N N

Nitrogen and Its

Compounds
Chapter 4
Jordan, Joshua, Kosheila, Poh Ping, Sophia
N is for Nitrogen
 1s2 2s2 2p3
 Achieves stable octet electron formation –

covalent triple bonding

◦ N2 molecule

N N
π
σ
π
Inert nature of Nitrogen
 Very stable and relatively inert
◦ Very strong triple bond
◦ Very short bond length
◦ High bond length energy

N2 (g) → 2N (g) △H = +945kJmol-1

 Bond must be broken with high energy before

N can react with other substance ∴ inert
Inert nature of Nitrogen
 Linear
 Non polar
 Distribution of electrons - symmetrical

∴ absence of polarity

X-
δ δX+

NN
X+
δ
●
●X δX-
X
●X
● x
●x
Reactivity of N2

N N N N N N
Very strong
δ+ δ-

Single Weaker
triple bond polar bond Single bond
Increasing
reactivity
Reactivity of N2
 At high temperature & pressure :
◦ N2 (g) + H2 (g) → 2NH3 (g)
◦ N2 (g) + O2 (g) → 2NO (g)
◦ N2 (g) + M (s) → MN (s)
e.g.
 N2 (g) + 2Al (s) → 2AlN (s)

 N2(g) + 3Mg (s) → Mg3N2(s)

Extraction of Nitrogen from Air
 fractional distillation of liquid air
Ammonia: Its Formation,
Properties and Uses
Formation and Properties of
Ammonia
Formation of Ammonia from
Ammonium Salts
 By heating a mixture of ammonium salt and
a base
NH4+ + OH- NH3 + H20

 Ammonia gas is dried by passing it through

anhydrous calcium oxide.

 Conc.H2SO4 & anhydrous CaCl2 can’t be

used because they react with ammonia
Industrial Preparation of
Ammonia
The Haber Process
Haber Process
 direct combination of N2 and H2 .
N2(g) + 3H2(g) Fe 2NH3(g)
-N2 from fractional distillation of liquefied air
-H2 from synthesis gas.

 Mixture of N2 and H2 passed over

◦ finely divided Fe , or
◦ Fe2O3 catalyst with K2O and Al2O3 as promoter
◦ (temp: 450-500o C, P: 200-500 atm).

 NH3 condensed in the condenser and collected as

liquid ammonia.
Physical Properties of
Ammonia
Properties of Ammonia
Physical Properties of NH3
 colourless
 pungent-smelling gas
 common alkaline gas.
 A covalent compound with a trigonal

pyramidal shape and with a lone pair of

electrons.
Properties of Ammonia
 a Lewis base (electron pair donor).

 Form dative bond by donating electrons to any

Lewis acid.

 a Bronsted-Lowry base (accepts a proton)

ammonium ion.
NH3 (g) + H2O (l) NH4+ (aq) + OH-
(aq)
base acid conjugate acid conjugate base
Properties of Ammonia
 b.p. - relatively high (presence of hydrogen bond)

 soluble in water  weak base solution with a low

base dissociation constant.
NH3 (g) + H2O (l) H3N.H2O

 liquid ammonia undergoes autoionisation NH4+

and NH2- ions.
 Liquid ammonia is a weak conductor of electricity.

2NH3 (l) NH4+ (l) + NH2- (l)

Chemical Properties of
Ammonia
As a weak base
 A lone pair on N atom in the molecule
act as proton acceptor
NH3 + H+ NH4+

 Dissolved in water, aqueous ammonia undergoes

partial dissociation NH4+ and OH- ions:
H3N.H2O(aq) NH4+ (aq) + OH- (aq)

 Aqueous ammonia reacts with acids to form salts

NH3(aq) + HCl(aq) NH4Cl(aq)
2NH3(aq) + H2SO4(aq) (NH4)2SO4(aq)
As a weak base
 Precipitates insoluble metallic hydroxides
from their salts (except Na+, K+ , and Ba2+ )

Cu2+(aq) + 2NH3(aq) + 2H2O(l) Cu(OH)2(s) +

2NH4+(aq)

 Some hydroxides dissolve in excess of NH3

 formation of water soluble complexes.
Cu(OH)2(s) + 4NH3(aq) [Cu(NH3)4]2+(aq) + 2OH-
(aq)
As Ligands in complex formation
 Form a dative bond by donating the lone pair
to the empty orbitals of metallic cations (esp.
transition metal ions).
 acts as Lewis base / ligand

 Examples of complex formation:

i. Tetraamminecopper(II), [Cu(NH3)4]2+
ii. Hexaamminenickel (II), [Ni(NH3)6]2+
Formation of addition compounds
 React with some substances
◦ addition compounds through the formation of
dative bonds.

 Examples:
i. NH3 + BF3 BF3 . NH3
ii. NH3 + AlCl3 AlCl3 . NH3
As a reducing agent
 Acts a reducing agent oxidised to nitrogen.
2NH3 N2 + 6H+ + 6e-

 Cl2 gas reacts with ammonia at room temp. N2 gas

8NH3(g) + 3Cl2(g) N2(g) + 6NH4Cl(s)

Excess of chlorine dangerously EXPLOSIVE OIL, NCl3

produced:
NH3(g) + 3Cl2(g) NCl3(l) + 3HCl(g)

 Reduces aqueous sodium chlorate(I) at room temp. to

the Cl- ion:
NH3 + 3ClO-(aq) N2(g) + 3Cl-(aq) + 3H2O(l)
Oxidation to nitrogen and steam
 - passing the dry gas over certain red hot
metallic oxides.
2NH3(g) + 3CuO(s) 3Cu(s) + N2(g) +
3H2O(l)
2NH3(g) + 3PbO(s) 3Pb(s) + N2(g) + 3H2O(l)

 Magnesium burns in dry ammonia magnesium

nitride &H2 gas
3Mg(s) + 2NH3(g) Mg3N2(s) + 3H2(g)
Combustion of ammonia
 Dry ammonia burns in oxygen to produce
nitrogen and steam.
4NH3(g) + 3O2(g) 2N2(g) + 6H2O(g)

 When dry ammonia and oxygen is passed

over heated platinum, nitrogen monoxide is
formed.
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)
- Involved in the Ostwald process .
Action of heat on ammonium
compounds
 Decompose when heated.
 Non-oxidising acids decompose to NH and the
3
corresponding acids.
NH4Cl (s) NH3(g) + HCl(g)
(NH4)2CO3(s) 2NH3(g) + CO2(g) + H2O(l)

 Oxidising acids decompose to either N2 or oxides of

nitrogen.
NH4NO2(s) N2(g) + 2H2O(l)
(NH4)2Cr2O7(s) N2(g) + Cr2O3(s) + 4H2O(l)

p/s : All these reactions can be EXPLOSIVE!!!

Reactions of aqueous ammonia on
certain cations
Cation Observations Solubility in excess NH3
 A reagent to identify cations in qualitative analysis.
Ag White ppt → light brown √
All cations  metal hydroxides (precipitates)
+


except
Zn 2+
Na+,ppt
White
K+, and NH4+. √

Mn2+ White ppt →brown X

Pb2+ White ppt X

Mg2+ White ppt X

Al3+ White ppt X

Cu2+ Blue ppt √(dark blue)

Cr3+ Great blue ppt X

Fe2+ Dirty green ppt X

Fe3+ Reddish brown ppt X

Ni2+ Green ppt √(light blue)

 USES OF AMMONIA
 Nitrogenous fertilisers.

 Manufacture of nitric acid in Ostwald process.

 catalytic oxidation of ammonia
 oxidation of nitrogen monoxide to nitrogen
dioxide
 formation of nitric acid from nitrogen dioxide

 Cooling agent / refrigerant

 Cleaning agent
Formation of Oxides of
Nitrogen
Nitrogen Monoxide
 colourless neutral gas, insoluble in water,
reducing agent

heptet electron configuration

( unpaired electron delocalised),
paramagnetic

 unstable, easily oxidised

2NO(g) + O2(g)  2NO2 (g)
Nitrogen Dioxide
brown acidic gas, pungent smell

 V-shaped, heptet configuration

(unpaired electron at nitrogen atom)

 double and dative bond delocalised actually

resonance hybrid structure
 in the environment

(disassociated by
lightning)
Nitrogen, N2(g) Oxygen, O2(g) 2 NO(g)

(Nitrogen monoxide)

2 NO2(g)

(Nitrogen dioxide)
 IN THE INTERNAL COMBUSTION
ENGINE

2800˚C

N2(g) + O2(g) => 2 NO(g) 2 NO (g)

2 NxOy

Volvo
 ATMOSPHERIC POLLUTANTS
FROM COMBUSTION OF FOSSIL
FUELS

Nitrogen oxides
Sulphur dioxides
Carbon monoxide
Unburnt hydrocarbon
Lead bromide(lead petrol)
 EFFECTS OF OXIDES OF
NITROGEN ON AIR POLLUTION

Acid Rain Photochemical Smog

 pH less than 5
ACID RAIN
Sulphur oxides and oxides of nitrogen are the
primary pollutants of the atmosphere.
Oxides of nitrogen dissolve in rain water to
produce nitrous acid and nitric acid.

2 NO2(g) + H20 -> HNO2 + HNO3

4 NO2(g) + 2 H20 + O2-> 4 HNO3

(one of the causes of acid rain)

 ACID RAIN
Nitrogen dioxide also catalyses the oxidation
of sulphur dioxide to produce sulphur
trioxide.
NO2 + SO2 -> NO + SO3

NO + ½ O2 -> NO2

SO2 + ½ O2 -> SO3

(also one of the causes of acid rain)
 ACID RAIN
The oxides of sulphur dissolve in rain water to
produce acid rain.

SO2 + H20 -> H2SO3 SO3 + H20 -> H2SO4

Sulphurous acid Sulphuric acid

ACID RAIN
PHOTOCHEMICAL SMOG
 Smoke & Fog
PHOTOCHEMICAL SMOG

Nitrogen dioxide Hydrocarbons Smog

2 Stages: uv light

Stage1 NO2(g) NO(g) + O

(g)
Stage2
O (g) + O2(g) O3(g)
Ozone molecule
 PHOTOCHEMICAL SMOG

combines Ozone molecule oxidize

Unsaturated hydrocarbon
(from incomplete combustion)

Organic radicles Less volatile organic

that form smog products that
when combined condenses on air
with nitrogen particles to form
monoxide smog
 View of Beijing 2005

After rain Before rain

Further Uses of Nitrogen

Hydrogen Laughing Gas

Tetranitrogen Cyanide
N4 N2O
HCN

Coolant agent Aircraft fuel