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The p-Block Elements

(Group 15-18)
 p-Block Elements

The p-block contains metals,

metalloids, as well as non–metals.
Group 13 to 18 of
the periodic table of
elements constitute
the p-block. General valence shell 2 1-6 1-6
electronic configuration ns2ns
npnp

Except He: 1s2

 Oxidation State

❖ Inert pair effect: Due to poor shielding effect of

the intervening d & f orbitals, increased Zeff
holds the ns2 electrons tightly, and hence ns2
electrons do not participate in the bonding.

❖ The inert pair effect predominates only in the

sixth period of the p-block.

❖ The highest oxidation state of p-block

elements = (group number-10)

❖ Down the group, stability of (highest O.S. - 2)

increases due to inert pair effect.
 Anomalous Behaviour

The first member of each group

from 13-17 of the p-block elements
differs in many respects from the other
members of their respective groups.

This is because of their small size,

high electronegativity, and
absence of d-orbitals.
 Anomalous Behaviour

The first member of the group has a

greater ability to form (as compared to
other members of the same group)

p𝝅-p𝝅 multiple bonds

With elements
With itself in the same period
of the p-Block

Example: C=C, Example: C=O, C=N,

C≡C, N≡N C≡N, N =O
 Group 15 Elements

Nitrogen (N)
Non-metals
Phosphorus (P)

Arsenic (As)
Metalloids
Antimony (Sb)

Bismuth (Bi) Metal

Group 15 Elements

Occurrence

Atomic properties

Physical properties

Chemical properties
 Nitrogen Occurrence

Molecular nitrogen comprises 78%

1 of earth’s atmosphere by mass.

It is an essential constituent of
2 proteins and amino acids.

It occurs as sodium nitrate,

3 NaNO3 (known as Chile saltpetre) &
potassium nitrate (Indian saltpetre).
 Phosphorus And Other Elements

Phosphorus occurs in minerals

of the apatite family,
1 Ca9(PO4)6.CaX2 (X = F, Cl, or OH)
which are the main components Arsenic, antimony,
of phosphate rocks. and bismuth are
found mainly as
sulphide minerals.

Phosphorus is an essential
2 constituent of animal
and plant matter.
 Atomic Properties

Electronic
Electronegativity
configuration

Covalent and Ionisation

ionic radii enthalpy
 Electronic Configuration

Valence shell
electronic
configuration

ns2 np3

Completely-filled Half-filled

Extra stability
 Covalent and ionic radii

1
Down the group, ionic and
covalent radii increases.

2
Down the group, covalent radii from N to P
increases considerably, but from As to Bi there
is only slight increase, because of poor
shielding effect of d and f orbitals.
 Ionisation Enthalpy

Down the
group
I.E. of Group 14
I.E. of Group < elements
15 elements
(ns2 np2)
Atomic Ionisation (ns2 np3)
size enthalpy

Because of extra stable

< < < < half-filled
N P As Sb Bi
p-orbital and smaller size

Order of successive ionisation enthalpy is ∆iH1 < ∆iH2 < ∆iH3

 Electronegativity

Down the
group Atomic
Electronegativity
size

< < < <

N P As Sb Bi

In heavier elements,
the difference is not
that much pronounced.
 Physical Properties

3. Metallic character
All the elements
1. Atomicity of group 15 are Due to decrease in
electronegativity
polyatomic.

Down the Metallic

group character

2. State N2 is diatomic gas

while all others are
solids.
N < P < As < Sb < Bi
 Physical Properties

4. Boiling Point

Generally, down the group boiling point

increases.

N < P < As < Sb > Bi

Sb to Bi, there is slight decrease in boiling point
due to inert pair effect.

5.Melting Point

Down the group melting point

Increases from N to As
Decreases from As to Bi.
 Physical Properties

Examples:
6. Allotropy
Phosphorus occurs in a wide range of
allotropic configurations. Red, black
It is the phenomenon where and white phosphorus are the three
most significant allotropic structures.
one substance exist in different
physical forms.
Allotropic structures of arsenic
are black, grey, and yellow.

All the elements show Yellow, metallic, and explosive

allotropy except nitrogen. are three significant allotropic
structures for antimony.
Anomalous
Properties Nitrogen
of Nitrogen (Analogous
to blue bird)

Other Elements
in this group
(Analogous to
brown birds)
 Anomalous Behaviour of Nitrogen

The catenation tendency

is weaker in nitrogen Another factor that
due to weak N-N single affects the chemistry of
bond. Nitrogen forms nitrogen in the absence of
p𝝅-p𝝅 multiple bonds
d-orbitals in its valence shell.
with itself and other
elements whereas heavier
elements of same group
can’t.
 Bonding And Covalency

Heavier elements
Besides restricting can form
its covalency to 4,
nitrogen cannot form a
p𝞹-d𝞹 bond.
d𝞹-p𝞹 bond

No d-orbital

It has one s and three

p-orbitals for bonding Eg: R3P=O
or R3P=CH2
(R: Alkyl group)
 Chemical Properties

Oxidation states and trends

in chemical reactivity

Reactivity towards
hydrogen (hydrides)

Reactivity towards oxygen

Reactivity towards halogens

Reactivity towards metals

 Oxidation States of Group 15 Elements

❏ Common oxidation state of group 15 elements are

-3, +3 and +5.

❏ The stability of -3 oxidation state decreases down

the group.

❏ Bismuth is more stable in +3 oxidation state than in

+5 due to inert pair effect.

❏ Stability of +5 oxidation state decreases down the

group.
 Stability of +5 Oxidation State

Order of stability of
+5 oxidation state

< < < <

P5+ Sb5+ As5+ N5+ Bi5+

The only well-

characterised BiF5
Bi (V) compound
 Other Oxidation States

Nitrogen
Compound O.S. of N

NH3 -3
Large number of
Exhibits oxidation states N2 0
from -3 to +5
N2O +1

NO +2
When it
reacts N2O3 +3
with oxygen
NO2/N2O4 +4

N2O5 +5
Note!!

Nitrogen does not form

compounds in +5 oxidation
state with halogens

As it does not have d-orbitals.

Phosphorous
shows +1 and
+4 oxidation
state in some
oxoacids.
 Disproportionation

Nitrogen

All oxidation tend to

states from disproportionate
+1 to +4 in an acid solution.

+3 +5 +2
3HNO2 HNO3 + H2O + 2NO
 Disproportionation

Phosphorus

For Sb and Bi, the +3

All intermediate oxidation state becomes
oxidation states both in alkaline increasingly stable
and acidic
disproportionate medium
into +5 and –3 with respect to
disproportionation

+3 +5 –3
4H3PO3 3H3PO4 + PH3
Reactivity Towards Hydrogen

All the elements

form hydrides
of the type

EH3

E = N, P, As, Sb or Bi
 Properties of Hydrides

Stability order: NH3 > PH3 > AsH3 > SbH3 > BiH3
Reducing character: NH3 < PH3 < AsH3 < SbH3 < BiH3
Basicity order: NH3 > PH3 > AsH3 > SbH3 ≥ BiH3
 Properties of Hydrides

Boiling Point

PH3 < AsH3 < NH3 < SbH3 < BiH3

van der Waals forces in bigger

Sb molecules dominates
the H-bonding in Ammonia
 Properties of Hydrides

Melting Point

NH3 > SbH3 > AsH3 > PH3

Due to
hydrogen-
bonding
Reactivity Towards Oxygen

All the elements But nitrogen forms

form two types various other oxides
of oxides also like NO, NO2,
N2O, etc.
E2O3 and E2O5

E = N, P, As, Sb or Bi
 The oxide in the higher oxidation
state of the element is more acidic
than that of the lower oxidation
state

Reactivity Down the group acidic

Towards character of oxide decreases.
Oxygen

The oxides in lower oxidation

state (i.e., +3) will act as
reducing reagents.The
reducing power of the oxides
decreases down the group
due to inert pair effect.
Note

Acidic nature of oxides

of nitrogen family

As the metallic nature increases on

going down the group, the acidic
nature of the oxides of nitrogen family
(oxidation state +3) decreases.
 Reactivity towards Halogens

These elements
react with halogens
to form two series
of halides

EX3 and EX5

E = N, P, As, Sb or Bi E = P, As, Sb or Bi
 Reactivity Towards Halogen

➢ Halides are of the form EX3 and EX5.

These elements ➢ Except NX3 all trihalides are stable.
react to form
two series of ➢ Except N all elements form pentahalides.
halides
➢ Pentahalides are more covalent than
EX3 and EX5 trihalides.

➢ Order of stability of halides: F > Cl > Br > I

E = N, P, As, Sb or
Bi except NX5
 Reactivity towards Metals

Ca3N2
Examples
All these elements react (Calcium nitride)
with metals to form
Ca3P2
their binary compounds
(Calcium phosphide)
exhibiting –3 oxidation
state. Na3As2
(Sodium arsenide)

Zn3Sb2
(Zinc antimonide)

Mg3Bi2
(Magnesium bismuthide)
 Dinitrogen

Preparation:

In the laboratory, it is prepared by reacting NH4Cl(aq) + NaNO2(aq)

aqueous solution of ammonium chloride with
sodium nitrite.
N2(g) + 2H2O(l) + NaCl(aq)

It is also prepared by heating Δ

NH4NO2 3N2(g) + H2O(l)
ammonium nitrite
 Dinitrogen

Preparation:

Very pure form of nitrogen can be prepared Δ

Ba(N3)2(s) Ba(s) + 3N2(g)
by thermal decomposition of azides.

Formation of dinitrogen from sodium Δ

2NaN3(s) 2Na(s) + 3N2(g)
azide in car airbags.

Industrially it is prepared from liquified

air by fractional distillation.
Physical Properties of Nitrogen Gas

Colourless, odourless, tasteless,

and non-toxic gas.

Having very low solubility

in water
 Chemical Properties

At higher temperatures
N2 is inert at room
temperature With metals With non-metals
because of the It directly combines with
high bond It forms
some metals to form
enthalpy of covalent
predominantly ionic
N≡N bond. nitrides
nitrides.

△
6Li + N2 2Li3N
Reactivity increases
rapidly with rise in △
3Mg(s) + N2(g) Mg3N2(g)
temperature.
 Chemical Properties

Dinitrogen combines with dioxygen

only at a very high temperature to
form nitric oxide (NO)
at about
2000 K

△
N2(g) + O2(g) 2NO(g)
 Uses of N2

1 In fertilizers.

2 In cryosurgery.

3 To prevent rancidity.

4 As refrigerant.
 Ammonia (NH3)
Nitrogen-Containing
Compounds
Oxides of nitrogen

Oxoacids of nitrogen
 Preparation of Ammonia

1 2
It is formed by the decay of Obtained from ammonium salts
nitrogenous organic matter that decompose on treatment with
caustic soda or calcium hydroxide.

NH2CONH2 + 2H2O (NH4)2CO3

(NH4)2SO4 + 2NaOH 2NH3 + 2H2O + Na2SO4

(NH4)2CO3 ⇌ 2NH3 + H2O + CO2 2NH4Cl + Ca(OH)2 2NH3 + 2H2O + CaCl2

 Preparation of Ammonia

1. Haber Process : Manufactured by Haber’s process.

❏ Optimum conditions for the production of ammonia:

Pressure(20 bar - 26 bar) and Temperature (～723 K).

❏ Catalyst used - Iron oxide with small amount of K2O and

Al2O3.

2. Manufactured by the hydrolysis of metal nitrides.

AlN + 3H2O Al(OH)3 + NH3

Mg3N2 + 6H2O 3Mg(OH)2 + 2NH3

 Physical Properties of Ammonia

1 Colourless gas

In solid and liquid states it

is associated through
2 Pungent odour
hydrogen bonds (same as
water).
Due to this association, it
3 Freezing point is 195.5 K has higher melting and
boiling points than
expected.
4 Boiling point is 240 K
 Physical Properties of Ammonia

6 Structure
Highly soluble in
7 water
Trigonal pyramidal

NH3(g) + H2O(l) ⇌ NH4+(aq) + OH─ (aq)

The aqueous solution is weakly

7 pm
1 . basic due to the formation of
10
OH─.
107.8o
 Ammonia as base

Chemical
Properties

Thermal decomposition
of ammonium salts
 Chemical Properties of Ammonia

Ammonia
as base

It forms ammonium salts with acids. As a weak base,

it precipitates
the hydroxides of
many metals
from their salt
NH3(g) + HCl(aq) NH4Cl(aq)
solutions.

2NH3(g) + H2SO4(aq) (NH4)2SO4(aq)

 Reaction of Ammonia with Metal Salts

Ammonia act as a weak base and precipitates the

hydroxides of many metals from their salt solutions.

2FeCl3(aq) + 3NH4OH(aq) Fe2O3.xH2O(s) + 3NH4Cl(aq)

Brown ppt

ZnSO4(aq) + 2NH4OH(aq) Zn(OH)2(s) + (NH4)2SO4(aq)

White ppt

2NH3 + 2H2O + CuSO4 Cu(OH)2 + (NH4)2SO4

Blue ppt
 Chemical Properties of Ammonia

Lone pair of electron on nitrogen in

ammonia makes
it a Lewis base and it helps in the
complex formation with metal ions.
Formation of ammonium complex with
Cu, Cd, Ag, etc.

Formation of a
complex of
ammonia and
NH3 copper results in
deep blue colour

[Cu(H2O)6]2+ [Cu(NH3)4(H2O)2]2+
 Thermal Decomposition of Ammonium Salts

● If the anion is not oxidising, then ammonia is evolved.

(NH4)2SO4(aq) 2NH3(g) + H2SO4(aq) NH4Cl(s) 2NH3(g) + HCl(g)

NH4HCO3(s) NH3(g) + H2O(g) + CO2(g)

● If the anion is more oxidising, then N2 or N2O is evolved.

Δ
NH4NO2(aq) N2(g) + 2H2O(l)

Δ
NH4NO3(aq) N2O(g) + 2H2O(l)
 Chemical Properties

Reaction with halogens

When ammonia is in excess;

8NH3 + 3Cl2 N2 + 6NH4Cl

When chlorine is in excess;

NH3 + 3Cl2 NCl3 + 3HCl

 Uses of Ammonia

Laboratory
Fertilizers
reagent

Refrigerant
 Oxides of Nitrogen

Oxides of Nitrogen

Dinitrogen oxide (N2O)

Nitrogen
In different Nitrogen monoxide (NO)
forms
oxidation
a number
states
of oxides Dinitrogen trioxide (N2O3)

Nitrogen dioxide (NO2)

Dinitrogen tetroxide (N2O4)

Dinitrogen pentoxide
(N2O5)
 Dinitrogen Oxide (N2O)

Preparation
△
NH4NO3(aq) N2O(g) + 2H2O(l)

Oxidation state N2O

2x + -2 = 0

x = +1

O.S. of nitrogen
 Dinitrogen Oxide (N2O)

Physical
appearance and
chemical nature
Stable

Relatively unreactive

Colourless gas

Neutral oxide
 Dinitrogen Oxide (N2O)

Structure

+ - - +

113 pm 119 pm

N N O
 Laughing Gas

Used as an anaesthetic and

also known as laughing gas
 Nitrogen Monoxide (NO)

Preparation

2NaNO2(aq) + 2FeSO4(aq) + 3H2SO4(aq)

Fe2(SO4)3(aq) + 2NaHSO4(aq) + 2H2O(l) + 2NO(g)

 Nitrogen Monoxide (NO)

Oxidation state Nature

NO

It is an odd electron
x + -2 = 0 molecule.
Hence, the gas is
paramagnetic in
x = +2 nature.

O.S. of nitrogen
 Nitrogen Monoxide (NO)

Physical appearance
Structure
and chemical nature

1 Colourless gas

2 Neutral oxide

Reacts instantly with

3
O2 to give NO2
N O
115 pm

2NO + O2 2NO2
 Dinitrogen Trioxide (N2O3)

Preparation

By condensing equimolar amounts

of NO and NO2 together or by reacting
NO with the appropriate amount of O2.

NO + NO2 N2O3

4NO + O2 2N2O3
 Dinitrogen Trioxide (N2O3)

Oxidation state

Physical appearance
N2O3 and chemical nature

Blue solid
2x + 3 × (‒2) = 0

Acidic
x = +3

It is anhydride of HNO2
O.S. of nitrogen
 Dinitrogen Trioxide (N2O3)

Structure –

+ +

pm
4
11
p m
1 21 186 pm

Planar
 Nitrogen Dioxide (NO2)

1. O.S. of nitrogen of NO2 is +4.

2. Red-brown poisonous gas and very reactive.
3. Structure: Bent
4. Dimerises into colourless N2O4.

Laboratory Method:

673 K
2Pb(NO3)2 4NO2 + 2PbO + O2

Yellow
solid
 Dinitrogen Tetroxide (N2O4)

Preparation
Cool
2NO2(g) N2O4(s)
Heat

Paramagnetic, Diamagnetic,
brown colourless

NO2─N2O4 system is a
strong oxidising agent
 Dinitrogen Tetroxide (N2O4)

Oxidation state
Physical
appearance and
N2O4 chemical nature

Colourless
2x + 4 × (─2) = 0 solid/liquid

x = +4 Acidic

O.S. of nitrogen
 Dinitrogen Tetroxide (N2O4)

Structure
– – –
+ + + +

m
175 pm

1p
o
135

12
Planar
 Dinitrogen Pentoxide (N2O5)

Preparation 4HNO3(aq) + P4O10(s) 4HPO3(aq) + 2N2O5(s)

N2O5
Oxidation state

2x + 5 × (─2) = 0

x = +5

O.S. of nitrogen
 Dinitrogen Pentoxide (N2O5)

Physical
appearance and 1 Colourless, deliquescent solid
chemical nature

2 Acidic

3 Anhydride of HNO3

4 Strong oxidising agent

 Dinitrogen Pentoxide (N2O5)

Structure

– – –

+ + + +
–

m pm
1p 11
9
15
o
134o
112

Planar
 Oxoacids of Nitrogen

Nitrogen forms
oxoacids such as

H2N2O2
(Hyponitrous acid)

HNO2 (Nitrous acid)

HNO3 (Nitric acid)

Most
important
 Preparation of Nitric Acid

1. Laboratory method: It is prepared by heating KNO3 or NaNO3

and concentrated H2SO4 in a glass retort.

NaNO3(aq) + H2SO4(aq) NaHSO4(aq) + HNO3(aq)

2. On large scale it is prepared by Ostwald's process.

Step 1: 4NH3 (g) + 5O2 (g) Pt/Rh Gauge Catalyst 4NO (g) + 6H2O (g)
500 K, 9 bar

Step 2: 2NO (g)+ O2 (g) ⇌ 2NO2 (g)

Step 3: 3NO2 (g) + H2O (l) 2HNO3 (aq) + NO (g)

By distillation, aqueous HNO3 can be concentrated up to ~68% by mass.

 Physical Properties

Colourless liquid On exposure to light, it turns

1
slightly brown because
4 of slight decomposition
Freezing point is 231.4 K and into NO2 and O2.
2 boiling point is 355.6 K.

4HNO3 4NO2 + O2 + 2H2O

Laboratory grade nitric acid
contains ~68% of the HNO3 by
3 mass.
 Physical Properties

In gaseous state
5
O

HNO3 exists as a
N O
planar molecule
H
O
102o

96
pm
130o
140.6 pm

Planar
 Chemical Properties of Nitric Acid

Reactivity

With water With non-metals and

With metals their compounds

In aqueous
Nitric acid behaves as a strong acid,
solution
releasing hydronium and nitrate ions

HNO3(aq) + H2O(l) H3O+(aq) + NO─

3
(aq)
 Reactivity with Metals

Concentrated nitric acid is a

strong oxidising agent.
Aqua regia is a mixture
of 25% conc. HNO3 and
75% conc. HCl. Cr, Al do
not dissolve in
concentrated nitric acid
It attacks most metals
because of the formation
of a passive film of oxide
on the surface.
Except,
noble metals
Examples: Au, Pt
 Factors Affecting Products of Oxidation

The products of oxidation depends

upon concentration of acid,
temperature and nature of material
undergoing oxidation.

4Zn + 10HNO3 (dil.) 4Zn(NO3)2 + N2O + 5H2O

Zn + 4HNO3 (conc.) Zn(NO3)2 + 2NO2 + 2H2O

 Reactivity with Non-Metals

Iodine to iodic acid I2 + 10HNO3 2HIO3 + 10NO2 + 4H2O

Carbon to carbon C + 4HNO3 CO2 + 4NO2 + 2H2O

dioxide

Sulphur to sulphuric S8 + 48HNO3 8H2SO4 + 48NO2 + 16H2O

acid

Phosphorus to P4 + 20HNO3 4H3PO4 + 20NO2 + 2H2O

phosphoric acid
 Brown Ring Test

Confirmatory Test for

Nitrate ion

Add dilute ferrous sulphate solution to aqueous solution

Process containing nitrate ion, then carefully add conc. sulphuric
acid along the sides of the test tube.

A brown ring appears at the interface between

Observation
the solution and H2SO4 layer
 Brown Ring Test

Depends on the ability of Fe2+ to reduce

nitrates to nitric oxide.

-
NO3 + 3Fe2+ + 4H+ NO + 3Fe3+ + 2H2O

Nitric oxide formed reacts with Fe2+ to

form brown-coloured complex

[Fe(H2O)6]2+ + NO [Fe(H2O)5(NO)]2+ + H2O

(Brown)

O.S of Fe is +1
 Uses of Nitric Acid

1 To manufacture Fertilizers.

2 In explosives.

3 Etching of metals

4 As oxidizer in rocket fuels.

 Allotropic Forms of Phosphorus

Physical Properties
Important Of White Phosphorous
allotropic forms
Translucent white
1 waxy solid
White phosphorus
2 Poisonous

Red phosphorus Insoluble in water but

3 soluble in carbon disulphide

Black phosphorus
Glows in the dark
4 (Chemiluminescence)
 Glows in the dark
(Chemiluminescence)
 White Phosphorus

Structure P

P P
P

Consists of discrete
tetrahedral P4 molecule
 Chemical Properties of White Phosphorus

White phosphorus is thermodynamically less stable.

In an inert atmosphere of CO2, it dissolves in

boiling NaOH solution to give PH3 and sodium
hypophosphite (NaH2PO2)

P4 (s) + 3NaOH (aq) + 3H2O (l) PH3 (g)+ 3NaH2PO2 (aq)

Readily catches fire to give white fumes of P4O10

With limited supply of oxygen, it forms P4O6

 Red Phosphorus

It is a polymeric chain of P4
1 tetrahedra linked to form giant
molecule.

2 Insoluble in H2O as well as in CS2

Does not ignite in air rapidly and

3
shows no reaction with NaOH.

When heated at very high

4 temperature under pressure
then forms black phosphorus.
 Black Phosphorus

● 𝛂-Black phosphorus:
Red phosphorus Sealed tube 𝛂-Black phosphorus
at 803 K
● 𝛃-Black phosphorus:
Under high pressure
White phosphorus 𝛃-Black phosphorus
473 K

Thermal Stability Order

White phosphorus < Red phosphorus < Black phosphorus
 Properties of Black Phosphorus

𝛂-Black phosphorus 𝛃-Black phosphorus

It does not burn

Can be sublimed in air
in air up to 673 K.

Thermally
Does not oxidise in air
most stable

Has opaque monoclinic

or rhombohedral
crystals
 Phosphorus-Containing
Compounds

Phosphine (PH3) Phosphorus halides Oxoacids of phosphorus

 Holmes signal

Sailors take a porous box of CaC2

and Ca3P2 and throw in water to form
gases (PH3 and C2H2) which burn
and thus guide the ships in sea.

Ca3P2 + 6H2O 2PH3 + 3Ca(OH)2

 Phosphine

Preparation of Phosphine

● By direct addition of water or dilute HCl to calcium

phosphide.

Ca3P2 (s) + 6H2O (l) 3Ca(OH)2 (aq) + 2PH3 (g)

Ca3P2 (s) + 6HCl (aq) 3CaCl2 (aq) + 2PH3 (g)

● Laboratory method: By addition of white phosphorus

to sodium hydroxide in an inert atmosphere.
 Physical Properties of PH3

1 Colourless gas

2 Rotten fish-like smell

3 Highly Poisonous Example: HNO3, Cl2

and Br2 vapours

Explodes in contact with

4
traces of oxidising agents

5 It is slightly soluble in water but

soluble in organic solvents.
Chemical Properties of Phosphine Gas

The solution of PH3 in water decomposes

1 in the presence of light giving red
phosphorus and H2.

When absorbed in copper sulphate or

2 mercuric chloride solution, the
corresponding phosphides are obtained.

3 Weakly basic and give phosphonium

compounds with HBr/HI only.
 Uses

The spontaneous combustion of

phosphine is technically used in
1
Holme’s signals.

Phosphine gas is used in

2 smoke screens

Containers containing calcium

carbide and calcium phosphide
3 are pierced and thrown in the
sea when the gases evolved
burn serve as a signal.
 Phosphorus halides

Preparation of PCl3

Obtained by passing dry

chlorine over heated P4 (s) + 6Cl2 (g) 4PCl3 (g)
1
white phosphorus

Obtained by the action of thionyl

2 chloride with white phosphorus

P4(g) + 8 SOCl2(l) 4PCl3 (l) + 4SO2(g) + 2S2Cl2(l)

 Properties of Phosphorus Trichloride

Chemical Properties

Physical Properties Pyramidal shape and sp3

hybridised.

On hydrolysis gives ortho

It is a colourless oily phosphorus acid.
liquid.

Act as reducing agent.

 Phosphorus halides

Preparation of PCl5
Reaction of white phosphorus
1 with excess of dry chlorine.

P4 + 10Cl2 4PCl5

Prepared by the action of

2 SO2Cl2 on phosphorus.

P4 + 10SO2Cl2 4PCl5 + 10SO2

 Properties of Phosphorus Pentachloride

Physical Properties PCl5 is a yellowish white

powder.

In moist air, it hydrolyses to POCl3 and finally gets

converted to phosphoric acid.
Chemical Properties

PCl5 (g) + H2O (l) POCl3 (g) + 2HCl (aq)

POCl3 (aq) + 3H2O (l) H3PO4 (aq) + 3HCl (aq)

Structure of Phosphorus Pentachloride

In gaseous and liquid phase, its

hybridisation is sp3d
and its shape will be trigonal
bipyramidal (TBP).
In solid state, it exists as
[PCl4]+ [PCl6]–.

Tetrahedral Octahedral
 Oxoacids of Phosphorus

Hypophosphorous Pyrophosphorous
Name Orthophosphorous acid
acid acid

Formula H3PO2 H3PO3 H4P2O5

Oxidation
+1 +3 +3
Number

Two P-OH
One P-OH Two P-OH
Two P-H
Characteristic Two P-H One P-H
Two P=O
One P=O One P=O
One P-O-P

Preparation White P4 + alkali P2O3 + H2O PCl3 + H3PO3

 Orthophosphorus Acid

Orthophosphorous acid
(or phosphorous acid) on heating
disproportionates to give
orthophosphoric acid (or
phosphoric acid) and phosphine.

4H3PO3 3H3PO4 + PH3

 Orthophosphoric Acid

Orthophosphoric
Name
O Acid

Formula H3PO4
H
P H
Oxidation +5
O O
O Three P-OH
Characteristic
One P=O

Preparation P4O10 + H2O

 Pyrophosphoric Acid

O O
Pyrophosphoric
Name
Acid
H
P P
OH O O Formula H4P2O7
H
O O Oxidation +5

Four P-OH
Characteristic Two P=O
One P-O-P

Heating
Preparation
phosphoric acid
 Hypophosphoric Acid

Hypophosphoric
O O Name
acid

Formula H4P2O6
P P
H
H
OH O
O
H
Oxidation +4
O
Four P-OH
Characteristic One P-P
Two P=O

Preparation Red P4 + alkali

Metaphosphoric Acid

Metaphosphoric
Name
Acid

Formula (HPO3)n

Oxidation +5

Three P-OH
Characteristic Three P=O
Three P-O-P

Phosphorus acid +
Preparation Br2, heat in a
sealed tube
 Group 16 Elements

16
Oxygen (O8 )

Non-metals Known as group

32 of chalcogens.
Sulphur (S16 )

Selenium Polonium is radioactive and

short-lived (half-life 13.8
Metalloids
days).
Tellurium
Radioactive
materials
Radioactive
Polonium
metal
 Occurrence

Oxygen

Most abundant Exists in free form as O2 and

of all elements makes up 20.9% by volume and
23% by weight of atmosphere.

Most of the oxygen is h𝛎

produced by 6CO2 + 6H2O C6H12O6 + 6O2
photosynthesis.
 Sulphur

Constitutes 0.034% by weight of earth’s crust and occurs

mainly in combined form as ores of sulphides and
sulphates (particularly gypsum).

Epsom Salt: Gypsum:

MgSO4.7H2O CaSO4.2H2O
Galena:
PbS
Baryte: Copper Pyrite:
BaSO4 CuFeS2

Zinc Blende:
ZnS
Atomic Properties

Electronic configuration

Atomic & ionic radii

Ionisation enthalpy

Electron gain enthalpy

Electronegativity
 Electronic Configuration Atomic And Ionic Radii

The elements of group 16 have

six electrons in the outermost
O < S < Se < Te
shell.

Down the group,

atomic and ionic
General valence shell radii increases due
electronic configuration to increase in
number of shells

ns2np4
 Ionisation Enthalpy

Group 15
elements > Group 16
elements

< < <

O S Se Te
ns2 np3 ns2 np4

Group 15 elements have higher

ionisation enthalpy because of
extra stable half-filled p subshell
 Electron Gain Enthalpy

Down
the group
For O From S to Po

Due to compact
The value again
nature, it has
becomes less
less negative
negative up to
electron gain
polonium.
enthalpy than S.
 Electronegativity

Order
O S Se Te Po
< < < <

Decreases
Down
the group

with increase in
atomic size.
 Physical Properties

1 Down the group Metallic character increases

with increase in atomic size

Down the group catenation decreases. But Sulphur

2 has higher catenation ability than Oxygen, due to high
interelectronic repulsions in O-O sigma bond.

3 Boiling point: O < S < Se < Te > Po

4 Melting point : O < S < Se < Te > Po

 Physical Properties

All elements
show allotropy.

Oxygen exists in two

allotropic forms

Dioxygen O2
O O

Ozone O3 (unstable and

decomposes to O2)
 Allotropes of Sulphur

1 Two common forms are 𝛼 or rhombic sulphur and

𝛽 or monoclinic sulphur.

Transition temperature is 95.5 0C, below which 𝛼

2 form exists and above which the 𝛽 form exists.

A third form known as 𝛾-monoclinic sulphur is

3
also present.

4 All three forms contain puckered S8 rings with a

crown conformation.
 Rhombic (𝛼-Sulphur)

It is yellow in colour and its

1 specific gravity is 2.06. Rhombic sulphur crystals are
4 formed on evaporating
the solution of roll sulphur in CS2.
2 Melting point = 385.8 K
It is insoluble in water but gets
5 dissolved to some extent in
benzene, alcohol and ether.
3 It is readily soluble in CS2.
 Monoclinic (𝛽-Sulphur)

3
This form of sulphur is prepared by
melting rhombic sulphur in a dish
1
Its melting point is 393 K and cooling it till crust is formed.
and specific gravity is 1.98.
Two holes are made in the
2 crust and the remaining
It is soluble in CS2. liquid is poured out.

On removing the crust,

colourless, needle-shaped
crystals of 𝛽-sulphur are
formed.
Allotropes of Sulphur

Several other modifications

of sulphur containing
6-20 sulphur atoms per
ring have been synthesised
in the last two decades.

In cyclo-S6, the ring

adopts the chair form.
 Anomalous
properties
of oxygen

Covalency Bonding
 Covalency

In case of other elements

The absence of of the same group,
d-orbitals in oxygen
restricts its covalency
to 4 and rarely
The valence shell can be
increases beyond 2.
expanded and covalency
exceeds four.
 Bonding

Oxygen has

High
Small size
electronegativity

Because of this, strong hydrogen

bonding is present in H2O which
is not found in H2S.
General Trends
& Chemical
Properties
 Oxidation State

Down the group tendency to exhibit

-2 oxidation state decreases.

Down the group tendency to exhibit

+4 oxidation state increases due to
inert pair effect.

Down the group tendency to exhibit

+6 oxidation state decreases.

The compounds in which these

elements are showing +4 and +6, are
predominantly covalent.
 Chemical Properties

Reactivity

Towards hydrogen Towards oxygen Towards halogens

 Properties of Hydrides

Thermal < < <

stability H2O H2S H2Se H2Te

Hydrides ∆dissH0 of H–E (kJ mol–1)

H2O 463

H2S 347

H2Se 276

H2Te 238

∆dissH0 : Bond dissociation enthalpy

 Properties of Hydrides

Acidity
< < <
H2Te H2Se H2S H2O

Hydrides Ka Value

H2O 1.8 × 10‒16

H2S 1.3 × 10‒7

H2Se 1.3 × 10‒4

H2Te 2.3 × 10‒3

Ka: Dissociation constant

 Properties of Hydrides

Boiling
< < <
H2O H2Te H2Se H2S
Point
Generally,

Molecular
Boiling point ∝ weight

Down Boiling
the group point
Due to
hydrogen bond
H2O has high boiling point as
compared to other hydrides.
 Properties of Hydrides

Reducing
property

All the hydrides except water

possess reducing property.

This character increases

from H2S to H2Te.
 Reactivity Towards Oxygen

All the elements form two types of

oxides EO2 and EO3.

Down the group, reducing power of

dioxide increases.

Trioxides act only as oxidising agents.

Both dioxides and trioxides are acidic

in nature.
 Reactivity Towards Halogens

These elements react to form

three series of halides.

E = Element of group 16,

EX6, EX4, EX2 X = Halogen

Stability Order of stability of halides

‒ < ‒ < ‒ < ‒

F Cl Br I
 Hexahalides

Amongst hexahalides,
hexafluorides are the Sulphur
1
only stable halides. hexafluoride (SF6) is
exceptionally stable due
to steric reasons.
All hexafluorides are
2 gaseous in nature.

They have an Sulphur

3 octahedral structure. Hexafluoride (SF6)
 Tetrafluoride

Tetrafluorides have
sp3d hybridisation.

Trigonal bipyramidal
geometry

One of the equatorial

See-saw shape
position is occupied by
a lone pair of electrons.
 Dihalides

All elements
except oxygen
form dichlorides
and dibromides.

Dihalides formed have

sp3 hybridisation.

Tetrahedral geometry
 Monohalides

These dimeric halides undergo

The well-known
disproportionation
monohalides are
dimeric in nature.

2Se2Cl2 SeCl4 + 3Se

S2F2, S2Cl2, S2Br2,

Examples
Se2Cl2, and Se2Br2
 Allotropes of
Oxygen

Oxygen (O2) Ozone (O3)

 Preparation of Oxygen Gas
1
Dioxygen is produced industrially by fractional
distillation of air.

2
Electrolysis of water leads to the release of hydrogen
at the cathode and oxygen at the anode.
150ºC
2KClO3 2KCl + 3O2 + traces of Cl2 or ClO2
MnO2

2H2O2(aq) 2H2O(l) + O2(g)

3
Metal oxides on decomposition gives Oxygen.
 Physical Properties

Pale blue liquid and a

1
colourless gas

2 Odourless gas

3 Strong supporter
of combustion

4 Paramagnetic in nature
 Oxides

Oxygen reacts with most of the Oxides

elements
of the periodic table to form oxides.

Simple Mixed
Eg., MgO, Al2O3 Eg., Pb3O4, Fe3O4
In many cases one element forms
two or more oxides. The oxides vary Metals are
Metals are
widely in their nature and present in more
present in single
properties. than one
oxidation states
oxidation states
 Simple oxides

Acidic Neutral

Basic Amphoteric

1 An oxide that combines with water

to give an acid.

Acidic oxides 2 Non-metallic oxides are generally

acidic in nature.

3 Example: SO2, Cl2O7, CO2, N2O5

 Basic Oxides

Oxides that
give a base
on reaction In general, metallic
with water. oxides are basic in
nature.

Example
Na2O, CaO, BaO

CaO + H2O Ca(OH)2

 Amphoteric Oxides

Some metallic oxides exhibit a dual

behaviour. They show characteristics
of both acidic as well as basic oxides.
Example: Al2O3

Al2O3(s) + 6HCl(aq) + 9H2O(𝓁) 2[Al(H2O)6]3+(aq) + 6Cl─(aq)

Al2O3(s) + 6NaOH(aq) + 3H2O(𝓁) 2Na3[Al(OH)6](aq)

 Neutral Oxides

Such oxides are known

Oxides that are as neutral oxides.
neither acidic
nor basic.

E.g., CO, NO, and N2O

 Ozone

Silent electrical
discharge is used in the
preparation of
ozone to prevent its
decomposition.

3O2 2O3; ΔH0 (298 K) = +142 kJ mol-1

 Preparation of Ozone

Dry O2 gas

Metal foil outside of the

outer glass tube

Metal foil inside of the

inner glass tube
Electric discharge
between the inner and O3 in O2
outer tubes
 Preparation of Ozone

Mixture obtained contains 5–10%

Silent electrical ozone by volume, and this mixture
discharge is used in the is called ozonised oxygen.
preparation of
ozone to prevent its
decomposition.
Higher concentration or pure O3
can be obtained by fractional
liquefaction of the mixture.
 Physical Properties of Ozone

Gas – dark blue

1 Liquid – blue
Solid – violet

It has a characteristic smell

2 and is toxic in high
concentrations (> 100 ppm)
 Chemical Properties of Ozone

O3 is thermodynamically
unstable with respect to O2
Exothermic
reaction
O3 O2 + O

Large
ΔG = -ve negative

High conc. of ozone can

be dangerously explosive.
Chemical Properties of Ozone

Ozone acts as a
powerful oxidising
agent due to the ease
with which it liberates
the atoms of nascent
oxygen.

O3 O2 + [O]
 Ozone

Buffered with a borate

buffer (pH = 9.2)

When ozone reacts with

an excess of KI solution

Iodine is liberated, which can

be titrated against a standard
solution of Na2S2O3
 Estimation of Ozone

O3 Na2S2O3

I2 liberated is
KI Solution I2 Solution estimated with
hypo solution
Ozone Hole
 Ozone depletion

Particularly
nitric oxide
Experimentally, nitrogen
oxide combine very NO (g) + O3 (g) NO2 (g) + O2 (g)
rapidly with O3

There is a possibility that nitrogen oxides emitted

from the exhaust systems of supersonic jet
aeroplanes might be slowly depleting the
concentration of the ozone layer in the upper
atmosphere.
 Ozone Structure

128 pm

The two O–O bond

lengths are identical

It is a resonance hybrid
Resonance Hybrid of the two possible
resonating structures.

+ +
‒ ‒
 Uses of Ozone

Sterilising

Disinfectant

Bleaching agent

Protects us from harmful UV radiation

of sun
 Sulphur Dioxide (SO2)

Both the bonds are equivalent

Molecule of SO2 is Bent or

V-shaped.
Resonance
hybrid It is a resonance hybrid of
the two canonical forms

+ +
‒ ‒
 Preparation of Sulphur Dioxide

1. Little amount of sulphur dioxide can be prepared by

direct heating of sulphur in air or oxygen.

Burn
S + O2 or air SO2

2. Sulphur dioxide can also be prepared by treating

sulphite with dilute sulphuric acid.

2─
SO3 (aq) + 2H+(aq) H2O(l) + SO2(g)
Physical Properties of SO2

Colourless gas with a

1 burning sulphur smell

Highly soluble in water

2
Then Now
 Chemical Properties of Sulphur Dioxide

1 Sulphur dioxide dissolves in water to form

sulphurous acid (H2SO3)

It reacts with NaOH to form sodium sulphite

2 (Na2SO3), then reacts with more sulphur dioxide
to form sodium hydrogen sulphite (NaHSO3)

3 It is a powerful reducing agent.

3+
2Fe + SO2 + 2H2O 2Fe2+ + SO42─ + 4H+

It decolourise the solution of potassium

4 permanganate KMnO4 (can be used a test for
SO2 gas).
 Uses of SO2

In refining sugar

In refining petroleum

As an anti-chlor
 Oxoacids of Sulphur

Sulphur forms a number of oxoacids

such as H2SO3, H2SO4, H2S2O7, H2S2O8

Some of these acids are unstable and

cannot be isolated.
Oxoacids of Sulphur
Oxoacids of Sulphur
 Sulphuric Acid

Contact Process
Preparation:

Sulphur or sulphide ores are

1 burnt in air to generate SO2
Sulphuric acid is
manufactured
by the contact process.
S+O2 (g) SO2 (g)

SO2 produced is purified by

Sulphuric acid obtained by removing dust and other
contact process is 96–98% impurities such as
pure. arsenic compounds
 Contact Process

Conversion of SO2 to SO3 by

reaction with oxygen in the
2 presence of a catalyst (V2O5)
Reaction is
exothermic, reversible

V2O5
2SO2(g) + O2(g) 2SO3(g)
Low temperature (not
too low) and high pressure
are the favourable conditions
for maximum yield.
 Contact Process

Absorption of SO2 in H2SO4

3 to give oleum (H2S2O7)

Dilution of oleum with water

gives H2SO4 of the desired
concentration
 Properties of H2SO4

Chemical Properties
Physical properties

Oxidising agent in
aqueous solution
Colourless, dense,
1 oily liquid
Characteristics of
sulphuric acid

Dissolves in water with

the evolution of a large
2 quantity of heat
Strong acidic Strong affinity
character for water
 Chemical Properties of H2SO4

1 Sulphuric acid ionises in two steps

─
H2SO4 (aq) + H2O (l) H3O+ (aq) + HSO4 (aq)

Ka = very large (Ka > 10)

1 1

2─
H3O+ (aq) + SO4 (aq)
─
HSO4 (aq) + H2O (l)

K a = 1.2 × 10─2
2
Chemical Properties of H2SO4

Larger value of Ka (Ka > 10)

1 1
means that H2SO4 is largely
–
dissociated into H+ and HSO4

Greater
Stronger is
dissociation
the acid
constant (Ka)
 Chemical Properties of H2SO4

Hot conc. H2SO4 is a moderately strong

oxidising agent (intermediate between
phosphoric and nitric acids). Both metals and
non-metals are oxidised

Cu + 2H2SO4 (conc) CuSO4 + SO2 + 2H2O

S + 2H2SO4 (conc) 3SO2 + 2H2O

C + 2H2SO4 (conc) CO2 + 2SO2 + 2H2O

Chemical Properties of H2SO4
 Uses of H2SO4

To manufacture
Petroleum
fertilisers refining

Lead storage
batteries
p-Block Elements

F ree
Group 13

Group 14
Cl asses
Group 15 Br ing
Group 16
I nfinite
Group 17
At tendance
Group 18
 Group 17 Elements

These are collectively

known as the
halogens.

Greek: halo Greek: genes

Meaning: salt Meaning: born

Salt producers
Group 17 Elements

Occurrence

Atomic properties

Physical properties

Chemical properties
Element Source

● Main Source: Fluorspar (CaF2) or fluorite

F ● Another Source: Fluorapatite [3Ca3(PO4)2.CaF2]
Cryolite: Na3AlF6

Most abundant compound of Cl: NaCl (Sea water)

Cl
Carnallite: KCl.MgCl2.6H2O

Bromides occur in sea

Br
water and brine lakes.

● Iodides occur in low concentration in sea water.

I
● Better source: Natural brines
 Atomic Properties

Electronic configuration

Covalent and ionic radii

Ionisation enthalpy

Electron gain enthalpy

Enthalpy of dissociation

Distance (X‒X)
 Atomic Properties

Electronic General valence shell

configuration ns2np5
electronic configuration

Electronic
Element
configuration

F [He]2s22p5

Cl [Ne]3s23p5

Br [Ar]3d104s24p5

I [Kr]4d105s25p5
 Atomic Properties

Covalent and Down the

ionic radii F < Cl < Br < I group the
number
of shells
increase.
Covalent radii Ionic radii
Element
(in pm) (in pm)

F 64 133

Cl 99 184

Br 114 196

I 133 220
 Atomic Properties

Ionisation Due to
enthalpy F > Cl > Br > I decrease in
size, removing
electrons
demands
Ionisation enthalpy higher energy.
Element
(in kJ/mol)

F 1680

Cl 1256

Br 1142

I 1008
 Atomic and Physical Properties

Electron gain
enthalpy < < <
Cl F Br I

Electron gain
enthalpy -349 -333 -325 -296
(in kJ/mol)

Maximum negative electron gain

enthalpy in the corresponding period
 Atomic and Physical Properties

Electron gain
enthalpy Due to small size of fluorine atom

There are strong interelectronic

repulsions in the relatively small
2p orbitals of fluorine.

Thus, the incoming electron does

not experience much attraction.
 Atomic and Physical Properties

Enthalpy of < < <

dissociation (X2) Cl–Cl Br– Br F–F I–I

Enthalpy of dissociation
Compound
(in kJ/mol)

F–F 158.8

Cl–Cl 242.6

Br–Br 192.8

I–I 151.1
 Atomic and Physical Properties

> > >

Bond length X–X F2 Cl2 Br2 I2

Compound Distance (in pm)

F2 143

Cl2 199

Br2 229

I2 266
 Physical Properties of Group 17 Elements

❏ All halogens exist as diatomic (X2) molecule.

❏ Boiling and melting point order: F2 < Cl2 < Br2 < I2
❏ Hydration energy order: F‒ > Cl‒ > Br‒ > I‒
❏ Fluorine is a pale green-yellow gas, chlorine is
greenish-yellow gas, bromine is reddish brown liquid
and iodine is dark violet solid.
❏ Fluorine and chlorine react with water. Bromine and
iodine are only sparingly soluble in water.
 Chemical
Reactivity

Reactivity towards Reactivity towards

hydrogen other halogens

Reactivity towards Reactivity towards

oxygen metals
 Reactivity Towards Hydrogen

Where
X2 + H2 2HX X = F, Cl, Br, I

Hydrogen
halides

Down Reactivity
the group towards H2

F2 reacts violently, whereas

I2 is slow at room temperature.
 Hydrogen Halides

Stability
< < <
HF HCl HBr HI

ΔdissH
574 432 363 295
(kJ/mol)

Acidic
Strength

HF < HCl < HBr < HI

Fluorine reacts readily with
oxygen & form OF2 which is
used as an oxidizer in
rocket.
 Oxygen Fluorides

1 Fluorine forms two

oxides, OF2 and O2F2.

Only OF2 is thermally

stable at 298 K.

2
These oxides are essentially oxygen
fluorides because of the higher
electronegativity of fluorine than oxygen.
Both are strong fluorinating agents.
 Halogen Oxides

3 4
Chlorine, bromine and iodine form oxides Considering kinetic and
in which the oxidation states of these thermodynamic factors,
halogens vary from +1 to +7. stability order of oxides
formed by halogens follow
the order:
Higher oxides of halogens tend to be Br < Cl < I
more stable than the lower ones.
 Stability of Halogen Oxides

Due to greater
polarisability
of I–O bond
Oxides of iodine
Stability
Cl–O multiple
bond formation
due to availability
Oxides of chlorine of d–orbitals

Oxides of bromine
 Chlorine Oxides

Cl2O, ClO2, Cl2O6, and Cl2O7

Highly reactive oxidising agents

and tend to explode.

ClO2 is used as a bleaching

agent for paper pulp and textiles
and in water treatment.
 Reactivity Towards Metal

Halogens react with metals Ionic character

to form metal halides.
< < <
MF MCl MBr MI
General reaction

nX2 + 2M 2MXn
Where M = Monovalent metal

Example
If a metal exhibits more than one
oxidation state, the halides in higher
Br2 (l) + Mg (s) MgBr2 (s)
oxidation state will be more covalent
than the one in lower oxidation state.
 Preparation

Physical properties

Chlorine

Chemical properties

Uses
 Preparation of Chlorine

1. By heating manganese dioxide with

concentrated hydrochloric acid

MnO2 + 4HCl MnCl2 + Cl2 + 2H2O

2. Air is used to oxidise HCl in the presence of Reaction is

reversible,and
CuCl2 (catalyst) at 713 K (Deacon’s Process).
the conversion is
65%
CuCl2
HCl + O2 o
2Cl2 + 2H2O + Heat
440 C
 Physical Properties of Cl2

Greenish yellow gas with

01 pungent and suffocating odour

About 2–5 times

02 heavier than air

03 Soluble in water
 Chemical Properties of Chlorine

Chlorine reacts with a number of metals and

non-metals.

2NaOH + Cl2 NaCl + NaOCl + H2O

Cold and dil.

6NaOH + 3Cl2 5NaCl + NaClO3 + 3H2O

Hot and conc.

Chlorine water on standing loses its yellow colour due to the

formation of HCl and HOCl.

HOCl gives [O], which is responsible for the oxidising and

bleaching properties of chlorine.
 Chemical Properties of Chlorine

Oxidising property

2FeSO4 + H2SO4 + Cl2 Fe2(SO4)3 + 2HCl

I2 + 6H2O + 5Cl2 2HIO3 + 10HCl

Chlorine is a powerful bleaching agent(due to

nascent oxygen) and the bleaching effect is
permanent

Cl2 + H2O 2HCl + [O]

Coloured [O] Colourless
Substance substance
 Chemical Properties of Chlorine

Reaction with dry slaked lime

2Ca(OH)2 + 2Cl2 Ca(OCl)2 + CaCl2 + 2H2O

Composition of bleaching powder: Ca(OCl)2.CaCl2.Ca(OH)2.2H2O

 Phosgene

Preparation CO(g) + Cl2(g) COCl2(g)

Properties 01 Highly toxic colourless

gas.

02 Planar geometry

03 Slightly soluble in
water
 Uses of Chlorine

Bleaching

Preparation of poisonous gases such as

phosgene (COCl2), tear gas(CCl3NO2) and
mustard gas (ClCH2CH2SCH2CH2Cl)etc.
 Preparation

Physical properties

HCl

Chemical properties

Uses
 Preparation of HCl

Heating sodium chloride with

concentrated sulphuric acid

150ºC
NaCl + H2SO4 NaHSO4 + HCl

550ºC
NaHSO4 + NaCl Na2SO4 + HCl
 Physical Properties of HCl

Colourless, pungent smelling

gas at room temperature.

Quiet soluble in water

HCl(g) + H2O(l) H3O+(aq) + Cl─(aq)

 Physical Properties of HCl

The aqueous solution is

called hydrochloric acid.

High value of Strong acid

dissociation in water
constant (Ka)

Ka ≈ 107
 Chemical Properties of HCl

➢ Acidic character:
It reacts with NH3 and gives off white fumes of NH4Cl

NH3 + HCl NH4Cl

➢ Hydrochloric acid decomposes the salts of weak acids.

Na2CO3 + 2HCl 2NaCl + H2O + CO2

NaHCO3 + HCl NaCl + H2O + CO2

Na2SO3 + 2HCl 2NaCl + H2O + SO2

 Uses of HCl

In manufacturing chlorine, NH4Cl,

and glucose (from corn starch)

In medicines

As a laboratory reagent
 Oxoacid of Fluorine

Hypofluorous acid (HOF)

Fluorine is unique among the halogens

in forming no species in which it has a
formal oxidation state other than -1.

The only known oxoacid is

hypofluorous acid, HOF.
 Oxoacids of Chlorine

Chlorous acid Chloric acid Perchloric acid

Interhalogen Compounds

Halogen atoms have different

electronegativity. Due to this
difference in electronegativity,
the halogen atoms combine
with each other.

This gives rise to the formation

of covalent compounds, which
are called interhalogen
compounds.
 Types and Examples of Interhalogen Compounds

There are four types of interhalogen compounds: XX’, XX’3 ,

1 XX’5, and XX’5. Where, X and X’ are halogen of
larger size and smaller size respectively.

2 X is more electropositive than X′

Examples: Iodine monofluoride (IF), chlorine trifluoride

3 (ClF3), bromine pentafluoride (BrF5).
 Types and Examples of Interhalogen Compounds

Iodine monofluoride

Bromine pentafluoride

Iodine heptafluoride Chlorine trifluoride

Interhalogen Compounds
 Preparation

By the direct Cl2 + F2 473 K

2ClF
combination (equal volumes)
of halogens:
Cl2 + 3F2 573 K 2ClF3
(excess)

I2 + Cl2
2ICl
(equimolar)

IF5 + I2 543 K
IF7

BrF3 + F2
BrF5
(excess)
 Physical Properties

These compounds may be All interhalogens are

1 gases, liquids, or solids. 2 covalent molecules and
are diamagnetic in nature.

Gases: ClF, BrF, ClF3, IF7

Electronegativity
3 difference ∝ Boiling point
Liquids: BrF3, BrF5

between
Solids: ICl, IBr, IF3, ICl3 X and X′ atoms
 Physical Properties

Electronegativity Thermal XX′ type

4 difference ∝ stability

between
X and X′ atoms

IF > ClF > ICl

More polar is the X–X′ bond, more

is the stability of interhalogen.
 Chemical properties of interhalogen
compounds

1 Interhalogen compounds are more reactive than the

parent halogens but less reactive than F2.

2 X–X' bond in interhalogens is weaker than the X–X bond

in halogens, except for F-F bond.

3 Polarity of the bonds make it more susceptible for the

other reactions.

4 All Interhalogen compounds undergoes hydrolysis.

AB + H2O HB + HOA
 Chemical Properties

A halide ion from smaller halogen A halide ion from smaller halogen
and a hypohalite (when AB) anion and a halite (when AB3), halate (when
derived from larger halogen. AB5) anion derived from larger halogen.

AB + H2O HB + HOA ICl3 + 2H2O 3HCl + HIO2

BrCl + H2O HCl + HOBr IF5 + 3H2O 5HF + HIO3

ICl + H2O HCl + HIO BrF5 + 3H2O 5HF + HBrO3

Note!!

Pseudohalide ions

Ions which consists of two or more atoms of

which at least one is nitrogen and have
properties similar to those of halide ions
example CN−, OCN−, SCN− etc.

Pseudohalogens

Some of the pseudohalide ions oxidises to

form covalent dimers comparable to X2
example (CN)2, (SCN)2, (SeCN)2
Uses of Interhalogen compounds

Interhalogen compounds are very useful

fluorinating agents.

Enrichment of uranium ore

U (s) + 3ClF3 (l) UF6 (g) + 3ClF (g)

 Group 18 Elements

Helium

Neon All these are gases and

are chemically unreactive.
Argon

Krypton They form very few

compounds, and hence
they are termed
Xenon
as noble gases.

Radon
 Occurrence and Isolation

Except radon

All noble gases present

in the atmosphere

Order of
abundance in air

Ar > Ne > Kr

> He > Xe
Atomic Properties
of Noble Elements
 Atomic Properties

Atomic radii
Electronic
configuration
Down
the group
Except Increases
All noble gases have Helium (1s2)
the general electronic
configuration ns2np6. Number of
Reason shells increases
Their inactive nature are
ascribed to their completely
filled electronic
He < Ne < Ar < Kr < Xe
configuration.
 Atomic Properties

Ionisation Due to the stable electronic

enthalpy configuration, they exhibit very
high ionisation enthalpy.

Down Decreases
the group

He > Ne > Ar > Kr > Xe

 Physical Properties

All the noble gases

1 are mono-atomic.

Colourless, odourless, and

2 tasteless.

Sparingly soluble
3 in water.

Very low melting and boiling This is because the only

4 points type of interatomic
interaction in these
elements is weak
dispersion forces.
Chemical Properties

Noble gases are

least reactive due to

Completely filled ns2 np6

electronic configuration
in their valence shell

High ionisation enthalpy

and more positive electron
gain enthalpy
 Reactivity of Noble Gas

The compounds of krypton are

fewer. Only the difluoride (KrF2)
has been studied in detail.

No true compounds of Ar, Ne or

He are yet known.
 Reactivity of Noble Gas

Neil Bartlett prepared a red compound

which is formulated as O2+PtF6─
He also prepared another red
coloured compound with Xe+PtF6─
He observed that,
by mixing PtF6 and xenon.

(I.E.1)
O2
≈ (I.E.1)
Xe
A number of xenon compounds,
mainly with most electronegative
elements like fluorine and oxygen,
have been synthesised.
1175 kJ/mol 1170 kJ/mol
Preparation of Xenon Fluoride Compound

Xenon forms three binary fluorides,

namely XeF2, XeF4, and XeF6, by
the direct reaction of elements
under appropriate experimental
conditions.

The products formed

depend
on the Xe/F2 ratio.
 Xe in excess

673 K, 1 bar
Xe (g) + F2 (g) XeF2 (s)

1:5 ratio

873 K, 7 bar
Xe (g) + 2F2 (g) XeF4 (s)

1:20 ratio

573 K, 60-70 bar

Xe (g) + 3F2 (g) XeF6 (s)
Properties of Xenon Fluoride Compound

XeF2, XeF4, and XeF6

Colourless crystalline solids

They are readily hydrolysed

even by traces of water

Powerful fluorinating agents

 Properties

Fluoride ion acceptors

to form cationic species

XeF4 + SbF5 [XeF3]+[SbF6]–

Xenon fluorides
react with

Fluoride ion donors

to form fluoroanions

XeF6 + MF M+[XeF7]–

(M = Na, K, Rb or Cs)
 Structure of Xenon-Fluoride Compounds

Compound Hybridisation Geometry Shape

Trigonal
XeF2 sp3d Linear
bipyramidal

Square
XeF4 sp3d2 Octahedral
planar

Pentagonal Distorted
XeF6 sp3d3
bipyramidal octahedron
 Preparation of Xenon Oxygen Compound

1. Hydrolysis of XeF4 and XeF6 gives XeO3.

4XeF4 + 12H2O 4Xe + 2XeO3 + 24HF + 3O2

XeF6 + 3H2O XeO3 + 6HF

2. Partial hydrolysis of XeF6 gives oxyfluorides, XeOF4, and

XeO2F2.

XeF6 + H2O XeOF4 + 2HF

XeF6 + 2H2O XeO2F2 + 4HF

Properties of Xenon Oxygen Compound

Physical Molecular
Compound
properties structure

Colourless,
XeO3 Pyramidal
explosive solid

Colourless, Square
XeOF4
volatile liquid pyramidal
 Uses of Noble gases

Helium is used in filling balloons and in gas

-cooled nuclear reactors.

Neon is used in fluorescent bulbs and

discharge tubes.

Argon is used in filling electric bulb and

in arc welding.