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.

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 Mo 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
 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 amino Fig. white ppt. of basic

mercurate nitrate amino mercuric chloride
 Uses of ammonia

TNT

Fertilizer

As coolant
Laboratory reagent
 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.