acid can react with sodium or potassium nitrate to form nitric acid as
shown below:
0
NaNO3 + HCl(conc.)
200 C
NaCl + HNO3(vapours)
However, the boiling point of conc. Hydrochloric acid is 109.8 0C, and hence is a volatile acid.
Thus, when the reaction mixture of sodium or potassium nitrate and conc. Hydrochloric acid is
maintained around 2000C, both nitric acid and hydrochloric acid change into vapours. Thus, in
the receiver is collected a mixture of nitric acid and hydrochloric acid.

LEVEL I
Objective type Questions:
1. On heating ammonium dichromate, the gas evolved is
a) Oxygen b) Ammonia c) Nitrous oxide d) Nitrogen
2. Ammonium dichromate is used in same fireworks. The green coloured powder blown is:
a) CrO3 b) Cr2O3 c) Cr d) CrO(O2)
3. When ammonia is passed over heated CuO, it is oxidized to
a) N2 b) NO2 c) N2O d) HNO2
4. Density of nitrogen gas prepared from air is slightly greater than that of nitrogen prepared by
chemical reaction from a compound of nitrogen due to the presence of the following in the
atmospheric nitrogen
a) Greater amount of nitrogen molecules derived from N 15 isotopes.
b) Some azide molecules analogous to O3 c) Carbon dioxide d) Argon
5. Animals die in nitrogen because
a) It destroys hemoglobin b) Of the want of oxygen
c) It is heavier than air d) It is poisonous
6. Which of the following burns in oxygen with great difficulty ?
a) S b) N2 c) P d) H2
7. The plant that has root nodules and fix Nitrogen is
a) Maize b) Beans c) Paddy d) Bamboo
8. Nitrogen is relatively inactive element because
a) Its atom has a stable electronic configuration
b) It has low atomic radius
c) Its electronegativity is fairly high
d) Dissociation energy of its molecule is fairly high
9. Nitrogen is used to fill electric bulbs because it
a) Is lighter than air b) Makes the bulb give more light
c) Does not support combustion d) Is non-toxic
10. Which of the following oxides of nitrogen is the anhydride of nitrous acid ?
a) NO b) N2O3 c) N2O4 d) N2O5
11. Which of the following oxides of nitrogen is the anhydride of HNO 3 ?
a) NO b) N2O3 c) N2O4 d) N2O5
12. Which of the following is known as mixed anhydride of nitrous and nitric acids?
a) NO b) NO2 c) N2O d) N2O5

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Nitrogen and its compounds
13. The starting material in Birkeland and Eyde process for manufacture of nitric acid is
a) Ammonia b) NO2 gas c) Air d) Chile saltpeter
14. Conc. HNO3 stains skin yellow because
a) The proteins are converted into xanthoproteins
b) The water is removed by the acid
c) The skin is burnt by acid d) Nitrocellulose is formed
15. Aqua regia is a mixture of
a) 3HCl + 1HNO3 b) H3PO4 + H2SO4 c) 3HNO3 + 1HCl d) HCl + CH3COOH
16. The bacteria that fix Nitrogen is
a) Ammonifying b) Nitrosofying c) Symbiotic d) Nitrifying
17. Nitrogen is essential consitutent of all
a) Proteins b) Fats c) Proteins and fats d) None of these
18. In Habers process for the manufacture of ammonia, the catalyst used is
a) Finely divided nickel b) Finely divided molybdenum
c) Finely divided iron d) Finely divided platinum
19. Ammonia gas can be collected by the displacement of
a) Conc.H2SO4 b) Brine c) Water d) Mercury
20. The ammonia is dried over
a) The slaked lime b) Quick lime c) Calcium chloride d) Mercury
21. The chemical used for cooling in refrigeration is
a) CO2 b) NH4OH c) NH4Cl d) Liquid NH3
22. The oxides that react with nitric acid of rain and form nitrates in the soil are
a) Acidic oxides b) Basic oxides c) Neutral oxides d) Amphoteric oxides
23. Catalytic oxidation of NH3 gives
a) Dinitrogen pontoxide b) Nitricoxide c) Nitrogen dioxide d) Nitorgen
24. The percentage of Nitrogen in ammonia is
a) 82.35 b) 21.45 c) 75.0 d) 28.5
25. 56g of CaO has been mixed with 63 g of HNO3, the amount of Ca(NO3)2 formed is
a) 4g b) 3.28 g c) 164 g d) 82 g
26. On heating a salt with NaOH, smell of NH3 is obtained the salt contains
a) NH4+ b) NO3- c) NO2- d) CH3COO-
27. Conc. HNO3 reacts with iron to:
a) Render iron passive b) Give ferrous nitrate and nitric oxide
c) Give ferric nitrate and ammonium nitrate d) Give ferric nitrate and nitrogen dioxide
28. Which does not give ammonia with water ?
a) Mg3N2 b) AlN c) CaCN2 d) Ca(CN)2
29. Nitric acid may be kept in a bottle of
a) Ag b) Cu c) Pb d) Al
30. The gas which is absorbed by ferrous sulphate solution giving blackish brown colour is
a) NH3 b) N2 c) CO d) NO
31. Which gas can be collected over water ?
a) NH3 b) N2 c) SO2 d) HCl

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Nitrogen and its compounds
32. N2 combines with metal to form:
a) Nitrite b) Nitrate c) Nitride d) Nitrosly chloride
33. Which among the following gives nitrogen on heating ?
a) NaNO2 b) AgNO2 c) Ba(NO2)2 d) NH4NO2

LEVEL II
1 Calcium cyanamide is used as a fertilizer, explain
2 A bottle of liquor ammonia should be cooled before opening, why ?
3 What happens when NH3 is passed into suspension of bleaching powder ?
4 What is effect of heat on NH4NO3 and NH4NO2 ?
5 Complete the following
a) NH3 + Cl2 ..+
excess

Cl2 ..+
b) NH3 + excess

6 Write chemical equations when


i) Ammonia gas burns in the atmosphere of oxygen.
ii) Ammonia gas reacts with limited amount of chlorine gas.
7 When HNO3 is exposed to light slowly turns yellow, why ?
8 Between NH4NO3 and (NH4)3PO4, which is better fertilizer ?
9 How can yellowish brown colour of nitric acid obtained in the laboratory be removed ?
10 Nitrogen gas can be obtained directly by heating NH 4NO2. Explain why we use a mixture of
NH4Cl solution and NH4NO2 solution in the laboratory preparation of nitrogen?
11 Why is freshly prepared ferrous sulphate solution used in brown ring test?
12 Give two examples with equations to show that ammonia is a good reducing agent.
13 Give two oxidizing reactions of nitric acid ?
14 How is brown ring test performed ?
15 What is meant by fixation of atmospheric nitrogen ?
16 State with balanced equations, what happens when
i) Aqueous solution of ammonia is added to sulphuric acid solution
ii) Zinc is treated with dilute nitric acid
17 Nitrogen obtained from air is known as atmospheric nitrogen while the one obtained from
nitrogenous compounds is Chemical nitrogen. Differentiate between the two with respect to
i) Density ii) Reactivity
18 Under what conditions do nitrogen and hydrogen combine to form ammonia ?
19 Glass rod dipped in hydrochloric acid gives white fumes with ammonia. Given relavent equation
20 Why does brown ring disappear when the contents of the test tube are shaken ?
21. Identify A and B in the following equation
Al(Red hot) + N2 A H O
2
B + Al(OH)3

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Nitrogen and its compounds

KEY TO LEVEL I
1.d 2.b 3. a 4. d 5. b 6. b 7. b
8. d 9. c 10. b 11. d
12. b (Hint Nitrogen dioxide dissolves in water to give a mixture of nitrous and nitric acids)
13. c 14. a 15. a 16. c 17. a 18. c 19. d
20. b 21. d 22. b 23. b 24. a 25. d 26. a
27. a 28. d 29. d (Hint remaining react with nitric acid)
30. d (Hint brown ring test) 31. b 32. c 33. d

KEY TO LEVEL II
2 Liquor ammonia is volatile. It escapes from the bottle at room temperature.
3 CaOCl2 + NH3 CaCl2 + H2O + N2
4 NH4NO3

N2O + 2H2O
NH4NO2 N2 + 2H2O
5 a) N2 + NH4Cl b)NCl3 + HCl 8 NH4NO3.( % nitrogen is more)
9 The yellow brown colour of nitric acid is due to the presence of dissolved nitrogen dioxide gas in
it. The colour can be removed by the following methods:
1. By passing dry carbon dioxide or dry air through nitric acid, which drives out nitrogen dioxide
gas. Thus, nitric acid decolorise.
2. By adding water in nitric acid drop by drop and shaking it vigorously removes its yellowish
brown colour. It is because nitrogen dioxide reacts with water in the presence of oxygen (from
air) to form colourless nitric acid.
4NO2 + 2H2O + O2 4HNO3
11 Ferrous sulphate (FeSO4) solution on exposure to air is oxidized to ferric sulphate (Fe 2(SO4)3)
solution. The nitric oxide molecule (NO) will not form additive compound with ferric sulphate and
hence, brown ring test will not succeed.
16 i) 2NH4OH + H2SO4 (NH4)2SO4 + 2H2O
ii) 4Zn + 10 HNO3 4 Zn(NO3)2 + N2O + 5H2O
20 When the contents of the test tube are shaken, some amount of conc. Sulphuric acid mixes with
water present in ferrous sulphate solution. This generates good amount of heat which is
sufficient to decompose FeSO4.NO to FeSO4 and nitric oxide gas which bubbles out. Thus,
brown ring disappears.
21 A AlN, B NH3

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Nitrogen and its compounds

WORK SHEET
1. Why nitrogen is less reaction explains?
2. What is formation equation of Nitrolim?
3. Any two methods of preparation of nitrogen?
4. Chemical properties of nitrogen
a) Combination with oxygen
b) Combination with hydrogen
c) Combination with calcium carbide
2. Preparation of ammonia ( NH 3 )
a) Habers process
b) Cyanamide process
c) From urea
3. Chemical properties of ammonia ( NH 3 )
a) Action of halogens
b) Action of metals
c) Action of Acids
4. Uses of ammonium nitrate ( NH 4 NO3 )
5. Preparation of nitric acid ( HNO3 )
a) Birk land process
b) Ostwalds process
6. Two chemical properties of nitric acid?
7. Action on organic compounds (as a nitrating agent) in the presence of ( HNO3 ) Nitric acid?
8. What is fixation of nitrogen?
9. Under what conditions do nitrogen and hydrogen combine to form ( NH 3 ) ammonia?

10. Air contains N 2 ------------------ % by weight and ----------------- % by volume


11. The full form of T.N.T is -----------------------
12. Ammonia gas is collected by ------------------------ ward displacement of --------------------
13. Amatol is mixture of ----------------------- and -----------------------
14. The full form of MAP and DAP are ---------------------------------------- and ------------------------
15. Ammonal is mixture of ----------------------- and ---------------------------
16. What is the catalyst in the preparation of NH 3 -----------------
17. What is the promotor in the preparation of preparation of NH 3 -----------------

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