P-BLOCK ELEMENTS

Inert Pair Effect

The reluctance of the ns electrons to participate in bonding due

to increased nuclear charge is called Inert Pair Effect.

Due to inert pair effect the oxidation state decreases by two

units.

The tendency to show inert pair effect increases on moving

down the group.

For upper elements higher oxidation state is more stable and

for lower element lower oxidation state is more stable.
 13th Group Elements (Boron Family)
Abundance :
# B is a rare element and mainly occurs as Boric Acid(H3BO3),
Borax(Na2B4O7.10H2O) and Kernite (Na2B4O7.4H2O).
# Al is the most abundant metal and third most abundant
element in earth crust after Oxygen & Silicon.
Ionization energy :
B > Tl > Ga > Al > In
Physical Properties
# B is an extremely hard and black colored solid and has
unusually high melting point(2092oC) due to formation of a
strong lattice.
# Ga has very low melting point of 303 K (30oC) but has high
B.P.(2676K) which makes it useful for measuring high
temperature.
 Oxidation states :
The general O.S. of the group is +3 but due to inert pair
effect lower elements also show +1.
# Boron due to its small size and high value of IE1+IE2+IE3
does not form B3+ ion and forms only covalent compounds.
 Boron & It’s Compounds
BORON (B)
Isolation Of Boron
1. Reduction of B2O3 by Li,Na,K at high temperature
gives crystalline boron
B2O3 + 3Mg  2B + 3MgO
the reaction is strongly exothermic .
If other electropositive metals like MG is used than
amorphous Boron is obtained.

2. High purity Boron is obtained by the reduction of a

volatile Boron compound by H2 on tungstan filament
2BCl3 + 3H2  2B(s) + 6HCl(g) at 1270 K
99.99% pure
 Structure & Properties of Boron
1. Boron is an extremely hard black solid with high
m.p. (2092oC).
2. Boron exist in different allotropic forms having
B12 icosahedral units which contains
- 20 triangular faces
- 12 corners
- 5 boron atoms equidistant from one Boron
 Compounds Of Boron
Borax or Sodium tetraborate
(Na2B4O7.10H2O)
a.k.a Tincal Or Suhaga
Structure
Borax contains tetranuclear units of [B4O5(OH)4]2- & correctly
formulated as Na2 [B4O5(OH)4].8H2O
Borax dissolves in water to form an alkali solution
Na2B4O7 + 7H2O  2NaOH + 4H3BO3
Borax Bead Test
On heating Borax it first looses water molecules and
swells up . On further heating it turns into a
transparent liquid which solidifies into a glass like
bead known as borax bead.
Na2B4O7 .7H2O  Na2B4O7  2NaBO2 + B2O3
Borax glass Borax Bead
Transition metals form characteristic coloured
beads due to formation of respective borates
e.g. Co(BO3)2  Blue
 Boric Acid H3BO3)
Preparation
1. Hydrolysis Of Boron Compounds
Boric acid is the end product of the hydrolysis
of Boron compounds
BX3 + 3H2O  H3BO3 +3HX
BN + 3H2O  B(OH)3 + NH3

2. It can also be prepared by the acidic

hydrolysis of aq. Borax solution
Na2B4O7 + H2SO4 + H2O  Na2SO4 + H3BO3
(Conc.)
 Properties
1. It is a weak monobasic
acid and releases H+ from water
owing to its Lewis acid character.

2. It behaves as a strong
monoprotic acid in presence of
Cis- diols (Glycol) due to
chelation.
3. In solid state B(OH)3
units are H-bonded into 2-D
sheets with almost hexagonal
symmetry.
4. Heating of Boric Acid
H3BO3  HBO2  B2O3
100oC metaboric acid
 Boron Hydrides or Boranes
Binary compounds of Boron and
Hydrogen are called Boranes. They fall into
two series –
(i) Nido-boranes  BnHn+4
(ii) Arachno boranes  BnHn+6
DIBORANE(B2H6)
Preparation
1. By the reduction of BCl3 over Cu-Al
catalyst at 450oC
2BCl3 + 6H2  B2H6 +6HCl
 2.Laboratory Method – In laboratory it is
prepared by the reduction of etherate complex of
BF3 .
BF3.O(C2H5)2 + 3LiAlH4  B2H6 + 3Li[AlF4] + 4Et2O

3. Industrial Method
Reduction of BF3 with NaH
2BF3 + 6NaH  B2H6 + 6NaF
 Properties
1. It is a colourless gas , highly reactive gas
and catches fire spontaneously in air.
B2H6 + 3O2  B2O3 + 3H2O
2. Structure and Bonding
 Properties
3. Hydrolysis
B2H6 is instantly hydrolyzed by H2O forming
Boric acid .
B2H6 +3H2O  2B(OH)3 + 6H2
4. Reaction with Ammonia(NH3) *
B2H6 + 2NH3(low temp)  [BH2(NH3)2]+[BH4]-
excess or B2H6.2NH3
B2H6 + 2NH3(high temp)  (BN)x(Inorganic graphite)
excess
B2H6 + 2NH3(High temp)  B3N3H6 (Borazine)
1 : 2 Inorganic Benzene
# Borazine is a p donor(6 e donor) ligand and forms p
complexes with transition metal compounds.

# On heating with water it hydrolyses slowly to form NH3

and H3BO3.
B3N3H6 + 9H2O  2NH3 + 3H3BO3 + 3H2
# On heating at around 200oC it forms boron nitride
B3N3H6  3BN + 3H2
 Boron Halides
# Boron from trihalide (BX3) which are all lewis
acids .
Lewis Acid Chracter
BF3 < BCl3 < BBr3 < BI3
 Aluminium & Its Compounds
Interesting Fact
The name was derived from Alums which were used
medicinally as an astringent in ancient Greece &
Rome. The initial name proposed was ‘Aluminum’
which than further modified to “Aluminium”.

Aluminium is the most abundant Metal in earth

Crust(8.3% by weight).
 Chemical Properties OF Aluminium
Reacts with both acids and bases to liberate
hydrogen gas .

 Finely powdered Al explodes with O2 but normal

samples become passive due to formation of oxide
film.

Aluminium Hydride (AlH3)-

 Aluminium Trihalides
Aluminium forms AlX3 type halide which can all
act as lewis acids & except AlF3 all are electron
deficient.
AlF3 being ionic in nature is not e-deficient.
 Structure Of AlCl3
In Vapour Phase
At high temperatures it exist as a monomer .

At low temperature in vapour phase and liq. Is exist

as a dimer(C.N. = 4) .

In solid state it exist as a polymeric solid(C.N. = 6).

# Bromides and halides form dimeric units in solid.

Alums are double salts with general formula [M(H2O)6][Al(H2O)6](SO4)2
PRACTICE SESSION-1
Q.1 The decrease in stability of higher oxidation state in p–
block with increasing atomic number is due to :
(A) increase in bond energy as going down the group.
(B) the reluctance of s-sub shell electrons to participate in
the chemical bonding.
(C) both are correct.
(D) none is correct.
Ans – B

Q.2 B3+ ion cannot exist in aqueous solution because of its :

(A) strong reducing ability.

(B) strong oxidizing ability.
(C) small size and ionization energy
(D) large size and small charge.
Ans -C
Q.3 From the B2H6 all the following can be prepared except :
(A) H3BO3 (B) [BH2(NH3)2]+ [BH4]–
(C) B2(CH3)6 (D) NaBH4

Ans – C

Q.4 Boric acid is polymeric due to :

(A) its acidic nature
(B) the presence of hydrogen bonds
(C) its monobasic nature
(D) its geometry
Ans –B
Q.5 The decrease in stability of higher oxidation state in p–
block with increasing atomic number is due to :
(A) increase in bond energy as going down the group.
(B) the reluctance of s-sub shell electrons to participate in
the chemical bonding.
(C) both are correct.
(D) none is correct.
Ans – B

Q.6 Amorphous boron is obtained by :

(A) heating B2O3 with H2 .
(B) heating B2O3 with Na at high temperature.
(C) heating KBF4 with Na or K.
(D) heating BBr3 with H2 in presence of a catalyst.
Ans -B
Q.7 Crystalline boron in small amounts may be obtained by :
(A) reducing BCl3 with H2
(B) pyrolysis of BiI3
(C) thermal decomposition of diborane
(D) all of these
Ans – D

Q.8 When borax is dissolved in water :

(A) B(OH)3 is formed only
(B) [B(OH)4]– is formed only
(C) both B(OH)3 and [B(OH)4]– are formed
(D) [B3O3(OH)4]– is formed only
Ans -C
Q.9 The borax bead is chemically :
(A) B2O3 (B) Na2B4O7 (C) Na3BO3 (D*) B2O3 + NaBO2
Ans – D

Q.10 On the addition of mineral acid to an aqueous solution of

borax, the compound formed is:
(A) borodihydride (B) orthoboric acid
(C) metaboric acid (D) pyroboric acid

Q.11 An aqueous solution of borax is :

(A) neutral (B) amphoteric (C) basic (D) acidic

Q.12 The product obtained in the reaction of diborane with

excess of ammonia at low temperature is :
(A) B2H6. NH3 (B) B2H6. 2NH3 (C) (BN)x(D) Borazine
Q.13 Diborane reacts with water to form :
(A) HBO2 (B) H3BO3 (C) H3BO3 + H2 (D) H2
Ans – C

Q.14 Aluminium is more reactive than iron. But aluminium is

less easily corroded than iron because:
(A) aluminium is a noble metal
(B) oxygen forms a protective oxide layer on aluminium
surface
(C) iron unergoes reaction easily with water
(D) iron forms both mono and divalent ions
Ans –C
Q.15 Aluminium does not react with:
(A) NaOH (B) conc. HCl (C) N2 (D) conc. HNO3

Q.16 On passing CO2 into aqueous solution containing Al3+ :

(A) Al2(CO3)3 is formed
(B) Al(OH)3 is precipitated
(C) Al2O3 is formed
(D) collodial Al(OH)3 is formed
Ans – B

Q.17 Alum is found to contain hydrated monovalent cation

[M(H2O)6]+ , trivalent cation [M¢(H2O)6]3+ and SO42– in the
ratio of :

(A) 1 : 1 : 1 (B) 1 : 2 : 3 (C) 1 : 3 : 2 (D) 1 : 1 : 2

Q.18 Aqueous solution of potash alum is:
(A) alkaline (B) acidic (C) neutral (D) soapy

Q.19 Which mixed sulphate is not an alum:

(A) K2SO4.Al2(SO4)3.24H2O (B) K2SO4.Cr2(SO4)3.24H2O
(C) Na2SO4.Fe2(SO4)3.24H2O (D) CuSO4.Al2(SO4)3.24H2O
Ans – D

Q.20 Borax is used as a buffer since :

(A) its aqueous solution contains equal amount of weak
acid and its salt
(B) it is easily available
(C) its aqueous solution contains equal amount of strong
acid and its salt
(D) statement that borax is a buffer, is wrong
Ans - A
Q.21 Select the incorrect statement about the boron.
(A) Pure form of the elements are obtained by the reduction of
BCl3 with zinc at 900ºC.
(B) Crystalline boron is attacked only by hot concentrated
oxidising agents.
(C) Amorphous boron and ammonia at white heat gives
(BN)x, a slippery white solid with a layer structure resembling
that of graphite.
(D) Boron does form B3+ cation easily.
Ans – D
Q.22 Which of the following statement is correct for diborane ?
(A) Small amines like NH3, CH3NH2 give unsymmetrical cleavage
of diborane.
(B) Large amines such as (CH3)3N and pyridine gives symmetrical
cleavage of diborane.
(C) Small as well as large amines both gives symmetrical
cleavage of diborane.
(D) (A) and (B) both
 14th Group Elements (Carbon Family)
C Si Ge Sn Pb

2nd most abundant element

# C has the highest m.p. in the group
# I.E. decreases down the group but Pb has slightly greater
I.E. than Pb due to lanthanide contraction.
 Chemical Properties
1. Oxidation States
# Common oxidation states +4 and +2 (Due to inert pair effect).

# C4+ ions does not exist in aq. Solution due to high value of
( IE1 + IE2 +IE3 + IE4 ) and due to high polarising power of C4+ ion
it can easily polarise the anion and thus the compounds are
predominantly covalent .
 2. Reactivity Towards Oxygen
# All members of the group form monoxides(MO) and
dioxides(MO2) type.
# SiO only exist at high temperature where it is assumed to be
formed by the reduction of SiO2 with Si.
# Oxides in higher oxidation states are acidic CO2,SiO2 and GeO2
whereas oxides of Sn& Pb are amphoteric.
# CO is neutral and GeO is acidic.
 3. Reactivity Towards water
# C,Si & Ge are not affected by water.
# On passing steam over red hot coke gives water gas
C(s) + H2O(g)  CO(g) +H2(g)

# Same reaction is shown by Si & Ge

Si(s) + 2H2O(g)  SiO2(g) + 2H2(g)
Sn(s) + 2H2O(g)  SnO2(g) + 2H2(g)

# Pb is unaffected by water but in water containing dissolved air

it is appreciably soluble forming lead hydroxide , this
phenomenon is called pulmbosolvency.
2Pb + 2H2O + O2  2Pb(OH)2
 Allotropes Of Carbon
# C atoms have tendency to link with other C atoms through
covalent bonds to form chains and rings , this property is called
catenation.
# The tendency to show catenation decreases on moving down
the group.
C >>Si > Ge ~Sn
# Due to property of C to show catenation and tendency to form
pp-pp multiple bond Carbon shows allotropy.
 Crystalline Allotropes
1. Diamond
# It has crystalline lattice.
# It has an FCC lattice in which C atoms forms form FCC lattice
and C atoms occupy alternate tetrahedral voids.(Zinc blende
type structure)
 2. Graphite
# Graphite is composed of 2-D sheets of hexagonal rings
formed by c atoms.

# In graphite 3 valence electrons of each carbon atom are

involved forming s bonds (using sp2 hybridised orbitals) and the
fourth electron forms p bond.
# The p electrons are delocalised over the entire sheet.
# The hexagonal layers are held through weak Vander Waal
forces and can slide over each other and hence Graphite act as
dry lubricant.
Graphite is thermodynamically more stable than diamond at
room temperature.

# Due to mobile electrons graphite conducts electricity along the

layer it donot consuct across the layer.
# Diamond is a better conductor of Heat than Graphite. In fact
diamond has the highest thermal conductivity of any substance
known.
 3. Fullerene
# Fullerenes are made by the heating of graphite in an electric arc
in the presence of inert gases such as helium or argon, When
electric spark is generated a soot is produced which contains
mainly C60 with smaller quantity of C70 and traces of fullerenes
consisting of even number of carbon atoms up to 350 or above.
# Fullerenes are the only pure form of Carbon
# The C60 molecule has a shape like soccer ball and is called
Buckminster fullerene or bucky balls.

# It contains 20 hexagonal rings and 12 pentagonal rings.

# A hexagonal ring can fuse with both pentagonal and hexagonal

rings but a pentagonal ring can only fuse with hexagonal rings.

# All C atoms are sp2 hybridized in Fullerene.

# The remaining electron on each carbon is delocalized in

molecular orbitals giving aromatic character to the molecule.
 Amorphous Allotropes
1. Coke & Charcoal
Obtained by heating Coal or wood at high temperature in
absence of air .
2. Carbon black or Lampblack(SOOT)
Made by the incomplete combustion of liquid hydrocarbons in
limited supply of air. Carbon black is used in tyres, paints & inks
as pigment.
 Compounds Of Carbon
Carbon Monoxide(CO)
# It is a colourless odourless neutral poisonous gas formed by
incomplete combustion of carbon.
# In laboratory it is prepared by dehydration of Formic acid with
conc. H2SO4.
HCOOH  CO + H2O
# CO burns with a blue flame.
# CO is toxic because it forms a complex with haemoglobin in
the blood which is more stable than the complex formed by
oxygen. This prevents the haemoglobin in the red blood
corpuscles from carrying oxygen causing oxygen deficiency
leading to unconsciousness and death.
# Some important industrial fuels
Water gas – equimolar mixture of CO & H2
Producer Gas – CO + N2
Coal Gas – CO + H2+ CH4 + CO2
# Water gas is prepared by passing steam over red hot coke.
C + H2O  CO + H2
Water gas is particularly a good fuel due to its high calorific
value as both Co and H2 burn to evolve heat.

# Producer gas ia made by passing air over red hot coke

C + O2+ N2  CO2 + N2  2CO + N2

# CO is a good reducing agent and can reduce many metal
oxides to the metal.
Fe2O3 + 3CO  3Fe + 3CO2
# Due to presence of an electron pair it act as a ligand and form
complexes with transition metals like Fe(CO)5, Cr(CO)6 etc.
# CO readily combines with Cl2 to form phosgene
CO + Cl2  COCl2
Phosgene is a poisonous gas and was used in world war I.
 Carbon Dioxide(CO2)
# It is a colourless odourless gas .
# Formed during fermentation of glucose by yeast
C6H12O6  2C2H5OH + 2CO2
# The main use of CO2 is as a refrigerant.Solid CO2 is known as
Dry Ice or Cardice and is used to freeze meat, frozen ice and in
laboratory as coolant.
# It is used for the production of urea
CO2 + 2NH3  NH2CONH2 + H2O
# On passing through lime water or Baryta water the solution
turns milky and the milkiness disappears on passing CO2 in
excess.
Ca(OH)2 + CO2  CaCO3 + H2O  Ca(HCO3)2

# CO2 is an acidic gas and forms H2CO3 on dissolving in water,

which is a weak diprotic acid.
# Carbonic acid has never been isolated but it gives two types of
salts carbonates and Bicarbonates.
 Carbon Suboxide(C3O2)
# It is a foul smelling gas .
# it is prepared by the deyhdration of malonic acid with P4O10 .
 Carbides
# Compounds of carbon with a less electronegative element are
called carbides, these are of three types –
1. Ionic/Salt Like Carbides
2. Covalent carbides
3. Interstitial Carbides
 1. Ionic / Salt like Carbides
These carbides are classified depending on the products
obtained on hydrolysis –
(i) Methanides (C4-)
These carbides on hydrolysis produces methane .
e.g. Be2C, Al4C3
 (ii). Acetylides(C22-)
These carbides on hydrolysis produces Acetylene .
e.g. CaC2

CaC2 is an important chemical intermediate and is used on

industrial scale to produce calcium Cynamide.
CaC2 + N2  CaCN2 or Ca(NCN) + C
Nitrolim

Calcium Cynamide actually contains NCN2- ion .

# Calcium cynamide on further heating with C produces calcium
Cynaide
CaCN2 + C  Ca(CN)2
 (iii). Allylides(C34-)
These carbides on hydrolysis produces Propyne .
e.g. Mg2C3
 2. Covalent Carbides
SiC and B4C are the most important .
# Both SiC and B4C are hard infusible and inert and are used as
an abrasive and shield for radiation.
# B4C is also used in break linings of cars and bulletproof
clothings.
 3. Interstitial Carbides
Due to small size of C atoms , c atoms occupy the interstitial
sites in the lattice of metal and these carbides are called
interstitial carbides.

# Thee carbides are mainly formed by transition metals and

some og the lanthanides and actinides.
For e.g. Cr4C3 ,Fe3C(Cementite) TaC,WC etc.

# These carbides are refdractory in nature Ii.e. Have high

melting point)
 Silicon & Its Compounds
# Si is the most abundant element in earth’s crust after Oxygen.
# Silicon has two allotropic forms –
1. Amorphous Silicon is obtained by heating SiO2 with Mg
SiO2 + 2Mg  Si + 2MgO
2. Crystalline Silicon is obtained by the reduction of SiO2 with C
SiO2 + C  Si + CO2
3. High purity Si is obtained by reduction of SiCl4 with Mg
SiCl4 + 2Mg  Si + 2MgCl2

Amorphous Si when heated fuses & recrystallises to form crystalline Silicon .

 Oxides Of Silicon
Two types of oxides of Silicon are formed –
(i) SiO (ii) SiO2
# SiO is assumed to be formed at high temperature by the reduction of SiO2 with Si
SiO2 + Si  2SiO
# SiO2 is called as Silica and is mainly found as sand and quartz.
# SiO2 is an acidic oxide and does not react with acids but reacts with HF to form
SiF4 which hydrolyses to form Silicic Acid
SiO2 + 4HF  SiF4 + H2O  Si(OH)4

Etching of glass- 6HF + SiO2  H2SiF6 + 2H2O

# SiO2 being acidic dissolves slowly in aq. NaOH and more rapidly in fused alkali or
carbonates forming silicates.
SiO2 + 2NaOH  Na2SiO3 + H2O
# Quartz is an important piezo-electric material for the crystals in Gramophone
pickups, lighters and for making Oscillators for radios and computers.

# Kieselguhr is another form of SiO2 used in filtration plants.

Silicates - Binary compounds of silicon with oxygen are called silicates but they
contain other metals also in their structures.

# Silicates mainly contains SiO44- tetrahedral units.

# SiO44– tetrahedral units may exist as discrete units or may polymerize into larger
units by sharing corners.

# Silicates are classified as :

1. Orthosilicates( Neso-Silicates) - These contain discrete [SiO4]4–

2. Pyrosilicates( Soro-Silicates) – two tetrahedral units are joined by sharing one O

at one corner.
3. Cyclic silicates – Two oxygen atoms are shared per unit
4. Chain silicates – Two oxygen atoms are shared per unit
1. Simple chain Silicates(Pyroxene) – Two O atoms shared per tetrahedral

2. Double Chain Silicates (Amphiboles)

5. Sheet silicates(Phyllo-silicates) –

O– O–

O– O–
O O
O O O O
O O
O– O– O–

O O O

O– O– O–
O O O O O O
O– O––

O– O–
6. 3-D Silicates –
 Silicones
Silicones are synthetic organosilicon compounds having repeated R2SiO units held by
Si – O – Si linkages. These compounds have the general formula (R2SiO)n
where R = alkyl or aryl group.
The silicones are formed by the hydrolysis of alkyl or aryl substituted chlorosilanes and
their subsequent polymerisation.

The starting material for silicones are alkyl or aryl substituted chlorosilanes .
Q.1 A colourless gas which burns with blue flame and
reduces CuO to Cu is :
(A) N2 (B) CO
(C) CO2 (D) NO2
Q.2 Producer gas is the mixture of :
(A) CO and N2 (B) CO and H2
(C) N2 and NH3 (D) CO, H2 and N2
Q.3 If CO2 is passed in excess into lime water, the
milkiness first formed disappears due to
(A) reversal of the original reaction
(B) formation of volatile calcium derivative
(C) formation of water soluble calcium bicarbonate
(D) the solution getting heated by exothermic reaction
Q.4 When steam is passed through red hot coke :
(A) CO2 and H2 are obtained (B) CO and N2 are formed
(C) CO and H2 are obtained (D) petrol gas is obtained

Q.5 Glass is soluble in

(A) HF (B) H2SO4 (C) HClO4 (D) aqua-regia

Q.6 Coal gas is a mixture of

(A) CO and H2
(B) H2, saturated and unsaturated hydrocarbons, CO, CO2, N2 and O2
(C) Saturated and unsaturated hydrocabons
(D) CO, CO2 and CH4
Q.7 Which of the following is not hydrolysed ?
(A) CCl4 (B) SiCl4 (C) SnCl4 (D) PbCl4
Q.8 When a mixture of carbon monoxide and chlorine is exposed to sunlight the
product formed is :
(A) thionyl chloride (B) phosgene (C) phosphine (D) carbon tetrachloride
Q.9 The carbide which give propyne on hydrolysis is/are :
(A) Al4C3 (B) CaC2 (C) Fe3C (D) Mg2C3

• Q.10 Allylides are ionic carbides. They contains :

• (A) C4– ions (B) C22– ions (C) C33– ions (D) C34– ions
Q.11 A bottle of fire extinguishers contain H2SO4 and :
(A) CaCO3 (B) MgCO3 (C) NaHCO3 (D) any carbonate
Q.12 Silicon reacts with hot solution of NaOH forming :
(A) Si(OH)4 (B) Si(OH)2 (C) SiO2 (D) Na4SiO4
Q.13 The ions present in Al4C3, CaC2 and Mg2C3 are respectively :
(A) C4–, C22–, C34– (B) C22–, C4–, C34– (C) C34–, C32–, C4– (D) C34–, C4–, C22–
Q.14 The silicate anion in the mineral kinoite is a chain of three SiO4 tetrahedral,
that share corners with adjacent tetrahedral. The charge of the silicate anion is
(A) –4 (B) –8 (C) –6 (D) –2
• Q.15 H2C2O4 gas (A) + gas(B) + liquid (C). Gas (A) burns with a blue flame
and is oxidised to gas (B).
Gas (A) + Cl2  D + NH3 E
A, B, C and E are
(A) CO2, CO, H2O, HCONH2 (B) CO, CO2, COCl2, HCONH2
(C) CO, CO2, H2O, NH2CONH2 (D) CO, CO2, H2O, COCl2
Q.16 In which of the following silicates, only two corners per tetrahedron are shared :
(i) Pyrosilicate (ii) Cyclic silicate
(iii) Double chain silicate (iv) Single chain silicate
(v) 3 D silicate (vi) Sheet silicate

(A) (i), (ii) and (v) (B) (iv) and (vi) only
(C) (i) and (vi) only (D) (ii) and (iv) only

Q.17 CCl4 is inert towards hydrolysis but SiCl4 is readily hydrolysed because
(A) carbon cannot expand its octet but silicon can expand its octet
(B) ionisation potential of carbon is higher than silicon
(C) carbon forms double and triple bonds
(D) electronegativity of carbon is higher than that of silicon
Q.18 The structural unit pesent in pyro sillicates is
(A) Si3O96– (B) SiO44– (C) Si2O76– (D) (Si2O52–)n

Q.19 Which one of the following anions is present in the chain structure of
silicates :
(1) SiO44– (2) Si2O76– (3) (Si2O52–)n (4) (SiO32–)n
Q.20 The straight chain polymer is formed by :-
(1) Hydrolysis of (CH3)2SiCl2 followed by condensation polymerisation
(2) Hydrolysis of (CH3)3SiCl followed by condensation polymerisation
(3) Hydrolysis of CH3SiCl3 followed by condensation polymerisation
(4) Hydrolysis of (CH3)4 Si by addition polymerisation
 15th Group Nitrogen Family (Pnicogens)

Nitrogen and phosphorus are non-metal, arsenic and antimony metalloid and
bismuth is a typical metal.
Oxidation States
# The common oxidation states of these elements are –3, +3 and +5. The
tendency to exhibit –3 oxidation state decreases down the group , bismuth
hardly forms any compound in –3 oxidation state.
# The stability of +5 oxidation state decreases down the group.
# Nitrogen exhibits +1, +2, +4 oxidation states also when it reacts with oxygen.
Phosphorus also shows +1 and +4 oxidation states in some oxoacids.
# In the case of nitrogen, all oxidation states from +1 to +4 tend to
disproportionate in acid solution.
For example, 3 HNO2  HNO3 + H2O + 2 NO
# Similarly, in case of phosphorus nearly all intermediate oxidation states
disproportionate into +5 and –3 both in alkali and acid.
# Nitrogen forms diatomic molecule due to its tendency to form effective pp-pp
bond, on moving down the group the strength of pis bond decreases due to
increase in size.
# Phosphorous exist as tetratomic molecules .
# The Single P-P bond is more stronger than single N-N bond.
 CHEMICAL PROPERTIES

1. Reaction with Hydrogen

# All the elements form Hydrides of type MH3.
# Thermal stability decreases on moving down the group due to increase in size and
consequently the reducing character of Hydrides increases.
# M.P. Order - NH3 > BiH3 > SbH3 >AsH3 > PH3
# B.P. Order – BiH3 > SbH3 > NH > AsH3 >PH3

# Basicity of these hydrides decreases down the group.

 2. Reactivity towards Oxygen
# All these elements form two types of oxides E2O3 & E2O5.
# Acidic nature increases with increase in oxidation state .
# The E2O3 oxides of N & P are acidic, that of As & Sb amphoteric and of Bi are
predominantly basic.

3. Reactivity towards Metals

# All these elements react with metals to form their binary compounds in -3
oxidation states.
Ca3N2 – Calcium Nitride , Ca3P2 – Calcium Phosphide
Na3As – Sodium Arsenide, Zn3Sb2 – Zinc antimonide
Mg3Bi2 -
 Oxy-acids of nitrogen
Nitrous Acid (HNO2)
By acidifying an aqueous solution of a nitrite
Ba(NO2)2 + H2SO4  2HNO2 + BaSO4
It is an unstable, weak acid which is known only in aqueous solution.

(ii) On trying to concentrate, the acid decomposes as given below.

3HNO2  HNO3 + 2NO + H2O
(iii) Nitrous acid and nitrites are good oxidizing agents and convert iodides to
iodine, ferrous salts to ferric, stannous to stannic and sulphites to sulphates eg.
2KI + 2HNO2 + 2HCl  2H2O + 2NO + 2KCl + I2
(iv) With strong oxidizing agents like KMnO4 nitrous acid and nitrites function as
reducing agents and get oxidized to NO3– ions :
2KMnO4 + 5KNO2 + 6HCl  2MnCl2 + 5KNO3 + 3H2O + 2KCl
 Nitric Acid (HNO3)
Preparation
(i) Ostwald’s process-
This method is based upon catalytic oxidation of NH3 by atmospheric oxygen.
4 NH3 (g) + 5 O2 (g) (from air)  4 NO (g) + 6 H2O (g)

Nitric oxide thus formed combines with oxygen giving NO2.

2 NO (g) + O2 (g)  2 NO2 (g)
Nitrogen dioxide so formed, dissolves in water to give HNO3.
3 NO2 (g) + H2O (l)  2 HNO3 (aq) + NO (g)
NO thus formed is recycled and the aqueous HNO3 can be concentrated by
distillation upto ~ 68% by mass. Further concentration to 98% can be achieved by
dehydration with concentrated H2SO4.
(ii) Birkeland Eyed’s process-
In this process N2 and O2 are sparked in an electric arc furnace and passing the
gas in water to form HNO3 . This method is now obsolete due to high cost of
electricity.

(iii) In the laboratory :

Nitric acid is prepared by heating KNO3 or NaNO3 and concentrated H2SO4 in a
glass retort.
NaNO3 + H2SO4  NaHSO4 + HNO3
Concentrated nitric acid is a strong oxidising agent and attacks most metals
except noble metals such as gold and platinum. The products of oxidation
depend upon the concentration of the acid , temperature and the nature of the
material undergoing oxidation.

(A) Metals placed above H in electrochemical series (ECS)

1. Mg, Mn cold and dilute M(NO3)2 M + 2HNO3  M(NO3)2 + H2

2. Zn, F
(a) very dilute NH4NO3 4Zn+10HNO3  4Zn(NO3)2 + NH4NO3 + 3H2O
(b) dilute N2O 4Zn + 10HNO3  4Zn(NO3)2 + N2O + 5H2O
(c) concentrated NO2 Zn + 4HNO3  Zn(NO3)2 + 2NO2 + 2H2O

Note – Sn forms NH4NO3 with dil HNO3 and Stannic acid with conc. HNO3.
(B) Metals placed below H in electrochemical series (ECS)- Cu,Ag,Hg ,Pb[Not below]

(i) dilute NO 3Pb + 8HNO3  3Pb(NO3)2 + 2NO + 4H2O.

Hg forms Hg2(NO3)2

(ii) concentrated NO2 Pb + 4HNO3  Pb(NO3)2 + 2NO2 + 2H2O

(C)Metals like Cr , Al are rendered passive due to formation of oxide film.

(D) Noble metals like Au,Pt don not react with HNO3 but dissolve in aqua regia
(3 :1 mixture of HCl & HNO3)
Au + 4H+ + NO3- +4Cl-  AuCl4- + NO + 2H2O
Pt + 16H+ + 4NO3- +18Cl-  3PtCl62- + 4NO + 8H2O
# Concentrated nitric acid is also oxidizes non-metals to their corresponding
“-ic’ Acid .
I2 + 10 HNO3  2 HIO3 + 10 NO2 + 4 H2O
C + 4 HNO3 CO2 + 2 H2O + 4 NO2
S8 + 48 HNO3 (concentrated)  8 H2SO4 + 48 NO2 + 16 H2O
P4 + 20 HNO3 (concentrated)  4 H3PO4 + 20 NO2 + 4 H2O

# Brown Ring Test : This test is carried out to detect the presence of NO3- ion.
The test is usually carried out by adding dilute ferrous sulphate solution to an
aqueous solution containing nitrate ion , and then carefully adding concentrated
sulphuric acid along the sides of the test tube. A brown ring at the interface between
the solution and sulphuric acid layers indicate the presence of nitrate ion in solution.
NO3– + 3 Fe2+ + 4H+  NO + 3Fe3+ + 2 H2O
[Fe (H2O)6]2+ + NO  [Fe (H2O)5 (NO)]2+ + H2O
Oxides Of Nitrogen
 White Phosphorous Red Phosphorous Black Phosphorous

It is a white translucent Obtained by heating a-Black P Obtained by

Solid , poisonous, white P at 573 K in an heating Red P at 803 K in
insoluble in water but inert atmosphere.it is a sealed tube.
soluble in CS2 non-poisonous, and b-Black P Obtained by
insoluble in both water & heating White P at 473 K
CS2. at high pressure.

Stability Order
Black > Red > White
 Phosphine (PH3)
Preparation :
(i) Phosphine is prepared by the reaction of calcium phosphide with water.
Ca3P2 + 6 H2O  3 Ca(OH)2 + 2 PH3
(ii) In the laboratory, it is prepared by heating white phosphorus with concentrated
NaOH solution in an inert atmosphere of CO2.
P4 + 3 NaOH + 3 H2O  PH3 + 3 NaH2PO2
When pure, it is non inflammable but
becomes inflammable owing to the presence of P2H4 or P4 vapors. To purify it from the
impurities , it is absorbed in HI to form phosphonium iodide (PH4I) which on treating
with KOH gives off phosphine.
PH4I + KOH  KI + H2O + PH3
# It is a colorless gas with a slightly garlic or rotten fish smell and is highly poisonous.
# PH3 catches fire with O2 when heated at 150oC
PH3 + 2O2  H3PO4
# It is slightly soluble in water but soluble in CS2 and other organic solvents. The
solution of PH3 in water decomposes in presence of light giving red phosphorus and H2.

# Test For PH3 When absorbed in copper sulphate or mercuric chloride, the
corresponding phosphides are obtained.
3CuSO4 + 2PH3 Cu3P2 + 3H2SO4
3HgCl2 + 2 PH3 Hg3P2 ¯ (brownish black) + 6 HCl

Holme’s Signal - Containers containing calcium carbide and calcium phosphide are
pierced and thrown in the sea when the gases evolved burn and serve as a signal.
Ca3P2 + H2O 3Ca(OH)2 + 2PH3
CaC2 + 2H2O  Ca(OH)2 + C2H2
Smoke Screen – Shells containing calcium phosphide are exploded where phosphine
burns to give clouds of P4O10.
Phosphorous Halides
Oxyacids of Phosphorous
PRACTICE SESSION-3
Q.1 The thermal stability of the hydrides of group 15 follows the order :
(A) NH3 < PH3 < AsH3 < SbH3 < BiH3 (B) NH3 > PH3 > AsH3 > SbH3 > BiH3
(C) PH3 > NH3 > AsH3 > SbH3 < BiH3 (D) AsH3 < PH3 > SbH3 > BiH3 > NH3

Q.2 .... is obtained when ammonium dichromate is heated.

(A) nitrogen (B) oxygen (C) ammonia (D) none

Q.3 In the ostwald’s process, nitric acid is prepared by the catalytic oxidation of :
(A) N2 (B) NH3 (C) N2O5 (D) NO2
Q.1 The thermal stability of the hydrides of group 15 follows the order :
(A) NH3 < PH3 < AsH3 < SbH3 < BiH3 (B) NH3 > PH3 > AsH3 > SbH3 > BiH3
(C) PH3 > NH3 > AsH3 > SbH3 < BiH3 (D) AsH3 < PH3 > SbH3 > BiH3 > NH3

Q.2 .... is obtained when ammonium dichromate is heated.

(A) nitrogen (B) oxygen (C) ammonia (D) none

Q.3 In the ostwald’s process, nitric acid is prepared by the catalytic oxidation of :
(A) N2 (B) NH3 (C) N2O5 (D) NO2
Q.4 Which of the following will combine with Fe(II) ion to form a brown complex compound ?
(A) N2O (B) NO (C) N2O3 (D) NO2
Q.5 NO2 can be prepared by heating :
(A) NH4NO3 (B) NaNO3 (C) Pb(NO3)2 (D) KNO3

Q.6 Cold solution of barium nitrite on mixing with sulphuric acid produces :
(A) BaSO4 + HNO2 (B) BaSO4 + HNO3 (C) BaSO4 + NO2 (D) BaSO4 + N2 + O2
Q.7 HNO3 + P4O10  HPO3 + X
in the above reaction the product X is :
(A) NO2 (B) N2O3 (C) N2O4 (D) N2O5

Q.8 Nitric acid usually turns yellow on standing. This is due to :

(A) absorption of yellow wavelength
(B) slow decomposition of HNO3 into NO2
(C) its oxidation by atmospheric air
(D) absorption of moisture by it
Q.9 Metaphosphoric acid exists in polymeric form and may have :
(A) a linear structure (B) a cyclic structure
(C) both linear as well as cyclic structures (D) none
Q.10 Nitrogen is obtained by the thermal decomposition of :
(A) NH4Cl (B) NH4NO3 (C) AgNO3 (D) none of these

Q.11 Which of the following compounds does give N2 on heating?

(A) NH4NO2 (B) NH4NO3 (C) NaN3 (D) Both (A) and (C)

Q.12 A mixture of alumina and coke is heated in a current of nitrogen to about

1800oC and the product obtained is treated with water. A gas is evolved.
The gas is :
(A) N2 (B) N2O (C) NH3 (D) NO
Q.13 Nitrolim is obtained by passing nitrogen over :
(A) heated mixture of Al2O3 and carbon (B) carborundum
(C) calcium carbide (D) heated aluminium
Q.14 NH3 can't be obtained by :
(A) heating of NH4NO3 or NH4NO2 (B) heating of NH4Cl or (NH4)2 CO3
(C) heating of NH4NO3 with NaOH (D) reaction of AIN or Mg3N2 or CaCN2 with H2O
Q.15 Which of the following is a mixed acid anhydride ?
(A) NO (B) NO2 (C) N2O5 (D) N2O
Q.16 Select the correct statement.
(A) Ostwald's method of preparation of HNO3 is based upon catalytic oxidation of
NH3 by atmospheric oxygen.
(B) HNO2 acts as both oxidising and reducing agents.
(C) NO2 reacts with O3 to form N2O5.
(D) All of these.
• Q.17 Red phosphorus can be prepared from white phosphorus by :
(A) adding red colour to white phosphorus
(B) heating white phosphorus to red heat
(C) heating white phosphorus at 250ºC or at low temperature in the presence of
sun light.
(D) dissolving white phosphorus in NaOH
Q.18 Holme's signals can be given by using :
(A) CaC2 + CaCN2 (B) CaC2 + Ca3P2
(C) CaC2 + CaCO3 (D) Ca3P2 + CaCN2
Q.19 Ortho phosphoric acid on heating above 300ºC gives :
(A) hypophosphorus acid (B) hypophosphoric acid
(C) metaphosphoric acid (D) phosphorous acid
Q.20 The number of P—O—P bonds in cyclic trimetaphosphoric acid is :[JEE 2000]
(A) zero (B) two (C) three (D) four
Q.21 Ammonia can be dried by : [JEE 2000]
(A) conc. H2SO4 (B) P4O10 (C) CaO (D) anhydrous CaCl2
Q.22 A pale blue liquid is obtained by equimolar mixture of two gases at –30oC.
[JEE 2005 ]
(A) N2O (B) N2O3 (C) N2O4 (D) N2O5

Q.23. Thermodynamically most stable allotrope of phosphorus is : [JEE 2005]

(A) Red (B) White (C) Black (D) Yellow
 16th Group -Oxygen Family Chalcogens)

Oxygen is the most abundant of all the elements on the earth. Oxygen forms about
46.6% by mass of earth’s crust . Dry air contains 20.946% oxygen by volume.

# O & S are non metal , Se and Te are metalloids , Po is a radioactive metal (half life
13.8 days).
Hydrides
# These elements form Hydrides of type H2E .

# Acidic character increases and thermal stability decreases down the group due to
increase in E-H bond length.

# All Hydrides except water posses reducing property and reducing character
increases down the group.
 Halides
# 16th group elements form a large number of halides.
# Stability of Halides Fluorides > Chlorides > Bromides > Iodides .
HEXAHALIDES
# Amongst hexahalides, hexafluorides are the only stable halides., due to steric
reasons.
# All hexafluorides are gaseous in nature and have octahedral structure.
TETRAHALIDES
# Amongst tetrafluorides, SF4 is a gas , SeF4 liquid and TeF4 a solid .

DIHALIDES
# All elements except selenium form dichlorides and dibromides. The well
known monohalides are dimeric in nature, Examples are S2F2, S2Cl2, S2Br2,
Se2Cl2 and Se2Br2.
# These dimeric halides undergo disproportionation as given below :
2Se2Cl2  SeCl4 + 3Se.
Dioxygen (O2)
Preparation :
(i) Laboratory method :
2 KClO3  2 KCl + 3O2
(ii) By thermal decomposition of oxides of metals.
2 HgO  2 Hg + O2 ; 2 Ag2O  4 Ag + O2
3 MnO2  Mn3O4 + O2 ; 2 Pb3O4  6 PbO + O2
2 PbO2  2 PbO + O2
(iii) Thermal decomposion of K2Cr2O7 and KMnO4
4 K2Cr2O7  4 K2CrO4 + 2 Cr2O3 + 3O2
2 KMnO4  K2MnO4 + MnO2 + O2
(iv) Decomposion of H2O2
2H2O2 (aq.)  2H2O (l) +O2
Industrially it is prepared by liquification of air and than fractional distillation.
Properties
(i) Colourless , odourless and tasteless gas. It is paramagnetic and exhibits allotropy.
Three isotopes of oxygen are , and . Oxygen does not burn but is a strong supporter
of combustion.
Ozone (O3) –
# Ozone is an allotropic form of Oxygen and is too reactive to remain for long
in the atmosphere at sea level.
# At a height of about 20 Km it is formed from atmospheric oxygen in presence
of sunlight.
Preparation :
(i) It is prepared by passing silent electric discharge through pure and dry oxygen.
O2  O + O
O2 + O  O3 ; DH = 2845 kJ mol-1
–––––––––––––––––––––––––––––––––
3O2  2O3
Since the conversion is endothermic the electric discharge should be silent to
prevent the decomposition of O3.
Properties
(i) Dark blue Diamagnetic gas which forms a blue liquid on cooling and on
solidification forms violet black crystals. The colour is due to intense absorption
of red light.
(ii) Ozone is thermodynamically unstable with respect to oxygen.

(iii) On decomposition it produces nascent oxygen and therefore is a powerful

oxidizing agent. It oxidises –
(a) PbS to PbSO4 - PbS(s) + 4O3(g) PbSO4(s) + 4O2(g)
(b) Neutral KI solution to I2
(c) Alkaline KI solution to KIO3 and KIO4
(d) H2S to S
Depletion of Ozone Layer : Nitric oxide emitted from the exhaust of Supersonic jets
combine with O3 and is slowly depleting the ozone layer.
NO(g) + O3(g)  NO2(g) + O2 (g)
 Sulphur
# Sulphur forms numerous allotropes of which the yellow rhombic (a - sulphur)
and monoclinic (b - sulphur) forms are the most important. The stable forms
at room temperature is rhombic sulphur, which transforms to monoclinic
sulphur when heated above 369 K(Transition Temperature).

Rhombic Sulphur (a - sulphur)

(i) This allotrope is yellow in colour, melting point 385.8 K and specific gravity 2.06.

(ii) Rhombic sulphur crystals are formed on evaporating the solution of roll sulphur in
CS2.
(iii) It is insoluble in water but dissolved to some extent in benzene, alcohol and
ether. It is readily soluble in CS2 .
Monoclinic Sulphur (b - sulphur)

(i) Its melting point is 393 K and specific gravity 1.98. It is soluble in CS2.

(ii) This form of sulphur is prepared by melting rhombic sulphur in a dish and cooling
till crust is formed.

(iii) Two holes are made in the crust and the remaining liquid poured out. On
removing the crust, colourless needle shaped crystals of b - sulphur are formed.

(iv) It is stable above 369 K and transforms into a - sulphur below it . Conversely, a -
sulphur is stable below 369 K and transforms into b - sulphur above this. At 369 K
both the forms are stable. This temperature is called transition temperature.

(v) Both rhombic and monoclinic sulphur have S8 molecules these S8 molecules are
packed to give different crystal structures. The S8 ring in both the forms is puckered
and has a crown shape.
 20 S
S
4 pm S
107o
S S
S
S S
(a)
The Cyclo S6 form consist of chair form. S
205.7 pm
S S
o
102.2
At 1000 K S2 is the dominant form and is S S
Paramagnetic like O2.
(b)
S
 Compounds Of Sulphur
Sulphur Dioxide(SO2)
Preparation :
S + O2  SO2
Industrially it is obtained as by product of the roasting of sulphide ores.
4FeS2 + 11O2 (g)  2Fe2O3 (s) + 8SO2(g)
Preparation
(i) Colourless gas with burning sulphur smell.

(ii) It is heavier than air and is highly soluble in water. SO2 in solution is almost
completely present as SO2.6H2O and only traces of H2SO3.
(iii) Addition Reaction :
SO2 + Cl2  SO2Cl2 (sulphuryl chloride)
SO2 can act as both reducing and oxidising agent.
 Compounds Of Sulphur
Sulphur Trioxide(SO3)
Preparation :
6H2SO4 + P4O10 6SO3 + 4H3PO4

Heating of ferric sulphate Fe2(SO4)3  Fe2O3 + 3SO3

It Is an Acidic Gas
Oxyacids Of Sulphur
 Sulphuric Acid (H2SO4)
Manufacture :
It is manufactured By Contact process which involves following three steps-
(i) Burning of sulphur or sulphide ores in air to generate SO2
(ii) Conversion of SO2 to SO3 by the reaction with oxygen in the presence of a
catalyst (V2O5)
(iii) Absorption of SO2 in H2SO4 to give Oleum (H2S2O7)
The oleum obtained is diluted with water to produce H2SO4 with desired
concentration. H2SO4 obtained is 96-98 % pure.
Properties :
# It is essentially strong for first dissociation.
# Because of its low volatility can be used to manufacture more volatile acid from
their corresponding salts.
2MX + H2SO4  2HX + M2SO4 (X = F, Cl, NO3)
# Concentrated sulphuric acid is a strong dehydrating agent. Many wet gases can be
dried by passing them through sulphuric acid, provided the gases do not react with
the acid. Sulphuric acid removes water from organic compound; it is evident by its
charring action on carbohydrates.
C12H22O11  12C + 11H2O ; H2C2O4  CO + CO2

# Hot concentrated sulphuric acid is moderately strong oxidising agent. Both metals
and non-metals are oxidised by concentrated sulphuric acid, which is reduced to SO2.
Cu + 2H2SO4 (concentrated)  CuSO4 + 2H2O
3S + 2H2SO4 (concentrated)  3SO2 + 2H2O
C + 2H2SO4 (concentrated)  CO2 + 2SO2 + 2H2O
H2SO4 + KBr KHSO4 + HBr
2HBr + H2SO4  2H2O + Br2 + SO2
PRACTICE SESSION-4
• Q.1 Sulphur on oxidation with hot sulphuric acid gives :
(A) SO3 (B) SO2 (C) H2SO3 (D) H2S2O3

Q.2. Which one of the following gives mixture of SO2 and SO3 on heating ?
(A) ZnSO4 (B) CuSO4 (C) Fe2 (SO4)3 (D) FeSO4

Q.3. SO2 can reduce :

• (A) HClO3 to HCl (B) Cr2O72– / H+ to Cr3+
(C) MnO4– / H+ to Mn2+ (D) IO3– to I2

Q.4 Out of H2S2O3 , H2S4O6 , H2SO5 and H2S2O8 peroxy acids are :
(A) H2S2O3 , H2S4O6 (B) H2S4O6 , H2SO5
(C) H2SO5 , H2S2O8 (D) H2S2O3 , H2S2O8
Q.5 Identify the incorrect statement with respect to ozone.
(A) Ozone is formed in the upper atmosphere by a photochemical reaction
involving ioxygen.
(B) Ozone is more reactive than oxygen
(C) Ozone is diamagnetic where as dioxygen is paramagnetic
(D) Ozone protects the earth's inhabitants by absorbing g radiations.

Q.6 When an article is bleached by SO2 it loses its colour. The colour can be restored by
(A) exposure to air (B) heating (C) dilution (D) none of these
Q.7 Which of the following statement is incorrect ?
(A) Sulphur molecule in vapour state exist as S2 and is paramagnetic in nature.
(B) Sulphur and selenium occur as S8 and Se8 molecules at room temperature
and have puckered ring structure.
(C) Ozone oxidises KMnO4.
(D) SO2 can act both as oxidising as well as reducing agent.

• Q.8 Which statement regarding sulphuric acid is incorrect?

• (A) It is responsible for charring of sugar due to its dehydrating property.
• (B) It is obtained in contact process by hydrolysis of oleum.
• (C) The value of Ka2 for H2SO4 is greater than its Ka1 value.
• (D) It consists of two dp-pp bonds and sulphur atom is sp3 hybridised in it.
• Q.9 Which statement regarding ozone is incorrect?
• (A) Ozone is powerful oxidising agent as compared to O2
• (B) Formation of ozone from O2 is endothermic
• (C) Ozone molecule is paramagnetic like oxygen molecule
• (D) O3 is estimated by KI in presence of Borate buffer followed by titration with
hypo
 17th Group -Halogen Family
Halogens – Salt producers

Physical Properties
# Fluorine and chlorine are gases, bromine is a liquid whereas iodine is a solid.
# Their melting and boiling points steadily increase with atomic number.
# All halogens are coloured. This is due to absorption of radiations in visible region
which results in the excitation of outer electrons to higher energy level. For example,
F2, has yellow, Cl2, greenish yellow, Br2, red and I2, violet colour.

# Bond Energy – Cl2 > Br2 > F2 > I2

 Chemical Properties
# All the halogens are highly reactive. They react with metals and non-metals to form
halides. The reactivity of the halogens decreases down the group.
# Their melting and boiling points steadily increase with atomic number.
# All halogens are coloured. This is due to absorption of radiations in visible region
which results in the excitation of outer electrons to higher energy level. For example,
F2, has yellow, Cl2, greenish yellow, Br2, red and I2, violet colour.

# Bond Energy – Cl2 > Br2 > F2 > I2

# All the halogens are highly reactive. They react with metals and non-metals to form
halides. The reactivity of the halogens decreases down the group.
 Oxidising Character
# Since halogens have higher tendency to accept electrons they are strong oxidizing.
# F2 is the strongest oxidising halogen and it oxidises other halogens in solution or
even in the solid phase.
F2 + 2X-  2F- + X2 (X = Cl,Br,I)
# The oxidising power decreases on moving down the group.
Reaction with water
# F2 being a strong oxidising agent oxidises water to oxygen.
2F2(g) + 2H2O(l)  4H+ (aq) + 4F– (aq) + O2(g)

# Cl2 and Br2 disproportionate in water

X2(g) + H2O (l)  HX(aq) + HOX (aq)
# Reaction of I2 is non-spontaneous . I– can be oxidised by oxygen in acidic medium;
just the reverse of the reaction observed with fluorine.
4I– (aq) + 4H+ (aq) + O2(g)  2 I2 (s) + 2H2O (l)
 Reactivity towards Hydrogen
# They all react with hydrogen to give hydrogen halides but affinity for hydrogen
decreases from fluorine to iodine with increasing atomic number.

# The acidic strength of these acids increases in the order : HF < HCl < HBr < HI.

# The stability of these halides decreases down the group due to decrease in bond
(H–X) dissociation enthalpy in the order :
H – F > H – Cl > H –Br > H – I .
# Melting point order - HI > HF > HBr > HCl

# Boiling point order – HF > HI > HBr > HCl

 Reactivity towards Oxygen
# Halogens form many oxides with oxygen but most of them are unstable.
# Fluorine forms two oxides OF2 and O2F2. However, only OF2 is the thermally stable
at 298 K. These oxide are essentially oxygen fluorides because of the higher
electronegativity of flurorine than oxygen .
# Both are strong fluorinating agents. O2F2 oxidises plutonium to PuF6 and the
reaction is used in removing plutonium as PuF6 from spent nuclear fuel.
# Chlorine oxides, Cl2O, ClO2, Cl2O6 and Cl2O7 are highly reactive oxidising agents and
tend to explode. ClO2 is used as a bleaching agent for paper pulp and textiles and in
water treatment.
# The bromine oxides, Br2O, BrO2, BrO3 are the least stable halogen oxides and exist
only at low temperature. They are very powerful oxidising agents.
# The iodine oxides, I2O4, I2O5, I2O7 are insoluble solids and decompose on heating.
I2O5 is very good oxidising agent and is used in the estimation of carbon monoxide.
# Stability Of Oxides I > Cl > Br
 Chlorine (Cl2)
Preparation :
(i) By heating MnO2 with concentrated HCl in presence of.
MnO2 + 4HCl  MnCl2 + Cl2 + 2H2O
A mixture of NaCl & H2SO4 is also used in place of HCl.
MnO2 + 4NaCl + 4H2SO4  MnCl2 + 4NaHSO4 + 2H2O + Cl2
(ii) By the action of KMnO4 with HCl
2KMnO4 + 16 HCl  2 KCl + 2 MnCl2 + 5 Cl2 + 8 H2O
(iii) Deacon’s Process : Oxidatio of HCl with atmospheric oxygen in presence of CuCl2
at 723 K.
4 HCl + O2 2 Cl2 + 2 H2O
(iv)
 (v) Electrolytic process : Chlorine is obtained by the electrolysis of brine
(concentrated NaCl solution). Chlorine is liberated at anode. It is obtained as a
by–product in many chemical industries e.g.; in manufacturing of sodium hydroxide.
NaCl (aq)  Na+ (aq) + Cl– (aq)
Anode : 2Cl–  Cl2 + 2e–
Cathode : 2H2O + 2e–  H2(g) + 2OH–

Overall reaction : 2NaCl + 2H2O  2NaOH + H2 + Cl2

 Properties
# It is a greenish–yellow gas with pungent and suffocating odour and soluble in water.
# Reaction with Ammonia
8NH3(excess) + 3Cl2  6NH4Cl + N2
NH3 + 3Cl2(excess)  NCl3 + 3HCl
Similar reaction is shown by Br2 .
Reaction with Iodine
NH3 (g) + I2  No Reaction

NH3 (aq) + 2 (s) N3 . NH3 + 3H

A slurry is formed
(Ammonia liquor) which can be dried an explosive
and on hammering it (Nitrogentriiodide
explodes causing ammoniated)
sound (crakers)
 Chlorine water -
Chlorine water on standing looses its yellow colour due to formation of HCl &
HOCl. HOCl thus formed decomposes to give Nascent oxygen , which is responsible
for oxidizing and bleaching property of Chlorine. It oxidises –
ferrous to ferric,
2 FeSO4 + H2SO4 + Cl2  Fe2(SO4)3 + 2 HCl
sulphite to sulphate
Na2SO3 + Cl2 + H2O Na2SO4 + 2 HCl
sulphur dioxide to sulphuric acid
SO2 + 2 H2O + Cl2 H2SO4 + 2 HCl
iodine to iodic acid.

# Chlorine oxidises both Br– and l– to Br2 and I2 respectively.

X– + Cl2  X2 + 2Cl–
Uses
1. For bleaching wood pulp (required for the manufacture of paper and
rayon), bleaching cotton and textiles.

2. In the manufacture of dyes, drugs and organic compounds such as CCl4 ,

CHCl3 , DDT, refrigerants, etc.

3. In the extraction of gold and platinum.

4. In sterilizing drinking water and

5. preparation of poisonous gases such as phosgene (COCl2), tear gas

(CCl3NO2), mustard gas (ClCH2CH2SCH2CH2Cl).
 Pseudo halogens and pseudo halides
Some inorganic compounds consisting of two or more atoms of which at least
one is N have been found to behave like halogens & they are known as pseudo halogen
solids, e.g. (CN)2 cyanogen, (SCN)2 thiocyanogen.

Similarly few ions are known that have properties similar to those of the halide ions.
They are therefore called pseudohalide ions, e.g. (CN–) cyanide ion, (SCN–) thiocyanate
ion, (SeCN)– selenocyanate ion, (OCN)– cyanate ion, (NCN)2– cyanamide ion,
(N3)– azide ion etc.
 Interhalogen compounds
Due to this difference in electronegativity the halogen atoms combine with each
other and give rise to the formation of binary covalent compounds, which are called
interhalogen compounds. These are of four types.
AB AB3 AB5 AB7
ClF ClF3 ClF5 lF7
Preparation :
(i) By the direct combination of halogens :
Cl2 + F2 (equal volumes)  2ClF Cl2 + 3F2 (excess) 2ClF3
I2 + Cl2  2ICl
(equimolar)
Properties :
# All interhalogens are covalent molecules and are diamagnetic in nature.
# Their m.p. and b.p’s are higher than corresponding halogens.
# In general interhalogen compounds are more reactive than normal halogens except
Fluorine.
 Hydrolysis Of Interhalogen compounds

These compounds are used a non aqueous solvents and are good fluorinating
agents . U(s) + ClF3(l)  UF6(g) + 3ClF(g)
 18th Group – Noble Gas
Occurrence
All the noble gases except radon occur in the atmosphere. Their atmospheric
abundance in dry air is ~ 1% by volume of which argon is the major constituent.
Helium and sometimes neon are found in minerals of radioactive origin e.g.,
pitchblende, monazite, cleveite. The main commercial source of helium is natural gas.
Xenon and radon are the rarest elements of the group. Radon is obtained as a decay
product of 226Ra.
# Noble gases have very low B.P. due to very weak Vander waal forces. He has the
lowest B.P.(4.2 K) of any substance.
 Clatherate compounds
Inert gas molecules get trapped in the cages formed by the crystal structure of
water. During the formation of ice Xe atoms will be trapped in the cavities (or cages)
formed by the water molecules in the crystal structure of ice. Compounds thus
obtained are called clatherate compounds.
There are no chemical bonds. They do not possess an exact chemical formula
but approx it is 6 water molecules : 1 inert gas molecule.
Chemical Properties