NITROGEN AND ITS

COMPOUNDS
 NITROGEN
• It was discovered in 1772 by a chemist Daniel Rutherford.
• Nitrogen gas occupies about 78% of atmospheric air.
• It occurs freely as diatomic molecules with the formula N2.
• The atoms are held together by strong tripple covalent bond
that require a lot of energy to break
• Nitrogen is a non metal in group V and period 2 of the periodic
table.
 Isolation of nitrogen from the air
• Nitrogen can be prepared by removing carbon(IV) oxide and oxygen from
atmospheric air.

• When water runs into the aspirator it pushes air into the wash bottle
containing concentrated sodium hydroxide or potassium hydroxide.
• Carbon(IV) oxide in the air reacts with sodium hydroxide forming sodium
carbonate.Thus all the carbon(IV) oxide in the air is removed.

CO2(s) + 2NaOH(aq) → Na2CO3(aq) + H2O(l)

• Oxygen in the air reacts with the copper turnings forming copper(II) oxide which
is a black solid.

2Cu(s) + O2(g) → 2CuO(s)

• The remaining gas, which is mainly nitrogen is collected over water.This is
possible because nitrogen is only slightly soluble in water.

• Nitrogen formed by this method is not pure.It contains several impurities,

mainly the noble gases as well as unreacted oxygen. It is therefore less
dense than pure nitrogen

• The noble gases cannot be removed by any chemical means.

Industrial isolation of nitrogen from air
• Large quantities of nitrogen are made by fractional distillation of liquid air.

• This method takes advantage of the different boiling points of the various
gases in air.

• Dust particles are first removed from air through electrostatic precipitation.

• The dust-free air is then passed through concentrated sodium hydroxide

solution to remove carbon (IV) oxide gas.
• The remaining air is passed into a condensation chamber and cooled to – 25 °C.
Water vapour seperates out as ice.

• The residiual gas is compressed to a pressure of 200 atmospheres.

• Repeated expansion and contraction of the air cools it to a liquid at temperature

of -200 °C.
• At this temperature, nitrogen argon and oxygen have changed into a blue liquid,
helium whose boiling point is much lower escapes as a gas.
• The liquid air is warmed to obtain nitrogen at – 196 °C , Argon distilled out at –
186 °C while oxygen distilled out at – 183 °C.
laboratoryPreparation of nitrogen gas
• Sodium nitrite reacts with ammonium chloride to form ammonium nitrite.
NaNO2(aq) + NH4Cl(aq) → NaCl(aq) + NH4NO2(aq)

• Ammonium nitrite is unstable and decomposes on heating giving out

nitrogen gas.
NH4NO2(aq) → 2H2O(l) + N2(g)

• Ammonium nitrite is very unstable and decomposes even at room

temperature.For this reason it cannot be stored.

• Overall reaction.
NaNO2(aq) + NH4Cl(aq) → NaCl(aq) + 2H2O(l) + N2(g)
laboratoryPreparation of nitrogen gas
• NO2-(aq) + NH4+(aq) → 2H2O(l) + N2(g)

• If required dry, nitrogen gas can be passed through

concentrated sulphuric acid to remove water vapour.
The gas is then collected in a syringe .
Physical properties of nitrogen gas

• It boils at -196 °C and freezes at -210 °C.

• It has a density of 1.25 g dm-3 which is slightly lower than that of air.

• It is neutral and has no effect on moist litmus paper and does not react
readily with other elements.

• Nitrogen is a colourless, odourless and tasteless gas.

• Nitrogen is distinguished from other gases by its negative results with all
the tests used to identify common gases.
Chemical properties of nitrogen gas

The strong tripple covalent bond between nitrogen atoms require high
temperatures to break. This makes nitrogen inert at room temperature.

• It does not support combustion.

• AIR: Nitrogen and oxygen will combine when heated to a high temperature
to form nitrogen(II) oxide: The reaction is reversible.
N2(g) + O2(g) ↔ 2NO(g)
 The nitrogen(II) oxide is immediately oxidized further by more oxygen to
nitrogen(IV) oxide:
2NO(g) + O2(g) → 2NO2(g)

• HYDROGEN: Nitrogen and hydrogen will combine when heated in the

presence of an iron catalyst at 5000C and high pressure to form ammonia:
N2(g) + 3H2(g) → 2NH3(g)
• Metals: Nitrogen will react with highly reactive metals when heated
to form metal nitrides.
Uses of nitrogen

• Manufacture of ammonia in the Haber process.

• In lights bulbs because of its inert nature it cannot react with the hot
filament of the bulb.

• As a refrigerant, e.g., in the storage of semen for artificial insemination

Uses of nitrogen
1.It is used in the Haber process to manufacture ammonia gas .

2.The boiling point of liquid nitrogen is almost -200°C. Therefore it is used to freeze
substances quickly. It can be used In hospitals to store body tissues that are
required to last a long period of time. semen for artificial insemination can be
stored for use in the future.

It can also be used when mending leaking pipes. When liquid nitrogen is poured
on the pipe it freezes the liquid inside while repair is done.

3.It is used in food processing. When food is being packed, nitrogen is used to
keep off oxygen and the food stays fresh for a long time because there is no
oxidation. Most bacteria cannot survive in abscense of oxygen.

4.Because of its inert nature, it is pumped in the ships' tanks that transport crude
oil to remove any oxygen. This prevents dangerous explosion that could occur
from crude oil vapours.
Answers

1. (a) i-) A: SODIUM HYDROXIDE

B: CONC. SULPHURIC ACID

ii-) Colour change from brown to black.

iii-) CO2(s) + 2NaOH(aq) → Na2CO3(aq) + H2O(l)

iv-) noble gases

v-) Nitrogen will react with highly reactive metals when heated to form metal
nitrides.

2. Nitrogen is an unreactive gas due to the strong covalent triple bond between
its atoms.
 OXIDES OF NITROGEN
Nitrogen forms the following three common oxides:
• Nitrogen(I) oxide, N2O nitrous oxide, dinitrogen oxide
• Nitrogen(II) oxide, NO, nitrogen monoxide
• Nitrogen(IV) oxide, NO2 ,nitrogen dioxide
All these are gases at room temperature and pressure.
Nitrogen(I) oxide (N2O )
• Nitrogen(I) oxide, N2O, is commonly called dinitrogen oxide or nitrous oxide.

• Nitrogen(I) oxide is a colourless gas with a pleasant smell.

• It is slightly denser than air.

• It is fairly soluble in cold water but insoluble in warm water.For this reason
it is usually collected over warm water.

• Nitrogen(I) oxide is a neutral gas.

• Ammonium nitrate melts and decomposes on heating to form
nitrogen(I) oxide and steam.

NH4NO3(s) → N2O(g) + 2H2O(g)

Ammonium nitrate should not be heated further if the
quantity remaining is small because it may explode. It is
advisable to use a mixture of sodium nitrate and
ammonium sulphate.
2NaNO3(aq) + ( NH4 )2SO4(aq) → Na 2SO4(aq) + 2NH4NO3(aq)

Ammonium nitrate then decomposes to form nitrogen

nitrogen (I) oxide.
NH4NO3(s) → N2O(g) + 2H2O(g)
Overall reaction
2NaNO3(aq) + ( NH4 )2SO4(aq) → Na 2SO4(aq) + 2N2O(g) + 4H2O(l)

Ionic equation
NO3 -(aq) + 2NH4+ (aq) → 2N2O(g) + 4H2O(l)

If the gas is required dry, pass it through anhydrous

calcium chloride in a U-tube to remove water vapour and
then collect it by downward delivery.
Chemical properties of nitrogen(I) oxide (N2O )
• Burning metals, for example, magnesium and non-metals like sulphur and
charcoal continue to burn in the gas forming the corresponding oxide and
nitrogen gas:
Mg(s) + N2O(g) → MgO(s) + N2(g)

S(s) + 2N2O(g) → SO2(g) + 2N2(g)

C(s) + 2N2O(g) → CO2(g) + 2N2(g)

• At a high temperature (about 600 °C ) it decomposes to oxygen and nitrogen.

This explains why it supports combustion of strongly burning elements

N2O(g) → O2(g) + 2N2(g)

• When nitrogen(I) oxide is passed over heated copper, a black residue of
copper(II) oxide and nitrogen is formed.

Cu(s) + N2O(g) → CuO(s) + N2(g)

Tests for nitrogen(I) oxide (N2O )
• Because of its ability to re-light a glowing wooden splint and to allow
various other substances to burn in it, nitrogen(I) oxide can be confused
with oxygen.

• Two gases can be distinguished by the properties shown in the table.

Uses of nitrogen(I) oxide (N2O )
• It was formerly used as an anaesthetic during dental surgery.Patients
recovering from it laugh hysterically hence the name ‘laughing gas’.

• It is used as a food additive.

• İt is used as an oxidiser in racing car engines and rockets.

• It is used to produce flames for analytical work.

Nitrogen(II) oxide (NO)

• Nitrogen(II) oxide, NO, is also called nitrogen monoxide or nitric oxide.

• It is a colourless gas.

• It is only slightly soluble in water, forming a neutral solution.

• Nitrogen(II) oxide is used in the manufacture of nitric acid.

• Nitrogen(II) oxide is produced when copper and dilute nitric acid react.

3Cu(s) + 8HNO3(aq) → 3Cu(NO3)2(aq) + 4H2O (l) + 2NO(g)

 Chemical properties of nitrogen(II) oxide (NO )
• Nitrogen(II) oxide does not burn or support combustion.However, it
decomposes to nitrogen and oxygen at temperatures above 1000 °C :
2NO(g) → N2(g) + O2(g)

• Nitrogen(II) oxide will support the combustion of fiercely burning substances,

e.g. Magnesium and phosphorous, which produce heat of over 1000 °C :
2Mg(s) + 2NO(g) → 2MgO(s) + N2(g)

P4(s) + 10NO(g) → 2P2O5(s) + 5N2(g)

• Nitrogen(II) oxide oxidizes hot metals, for example, copper and iron to their
oxides and is itself reduced to nitrogen:
2Cu(s) + 2NO(g) → 2CuO(s) + N2(g)

2Fe(s) + 2NO(g) → 2FeO(s) + N2(g)

• Nitrogen(II) oxide is instantly oxidized by atmospheric oxygen to nitrogen(IV)
oxide:
2NO(g) + O2(g) → 2NO2(g)

• Nitrogen(II) oxide dissolves in cold iron(II) sulphate solution to give a dark-

brown solution of nitroso-iron(II) sulphate:

2FeSO4(aq) + NO(g) → FeSO4.NO(aq)

This reaction used for detecting nitrogen(II) oxide.

Nitrogen(IV) oxide
• Nitrogen(IV oxide), NO2 , is commonly called nitrogen dioxide.

• It is a poisonous substance and should therefore be prepared in a fume chamber or in

the open.

• It is irritating pungent smell and dark brown in colour.

• It is soluble in water and denser than air.

• It is easily liquefied on cooling (boiling point is 22 °C ).

• The main use of nitrogen(IV) oxide is in the manufacture of nitric acid.

• It is usually prepared by the action of concentrated nitric acid on copper.
Cu(s) + 4HNO3(l) → Cu(NO3)2(aq) + 2NO2(g) + 2H2O(l)

• The gas is collected by downward delivery because it is denser than air.

• Nitrogen(IV) oxide may also prepared by thermal decomposition of nitrates of metals
below in the reactivity series.

• Lead(II) nitrate is the most suitable because it is not hydrated.

Pb(NO3)2(s) → 2PbO(s) + 4NO2(g) + O2(g)

• The gases produced are passed through a U-tube surrounded by ice cold
water.

• On cooling , nitrogen(IV) oxide condenses to form dinitrogen tetraoxide, N2O4

, which is a pale-yellow liquid.

• Oxygen gas is collected over water.

2NO2(g) ↔ N2O4(l)
Reddish brown pale yellow
Chemical properties of nitrogen(IV) oxide
• Nitrogen(IV) oxide reacts with water on dissolving to form a solution which contains nitric
acid and nitrous acid.
2NO2(g) + H2O(l) → HNO2(aq) + HNO3(aq)

• Nitrogen(IV) oxide does not burn or support combustion.However, it decomposes to

nitrogen(II) oxide and oxygen at high temperatures.
2NO2(g) → 2NO(g) + O2(g)

• Magnesium ribbon continues to burn in nitrogen(IV) oxide to form white fumes of

magnesium oxide and nitrogen.
4Mg(s) + 2NO2(g) → MgO(s) + N2(g)

• Burning phosphorus continues to burn in nitrogen(IV) oxide to form phosphorus(V) oxide.

2P4(s) + 10NO2(g) → 4P2O5(g) + 5N2(g)
Ammonia

• Ammonia, NH3, is a compound of nitrogen and hydrogen.

• It is a gas at room temperature.

• Ammonia is a colourless gas with a characteristic choking smell.

• It is less dense than air and is easily liquefied under pressure.

• It is very soluble in water.

Preparation of ammonia

• Ammonia can be prepared by heating a mixture of any ammonium salt and

alkali.
• The commonly used reagents are ammonium chloride and calcium
hydroxide(slaked lime).
2NH4Cl(s) + Ca(OH)2(s) → CaCl2(s) + 2NH3(g) + 2H2O(l)
• On heating the mixture, ammonia gas is evolved.Once the gas jar is full, the
moist red litmus paper turns blue.

• The gas is less dense than air and is therefore collected by upward delivery.

• It is highly soluble in water and cannot be therefore be collected over water.

• The flask containing the mixture is set in a slanting position to prevent water
which condenses on the cooler parts of the apparatus, from running back into
the flask and causing it to crack.

• Calcium oxide is used as a drying agent. This is because ammonia reacts with
the other common drying agents.
• Ammonia turns moist red litmus paper blue showing that it is alkaline.This is
the confirmatory test for ammonia

• When a glass rod dipped in concentrated hydrochloric acid is brought to the

mouth of a gas jar full of ammonia, hydrogen chloride fumes react with
ammonia to form white fumes of ammonium chloride.

NH3(g) + HCl(l) → NH4Cl(s)

How is an aqueous solution of ammonia prepared?
• Ammonia dissolves in water to form an alkaline solution.A little of the dissolved
gas combines with water to form ammonium ions and hydroxide ions.

• The hydroxide ion, OH- , gives the solution its alkaline properties.

• A funnel is used to prevent the water from ‘sucking back’ into the flask by
providing a large surface area for absorption of ammonia.
How soluble is ammonia in water?
• When the glass tube is placed into litmus solution, water slowly rises up the tube.

• When it enters the flask it dissolves so much ammonia that there is a partial vacuum in the flask.

• Water is then forced rapidly up the tube and enters the flask as fountain.

• The litmus indicator turns blue because ammonia solution is alkaline.

• The fountain experiment shows that ammonia is a very soluble gas.In fact at room temperature
1 cm3 of water dissolves 800 cm3 of ammonia.

• It is in fact the most soluble of all the known gases.

How does aqueous ammonia react with dilute acids?
Does ammonia burn in air?
• Ammonia does not burn in air.

• However, it will burn in pure oxygen or in an atmosphere rich in oxygen with

a greenish-yellow flame forming nitrogen and water vapour.

4NH3(g) + 3O2(g) → 6H2O(g) + 2N2(g)

 How does ammonia react with air in the presence of a platinum wire?
• Ammonia and oxygen react on the surface of the platinum which acts as a catalyst.

• A lot of heat is produced during the reaction that enables the platinum coil to
continue glowing.

• Ammonia is oxidised to nitrogen(II) oxide in the presence of a platinum catalyst.

4NH3(g) + 5O2(g) → 4N0(g) + 6H2O(g)

• Reddish-brown fumes of nitrogen(IV) oxide are produced due to the further oxidation
of nitrogen(II) oxide.
2NO(g) + O2(g) → 2NO2(g)
 How does ammonia react with copper(II) oxide
• When ammonia is passed over heated copper(II) oxide, the black copper(II) oxide
turns into a brown solid as copper(II) oxide is reduced to copper metal by ammonia.

3CuO(s) + 2NH3(g) → 3Cu(s) + N2(g) + 3H2O(g)

• Ammonia is the reducing agent and copper(II) oxide is the oxidizing agent.

• Lead(II) oxide or iron(II) oxide can be used in place of copper(II) oxide.

 Large scale manufacture of ammonia, the Haber Process
• The raw materials for the process are nitrogen and hydrogen.

• Nitrogen is obtained by the fractional distillation of liquid air.Hydrogen is obtained from

natural gas or as a by-product of cracking long chain alkanes.

• The mixture of nitrogen and hydrogen is first passed through a purifier, which removes
moisture, sulphur compounds, carbon(II) oxide, carbon(IV) oxide, oxygen and some dust
particles.

• The mixture of nitrogen and hydrogen is then compressed to between 200 and 500
atmospheres and passed into a catalytic chamber maintained at temperatures of between
400 °C and 500 °C .
• Iron is used as catalyst. The reaction is exothermic(releases heat).

• The hot mixture of ammonia and gases which have not reacted are passed into the
exchanger where cooling takes place.

• The heat is used to heat the incoming mixture of nitrogen and hydrogen, this makes
the process economical.

• The ammonia produced is liquefied in the condenser and stored in cylinders .

Uses of ammonia
• As a fertiliser.

• Manufacture of nitrogenous fertilisers.

• As a refrigerant; e.g., in large scale refrigerating plants such as ships and

warehouses

• Softening water.

• Removal of greasy stains.

• Manufacture of hydrazine that is used as rocket fuel.

Nitrogenous Fertilisers
• Nitrogen one of the most important elements required for the growth of
plants.However, plants are not able to take in elemental nitrogen.

• They obtain it in the form of nitrates. Ammonium salts can also supply
plants with nitrogen.
Nitric(V) Acid
• Nitric acid is one of the common mineral acids.

• It is extremely corrosive and will attack almost all metals, rubber and cork.All
apparatus used in its preparation and storage must be of glass.

• In the laboratory, it is made by reacting concentrated sulphuric acid with

potassium or sodium nitrate.
• On heating the retort, potassium nitrate gradually dissolves and effervescence
occurs giving out brown fumes.

• The fumes condense in the cooled flask and nitric acid collects as a yellow liquid.

• Pure nitric acid is colourless.However, the fumes appear brown due to the
presence of nitrogen(IV) oxide which is produced by slight decomposition of
nitric acid by heat:
• The nitric acid collected is yellow in colour due to the presence of dissolved
NO2(g)

• The yellow colour can be removed by bubbling air through the acid.

• The acidic salt KHSO4 is formed instead of the normal salt K2SO4 because the
normal salts require high temperature that can not be achieved in glass
apparatus.
Industrial manufacture of nitric(V) acid (OSTWALD PROCESS)
Chemical properties of dilute nitric acid
Chemical properties of concentrated nitric acid
Uses of nitric(V) acid
• Manufacture of fertilisers, e.g ,ammonium nitrate

• Manufacture of explosives

• Manufacture of dyes and drugs.

• Purification of metals such as silver and gold.

• Etching designs on some metals.

NITRATES
• The nitrates are salts that derived from nitric acid.

• They are organic compound which are all soluble in water.

 Test for Nitrates

• When concentrated sulphuric acid is added to the mixture of sodium nitrate and
iron(II) sulphate solution, the acid sinks to the bottom.

• The reaction produces heat. A brown ring is formed at the junction of the two
layers.

• The brown ring is due to the formation of FeSO4.NO

• All nitrates give the same result hence this reaction is referred to as the brown
ring test for nitrates.
• A safer method of testing for the presence of nitrate ions is by warming a
mixture of concentrated sulphuric(VI) acid and the suspected nitrate in the
presence of copper turnings.

• When sodium nitrate is mixed with concentrated sulphuric acid and the
mixture warmed in the presence of copper turnings, brown fumes of
nitrogen(IV) oxide are produced.

• This reaction takes place in two stages.

 Homework (page 154-155)
• Pollution effects of nitrogen compounds in the atmosphere

• Reducing environmental pollution by nitrogen compounds

QUESTION 1
QUESTION 2
QUESTION 3
QUESTION 4
QUESTION 5
QUESTION 6
QUESTION 7
QUESTION 8
QUESTION 9
QUESTION 10
•
• 12. The flow chart below represents the
industrial preparation of nitric acid. Study it
and answer the questions that follow.
• (a) State what happens in the heat exchanger.
• (b) Give an equation for the reaction that
takes place in the catalytic chamber and name
the catalyst,
• (c) Name the gases in mixture R that are
important for the subsequent steps.
• (d) State what happens in chamber Y.
• (e) Give the equation for the overall reaction that takes
place in chamber Z.
• (f) How is the operating temperature in this process
maintained?

• (g) The final product from this process contains 60-65%

nitric acid. How is the concentration of nitric acid increased?
•
•
• 13. Calculate the maximum volume of ammonia gas that
would be collected at 26o C and 780 mmHg when 2.14 g
ammonium chloride is heated with excess potassium
hydroxide.
• (N=14, H=1, Cl = 35.5, molar gas volume at
s.t.p=. 22.4 dm3)
•
• 14. Explain how you would carry out the
following activities:
• (a) Distinguish nitrogen (Il) oxide from
nitrogen (I) oxide.

• (b) Remove some nitrogen (IV) oxide present

as an impurity in nitrogen (Il) oxide.

• (c) Obtain nitrogen gas from nitrogen (Il)

oxide.
• 15. (a) If you are provided with concentrated
nitric acid, distilled water and copper turnings,
describe briefly how you would prepare
samples of:
• (i) Nitrogen (Il) oxide.
• (ii) Nitrogen (IV) oxide.
• (b) Give three properties that would help you
to distinguish between nitrogen (Il) oxide and
nitrogen (IV) oxide.