Nitrogen

Nitrogen

Symbol :N Molecular formula : N2

Atomic number :7 Atomic weight : 14 amu
Molecular weight : 28 Vapour Density : 14
Electronic configuration : 1s2, 2s2, 2p3, Block : p-block
Nature of element : Non metal Valency :3
Rutherford Discovered by : Daniel

Isotopes :

Introduction
Nitrogen was discovered by Daniel Rutherford (Scottish
Scientist), in 1772 by burning phosphorus with air. He called it
Mephitic air (poisonous air) as it does not support life.
Lavoisier studied its properties in 1776 and called it Azote
(Azote: no life). The name nitrogen, given by Chaptal (1790)
this name was derived from nitre (KNO3) which is a mineral
containing nitrogen.
Occurrence
Nitrogen exists in free state about 78% volume in earth atmosphere. In
combined state all living matter including plants and animals contain
nitrogen in the form of proteins. It also presents in many compounds as
nitre (KNO3), chile saltpetre (NaNO3), salammoniac (NH4Cl), ammonium
sulphate ((NH4)2SO4).

Position of nitrogen in periodic table

Nitrogen is the first member of group VA in periodic table. The group VA
comprises nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb), and
bismuth (Bi). They are called pnicogens and their compounds are called
pnictides.
All the elements have five electrons (ns2, np3) in their valence shell, so
called p-block elements.
(According to Hund’s rule) these elements are not very reactive. Hence
p-orbitals are half filled and posses some extra stability.
As their p-orbital electrons are in the unpaired state (i.e np1 , np1 , np1 )
X y z
Reasons for inertness of nitrogen

Reactivity of any elements in chemical reactions is determined by the state of

valence electrons. The ground state electronic configuration of nitrogen atom is
1s22s22p3.
1s2 and 2s2 are completely filled
orbitals. These have little role in
chemical reaction. It is the electrons of
2p3 orbitals which decides the fate of chemical reaction of nitrogen atom.
Half – filled and fulfilled atomic orbitals are stable towards chemical reaction.
-As nitrogen has half –filled p orbitals, it is less reactive under ordinary
condition. However, it lacks the octet state and tend to undergo chemical
combination to attain octet state.

-Its high bond order i.e two nitrogen atoms are held
together by very strong triple bond in N2 molecules.
 Active nitrogen:
In 1900, Lewis observed the persistence of a golden –yellow
afterglow for several seconds even after the switching off an
electric discharge of nitrogen at low pressure .
In 1911, Strutt named the glowing gas as “active nitrogen” and
suggested that many of the properties could be due to atomic
nitrogen.
The energized nitrogen atom which can play an active role in
chemical transformation is called active nitrogen such active
nitrogen may be atomic nitrogen or excited neutral nitrogen
molecule. Besides these, excited nitrogen containing molecule
such as graphitized carbon nitride (g-C3N4) may also serve as the
source of active nitrogen.
Active nitrogen can be made by passing an electric spark through N2 gas at a
very low pressure (2 mm Hg). Yellow – pink luminiscence observe persist even
after discharge is stopped.
Dinitrogen after discharge becomes more active. This form of nitrogen is
called active nitrogen and it contains some nitrogen in the atomic state and
reacts readily with no. of metals to form nitrides. It reacts with many non-
metals such as sulphur, phosphorous , iodine etc.
It is able to break many normally stable molecules.
In other word the odd electron present in the nitrogen species are active
nitrogen. Eg. NO, NO2 etc

How is active nitrogen generated?

It can be generated by:
a) discharge method
b) bombarding the nitrogen gas with energized electrons
c)surface cracking of nitrogen containing molecules
d) Activation of nitrogen gas by radio frequency
Ammonia (NH3)

Ammonia is hydride of nitrogen. It exists in free state in

small quantities in air where organic nitrogeneous
compounds decay. In combined state, it occurs in the
forms of ammonium salts as NH4Cl (Salammoniac),
Ammonium sulphate etc.

Ammonia is a colorless and pungent

smelling water soluble gas.
Ammonia molecule has a pyramidal
or distorted tetrahedral shape with one
lone pair of electron on nitrogen atom.
Fritz Haber, c. 1919 Born 9
December 1868 Breslau,
Prussia[1] (now Wrocław,
Poland)
Died 29 January 1934 (aged 65)
Basel, Switzerland
 Principle
Hydrogen doesn’t react with Nitrogen at ordinary temperature
. But when the mixture of pure Nitrogen and Hydrogen in
ratio 1:3 by volume is heat at 450°C -500°C under a
pressure 200-900 atm in presence of Fe and metal oxide
(eg. Al2O3) as catalyst and promoter, Ammonia gas is
obtained .
N2 + 3H2 ⇌ 2NH3 + 22.4Kcal

.
 Conditions to get better
yield of ammonia
 High concentration
 Low temperature
 High pressure
 Use of catalyst
 Purity of hydrogen and
nitrogen
Explain all points in short
 Detail of process
Mixture of pure and dry Nitrogen and Hydrogen in the
ratio 1 : 3 by volume is compress to (200 – 900) atm
pressure are taken in catalyst chamber in presence of
catalyst Fe and Mo . The chamber is initially heated to
about 450°C-500°C . Under this reaction , Nitrogen
combines with Hydrogen in catalyst chamber by
converting 15% of mixture to Ammonia . Then resulting
Ammonia , Hydrogen and Nitrogen are pass through
condenser (Refrigerator) is collected into receiver called
liquor Ammonia . The uncombined Hydrogen and
Nitrogen are recycled and reprocessed .
 Physical properties: Ammonia
Its boiling point is -33.35 °C, and its freezing point is
-77.7 °C.
NH3 gas can be liquefied, however, due to its extremely
low boiling point,
liquid ammonia must be stored at low
temperature and high pressure.
ammonia is a colorless gas with a sharp, pungent
odour.
 It is highly soluble in water as it can form
intermolecular hydrogen bonding with water.
Fig. Intermolecular H- bonding
between ammonia and water
 Chemical properties of ammonia
 Action of ammonia with air
Ammonia gas burns with oxygen with greenish yellow
flame and get oxidized into nitrogen gas.
4NH3 + 3O2 → 2N2 + 6H2O

However in presence of platinum at 800°C, ammonia is

oxidized to nitric oxide .This reaction is used for the
manufacture of nitric acid by Ostwald’s process.

Pt/800°C
4NH3 +5O2 4NO↑+ 6H2O
 Action with dry conc. HCl
Ammonia is considered to be a weak base. It combines with
acids to form salts; thus with hydrochloric acid it forms
dense white fume of ammonium chloride.
NH3 (g) + HCl (g) → NH4Cl ↑

Basic property of ammonia

ammonia ionizes to a very small extent in aqueous solution. The
aqueous solution of ammonia acts as a weak base due to the
presence of OH- ions therein. Therefore, ammonia turns red
litmus blue and phenolpthalein solution into pink also reacts with
acids to form salt.

+ -
NH3 + H2O → NH4OH⇌ NH4 + OH
NH4OH + HCl → NH4Cl + H2O
 Reducing property of ammonia
NH3 reduces CuO into Cu and it self get oxidizes to N2.
3CuO +2 NH3 → 3 Cu +N2+3 H2O
3PbO +2NH3 → 3Pb+ N2 +3H2O
When ammonia gas is heated with bleaching powder, it reduces
CaOCl2 into CaCl2.

2NH3+3CaOCl2 → 3CaCl2 + 3H2O + N2

(Bleaching powder)

 Action with Carbondioxide:

Ammonia reacts with carbondioxide at 130-150°C

under pressure 220atm to give urea,a good nitrogenous
fertilizer.
130-150°C
CO2 + 2 NH3 220 atm
NH2CONH2 + H2O
Urea
• Action of ammonia with alkali metals
Ammonia gas reacts with molten sodium or potassium metal
at 300°C to form amide and hydrogen gas. The chemical
reaction is as:
2NH3+2Na→2NaNH2+H2
Sodamide
2K + 2NH3 2KNH2 + H 2 ↑
potasamide
Lithium and magnesium give nitride instead of amide with
ammonia.
3Mg + 2NH3 Mg3N2 + 3H 2 ↑
6Li +2NH3 magnesium niride
2Li3N + 3H 2 ↑
lithium nitride
 Action with mercurous nitrate paper
When ammonia reacts with mercurous nitrate paper, it produce
ammonium nitrate, mercury and insoluble HgNH2NO3. Due to the
formation mercuric amino nitrate and finely divided
mercury,ammonia turns Mercurous nitrate paper black

Hg2(NO3)2 + 2NH3(aq) → Hg+Hg(NH2)NO3(aq)↓ +NH4NO3(aq)

black ppt.

• Action with Mercuric chloride:

HgCl2 + NH3 Hg(NH 2 )Cl↓ +NH4Cl
white
 Action with Nessler's reagent
Nessler’s reagent is an alkaline solution of Potassium
tetraiodomercurate (II) (K2HgI4).When ammonia reacts
with Nessler's reagent, Iodide of Million's base(insoluble/
brown ppt) & potassium iodide is formed.

K2HgI4 + NH3 NH4I + 2KI + Hg(NH2)I

Pot.mercuric iodide basic amino mercuric iodide
2Hg(NH2)I + NH2.HgO.HgI↓ + NH4I
reddish brown ppt
H2O
(Amidoiodomercury)

Note: This reaction is used to detect ammonia or ammonium salts.

Complex formation
Ammonia is good complexing agent due to presence of lone pair
of electron in its nitrogen.

i) Action with copper sulphate solution :

When ammonia gas is passed into copper sulphate solution, at first
bluish white ppt of Cu(OH)2 is formed which disolves in excess of
ammonia forming deep blue coloured soluble complex compound.
NH3 + H2O→ NH4OH
CuSO4 + 2NH4OH → Cu(OH) 2 ↓ + (NH4)2SO4
(bluish whit ppt.)
Cu(OH)2 + 2NH4OH + (NH4)2SO4 →[Cu(NH3)4]SO4 + 4H2O
(deep blue colour)
Tetramine copper sulphate
ii) Action with silver chloride :
Silver chloride dissolves in ammonia solution forming a complex
compound, diammine silver (I) chloride. This reaction shows white
precipitate of AgCl dissolves in ammonia solution.

AgCl + 2NH4OH → [Ag(NH3)2]Cl + 2H2O

(soluble complex)

Some complex forming reactions of ammonia are:

NiCl2 + 4NH4OH →[Ni(NH3)4]Cl2 + 4H2O

tetrammine nickel (II) chloride

CoCl2 + 6NH4OH → [Co(NH3)6]Cl2 + 6H2O

hexammine cobalt (II) chloride
 Action with halogen
a)with excess of ammonia
8NH 3+ 3Cl 2 → N2+6NH4Cl
(excess)
b)with excess of chlorine
4NH3+ 3Cl 2 ⟶ NCl3 + 3NH4Cl
(excess) (nitrogen trichloride)
 Precipitation reaction
when aqueous solution of ammonia is treated with
metallic salts solutions then different coloured ppt of
metallic hydroxide is formed.
FeCl3 + NH4OH → Fe(OH)3↓(reddish brown ppt) + NH4Cl .
FeCl2+ NH4OH →Fe(OH)2 ↓(grennish ppt) + NH4Cl
AlCl 3 + NH 4OH⟶ Al(OH) 3 ↓ (white ppt) + NH4Cl
fig. Reddish brown ppt. of iodide
of millions base Fig. complex formation
(tetramine copper
sulphate)

Fig. black ppt. of basic Fig. white ppt. of basic

amino amino mercuric
 Uses of
ammonia

TNT

Fertilizer

As coolant
Laboratory
 Uses of ammonia:
1) Liquid ammonia is used as refrigerant.
2) Used for making dyes, plastic , explosives,
fertilizers and synthetic fibres.
3) Used as laboratory reagent.
4) Used in manufacture of washing soda by Solvay
ammonia soda process
5) Used in manufacture of nitric acid by Ostwald’s process
6) Used as cleaning agent for removing oils and grease
etc.
 Harmful effects of Ammonia:
 When large concentrations of ammonia are inhaled, the most
common symptoms that arise include an immediate burning of the
throat, nose, and respiratory tract. Eventually, this can lead to
respiratory distress or respiratory failure. If the concentration of
ammonia in the atmosphere is low, the common side effects are
throat irritation and nose irritation.
 Chronic exposure of ammonia may lead to pneumonia, kidney
damage, cataracts, ulceration etc.
 Persistent exposure of ammonia to mother may affect her
newborn offspring.
 Ammonia is one of the main sources of nitrogen pollution,
alongside nitrogen oxides. Ammonia pollution also effects species
composition through soil acidification, direct toxic damage to
leaves and by altering the susceptibitity of plants to frost, drought
and pathogens.
 Assignments
1. Write the action of Ammonia with i)dry conc. HCl
ii) FeSO4
iii)CO2 at 130-150°c
iv)excess Cl2
v) AgCl
vi) CaOCl2
2. What happens when ammonia is reacted with
(a) Nesseler’s reagent (b) Mercurous nitrate paper
(c) CuSO4 solution (d) CuO (e) Excess of chlorine
(f)sodium metal
3. Write reactions which show reducing action of
ammonia.
4. What is optimum temperature in Haber’s process.
Write the condition to get better yield of ammonia.
5. Write the principle and flowsheet diagram of
manufacture of NH3.
Oxy acids of nitrogen:
HYPONITROUS ACID (H2N2O2)

NITROUS ACID (HNO2 )

NITRIC ACID ( HNO3 )

Resonating Structure Resonating Structure

 Oxyacid of nitrogen…..

• They all are oxidizing acid.

• Acidity increases on increasing the oxidation
number of nitrogen, higher Oxidation state of
nitrogen increases polarity of O-H bond
making more feasible to loss the protn.
 Physical properties of nitric acid
• Pure acid is colourless but on long standing
some brown colour may appear due to
dissolved nitrogen dioxide.
• Water soluble acid.
• Corrosive to skin.
• MP is -420C and BP is 860C.
 Nitric Acid
Chemical properties of nitric acid:
It keeps on oxidizing and forms nitrogen dioxide that is why we see brown color fumes
coming out from the bottle.

1. Acidic nature: Nitric acid is acidic in nature because it dissociates to give

hydrogen ion when dissolved in water:

Because this is acidic therefore, it reacts with base showing neutralization reaction:
HNO3 + NaOH → NaNO3 + H2O
Nitric Acid (Sodium Hydroxide) (Sodium Nitrate) Water

Blue litmus turns to red

Pink colour of phenolphthalein to colourless
Light yellow colour of methyl orange into pink
 2. Oxidizing agent
• Nitric acid is a very good oxidizing agent at its any
concentration.
a) Action of nitric acid on metal( Zn, Mg, Fe, Cu)
Nitric acid dissolves all metal except gold and platinum. In every
reaction first of all metal is converted into its nitrate and nascent
hydrogen is generated. This hydrogen atom reacts with nitric acid
to form NO2, NO, N2O etc and it is oxidized to H2O.
Metal more electropositive than hydrogen reacts with
nitric acid via the formation of nascent hydrogen
whereas metals less electropositive than hydrogen and
non metals react with nitric acid via the formation of
nascent oxygen. So Zn, Mg, Fe react by forming
nascent hydrogen but copper metal react with the
formation of nascent oxygen.
Product formed by different concentration of nitric
acid
• i. with very dil. HNO3
With very dil. HNO3, metal (like Zn)gives ammonium
nitrate
4Zn + 10HNO3 → 4Zn(NO3)2 + NH4NO3 + 3H2O
• ii. with dil. HNO3
Zinc reduces dil. HNO3 to nitrous oxide (N2O)
4Zn + 10HNO3 → 4Zn(NO3)2 + N2O + 5H2O
• iii. With moderately conc. HNO3
Zinc reduces moderately conc. HNO3 to NO (nitric
oxide)
3Zn + 8HNO3 → 3Zn(NO3)2 + 2NO + 4H2O
• iv. With conc. HNO3
Zinc reduces conc. HNO3 to NO2 (nitrogen dioxide)
Zn + 4HNO3 → Zn(NO3)2 + 2NO2 +2H2O
b) Action of nitric acid on non-metals

Nitric acid oxidizes non metals like sulphur, carbon, phosphorous

and iodine into their respective oxy-acids and is itself reduced to
NO2.
Sulphur is oxidized to sulphuric acid.
2HNO3 H2O+ 2NO2 + 3[O]
S+ 3[O] SO3
SO3 + H2O H2SO4
S+ 6 HNO3 H2SO4 + 6NO2 + 2H2O
Carbon is oxidized to carbon dioxide.
2HNO3 H2O+ 2NO2 + 2[O]
C+ 2[O] CO2
C+ 4HNO3 CO2 + 4NO2 + 2H2O
c) Action of Nitric acid with compounds (SO2 , H2S)

With SO2: SO2 is oxidized to sulphuric acid.

Conc. 2HNO3 H2O+ 2NO2 + [O]
SO2 + [O] SO3
SO3 + H2O H2SO4
SO2+ 2HNO3 2NO2 + H2SO4

With H2S: H2S is oxidized to sulphur.

Conc. 2HNO3 H2O+ 2NO2 + [O]
H2S + [O] H2O + S
H2S + 2HNO3 2NO2 + 2H2O + S

#Write the reaction of HNO3 with Zn, Fe, Mg, Cu, H2S, SO2 .
Uses of nitric acid:
i) Nitric acid is used for the nitration of different compounds
like benzene to yield nitrobenzene.

ii) It is used in manufacture of fertilizers like ammonium nitrate,

basic calcium nitrate and etc.

iii) Nitric acid is used making plastics, and in the manufacture

of dyes.

iv) It is also used for making explosives.

v) When it is combined with hydrochloric acid, an element
called aqua Regia is formed.
Test for Nitrate ion(Ring test)
Salts of nitric acid is known as nitrates which are usually water
soluble. For nitrate test take about 1 mL of HNO3 in a test tube
and add about double volume of conc. H2SO4 to it. Cool the
mixture in tap water then add freshly prepared FeSO4 slowly into
the test tube of mixture maintained in inclined position. Brown
ring is formed at the surface of contact of the liquids.
Nitric acid oxidizes FeSO4 in presence of H2SO4 into Fe2(SO4)3
and itself reduce to NO. This NO dissolve in excess of FeSO4
solution giving the brown coloured ring of FeSO4.NO
(nitrosoferrous sulphate).

6FeSO4 + 3H2SO4 + 2HNO3→ 3 Fe2(SO4)3 + 2NO+ 4H2O

FeSO4 + NO → FeSO4.NO
[nitrosoferrous sulphate]
(brown ring)
Technical Production of
Nitric Acid by Ostwald's
Process (Manufacture
of HNO3 by Catalytic
Oxidation of Ammonia)
Principle
• 1. A mixture of ammonia gas with air (or oxygen) in
the ratio of 1:8 by volume is passed through a
catalyst chamber packed with platinum gauze or a
rhodium-platinum alloy maintained at a
temperature of 800°C.
• The ammonia is oxidized under these conditions to
nitric oxide.
• 2. The nitric oxide so formed is cooled rapidly down
to 50°C and led to an oxidizing tower where it
combines with oxygen of the air to form nitrogen
dioxide at low temperature (50°C) under pressure
because the reaction is reversible, exothermic and
involves the decrease in volume.
• 3. The resulting NO2 gas mixed with oxygen of the
air passes up a tower packed with acid proof stone
balls down which a spray of water trickles.
• Nitrogen dioxide reacts with water in the presence
of oxygen forming nitric acid.

• The reaction is exothermic and once the reaction

starts it proceeds automatically.
 Working of the plant [Flow sheet
Diagram]
NO
Oxidation chamber Water

NO2
Waste gases
Platinum gauze NO2

Acid proof quartz

NO + O2

Converter
Cooler
O2
dil. HNO3
Absorption tower
NH3 + dry air
1. Oxidation of Ammonia
• Ammonia is prepared by Haber's process. It is mixed
with 8 times its vol. of pure, dust free, dry air (or
oxygen).
• The mixture is passed through a converter made of
either steel or aluminium with platinum gauze placed in
it.
• The temperature of the converter is kept at about
800°C.
• In course of the reaction, the catalyst Pt gauze gets a
deposit of dust on it.
• Thus its efficiency is reduced.
• These days a more efficient catalyst consisting of an
alloy of 90% Pt and 10% Rh is being used.
• Here the ammonia is oxidized to nitric oxide.

• This reaction is exothermic. Therefore heating of

the converter is required initially.
• Later on, the heat of reaction maintains the
required temperature and no external heating is
required.
• About 90-95% of the ammonia is oxidized to nitric
oxide.
2. Oxidation of Nitric oxide
• The nitrogen oxide so formed is rapidly cooled and
passed through a chamber where it mixes with
oxygen of the air and oxidized to nitrogen dioxide.
• It is called oxidizing chamber.

• In the cooling chamber gases are cooled to 50°C.

• The oxidation of nitric oxide to nitrogen dioxide
which is a slow process at high temperature being
favored at a low temperature.
3. Absorption of Nitrogen
dioxide
• The NO2 from oxidizing tower is then passed
through absorption tower.
• This tower is packed with acid proof stone.
• The NO2 comes into contact with spray of hot water
and oxygen of the air with acid proof stone balls,
where it is oxidized to HNO3 and then dilute nitric
acid is collected at the bottom of the tower.
Concentration and Purification
• The dilute acid so collected at the foot of the tower, is
sprayed from top of the absorption tower repeatedly
and it gets concentrated, to obtain 60% HNO3 by mass.
• Thus obtained concentrated HNO3 by distillation gives
68% concentrated acid at maximum because it forms
here a constant boiling mixture.
• Concentrated HNO3 upto 98% pure can be obtained
under reduced pressure distillation in presence of
dehydrating agent conc. H2SO4 or with 72% Mg(NO3)2.
• Finally pure anhydrous nitric acid liquid is obtained by
its further distillation with P2O5.