s and p-Block Elements 733

Table : 18.4 Oxides of Nitrogen

Physical
Oxide Structure appearance
Preparation

Nitrous oxide ( N 2 O ) By heating ammonium nitrate upto 240 C 0

Colourless
N  N O gas 
+1 NH NO 
4 3
N O + 2H O, It is Collected over hot water
2 2

(a) By the action of cold dil. HNO on copper turnings (Laboratory 3

method)
3Cu + 8 dil. HNO  3Cu(NO ) + 4H O + 2NO 3 3 2 2

Nitric oxide (NO) (b) By the action of H SO on a mixture of FeSO and KNO (4:1)2 4 4 3

N=O Colourless 2KNO + 5H SO + 6FeSO  2KHSO + 3Fe (SO ) + 4H O + 2NO

+2 3 2 4 4 4 2 4 3 2

(c) By catalytic oxidation of ammonia.

4NH + 5O 
3
Pt
 4NO + 6H O 2 2

850 0 C

(a) By the action of 50% HNO on arsenious oxide. 3

Dinitrogen trioxide ( N 2 O 3 ) O 2HNO + As O + 2H O  NO + NO + 2H AsO

3 2 3 2 2 3 4

O NN Blue solid

+3 O  250 K
NO 2 3

Dinitrogen tetraoxide ( N 2 O 4 ) O O (a) By heating nitrates of heavy metals, e.g., lead nitrate.
Colourless
N N liquid
+4 O O 2Pb(NO )   4NO + 2PbO + 2O
673 K
3 2 2

Nitrogen dioxide ( NO 2 ) (b) By heating copper turnings with conc. HNO 3.

N Brown gas Cu + 4 HNO (conc.)  Cu(NO ) + 2H O + 2NO

+4 O O 3 3 2 2 2

Dinitrogen pentoxide ( N 2 O5 ) O O O (a) By dehydrating HNO with phosphorus pentoxide

Colourless 3

N N gas 4HNO +P O  2N O + 4HPO

+5 O O 3 4 10 2 5 3

(3) Oxyacids of nitrogen : Oxyacids of nitrogen are 4 NH 3  5 O2    4 NO  6 H 2 O

Pt. 1975 K

HNO 2 , HNO 3 , H 4 N 2 O 4 and HNO 4 , which are explosive.

(Nitroxylic acid) (Pernitric acid)
2 NO  O2 ⇌ 2NO 2 ; 4 NO 2  2 H 2 O  O2  4 HNO 3
(i) Nitrous acid (HNO ) : It is prepared by adding ice cold dil, HCl
2
From air (Birkeland Eyde electric arc process)
or dil, H 2 SO 4 to a well cooled solution of any nitrite
N 2  O 2 ⇌ 2 NO ; H of  135 kJ mol 1
(NaNO 2 , Ba(NO 2 )2 etc.).
o

NaNO 2  HCl  NaCl  HNO 2 2 NO  O 2   2 NO 2

50 C

2 KNO 2  H 2 SO 4  K 2 SO 4  2 HNO 2 2 NO 2  H 2 O  HNO 2  HNO 3

It oxidises H 2 S to S, Kl to I 2 and acts as a reducing agent in 3 HNO 2  HNO 3  H 2 O  2 NO

presence of strong oxidising agent, i.e., it reduces acidified
KMnO4 , K 2 Cr2 O7 ,H 2 O2 etc. to Mn 2  , Cr 3  and H 2 O respectively.
(ii) Nitric acid (HNO ) : HNO 3 is called aqua fortis. It is prepared
3
Properties : It is a very strong acid and decomposes on boiling or in
presence of sunlight. It acts as a strong oxidising agent. It oxidises
nonmetals and metalloids to their respective oxy-acids, i.e., C to

in the laboratory by distillation of nitre with conc. H 2 SO 4 .
2 NaNO 3  H 2 SO 4  2 HNO 3  Na 2 SO 4 .
Commercially, it is obtained by Ostwald’s process. In this process,
NH 3 is first catalytically oxidised to NO which is cooled to about
300 K and then oxidised by air to NO 2 . Absorption of NO 2 in water in
presence of oxygen gives HNO 3
H 2 CO 3 , S to H 2 SO 4 , P to H 3 PO4 , l2 to HlO3 , As to
H 3 AsO4 (arsenic acid) and Sb to H 3 SbO 4 (antimonic acid), while
nitric acid itself is reduced to NO 2 .
I2  10 HNO 3  2 HIO3  10 NO 2  4 H 2 O
Nitric acid reacts with metals to form nitrates and is itself reduced
to NO , N 2 O, NO 2 or NH 3 (which further reacts with HNO 3 to give
 734 s and p-Block Elements
NH 4 NO 3 ) depending upon the concentration of the acid, activity of the Nitric acid has no action on noble metals ( Au, Pt) but these metals
metal and the temperature of the reaction. dissolve in aqua regia (3 vol. HCl  1 vol. HNO 3 ) forming their respective
(i) Very active metals such as Mn, Mg, Ca , etc. give H 2 on chlorides.
treatment with very dilute HNO 3 (2%). HNO 3  3 HCl  2 H 2 O  NOCl  2[Cl]
(ii) Less active metals like Cu, Hg, Ag, Pb etc. give NO with dil.
Au  3[Cl]  AuCl3 ; Pt  4[Cl]  PtCl4
HNO 3 . Zinc, however, gives N 2 O with dil HNO 3 and NH 4 NO 3
with very dilute HNO 3 . These chlorides subsequently dissolve in excess of HCl forming
their corresponding soluble complexes. Thus,
Zn  10 HNO 3 (dilute) 4 Zn(NO 3 )2  N 2 O  5 H 2 O
AuCl 3  HCl  HAuCl4
Zn  10 HNO 3 (very dilute) 4 Zn(NO 3 )2  NH 4 NO 3  3 H 2 O Auric chloride Aurochloric acid

Similarly, Fe and Sn react with dilute nitric acid to give PtCl4  2 HCl  H 2 PtCl6
Platinic chloride Chloro platinicacid
NH 4 NO 3 .
Sugar on oxidation with nitric acid gives oxalic acid. Nitric acid
(iii) Conc. HNO 3 gives NO 2 both with active metals (Zn, Pb reacts with glycerine to give glycerol trinitrate or nitro glycerine, with
etc.) and less active metals ( Cu , Hg, Ag etc.) toluene it gives 2, 4, 6-trinitrotoluene (T.N.T.) and with cellulose (cotton) it
gives cellulose trinitrate (gun cotton). All these are used as explosives.
Cu  4 HNO 3 (Conc.)  Cu(NO 3 )2  2 NO 2  2 H 2 O
COOH
Tin is, however, oxidized by conc. HNO 3 to metastannic acid C12 H 22 O11  18[O]  6 |  5 H 2O
Cane sugar From HNO 3
(H 2 SnO 3 ) . COOH
Oxalic acid
Sn  4 HNO 3  H 2 SnO 3  4 NO 2  H 2 O

Passivity : Fe, Cr, Ni and Al become passive in conc. HNO 3

(i.e., lose their normal reactivity) due to the formation of a thin protective
layer of the oxide on the surface of the metal which prevents further action.
Table : 18.5 Oxyacids of nitrogen

Name
M. ofF. oxoacid
Formula M. F. Structure Oxidation State of N Basicity pK a
Nature

Hyponitrous acid HNO

2 2 2
.. +1 2(dibasic) Very weak Highly explosive
N  OH
||
HO  N
..

Nitrous acid HNO 2 HN O +3 1 (monobasic) 3.3 Unstable, Weak acid




Nitric acid HNO 3 H O  N  O +5 1 (monobasic) -3.0 Stable, Strong acid




Pernitric acid HNO 4 O  NO O  H +5 1 (monobasic) Unstable and


 explosive

Phosphorus and its compounds
It is the second member of group 15 (VA) of the Periodic table.
Due to larger size of P, it can not form stable P  - P  bonds with
other phosphorous atoms where as nitrogen can form P  – P  bonds .
(1) Occurrence : Phosphorous occurs mainly in the form of
phosphate minerals in the crust of earth. Some of these are :
(i) Phosphorite Ca 3 (PO4 )2 , (ii) Fluorapatite Ca5 (PO4 )3 F ,
Ca5 (PO4 )3 OH . Phosphates are essential constituents of plants and
animals. It is mainly present in bones, which contains about 58% calcium
phosphate.
(2) Isolation : Elemental phosphorus is isolated by heating the
phosphorite rock with coke and sand in an electric furnace at about 1770K,
2Ca 3 (PO4 )2  6 SiO2  6 CaSiO3  P4 O10 ;
Calicum silicate

(iii) Chlorapatite 3 Ca3 (PO4 )2 .CaCl 2 , (iv) Hydroxyapatite; P4 O10  10C  P4  10CO
 s and p-Block Elements 735

(3) Allotropic forms of phosphorus : Phosphorus exists in three
main allotropic forms,
(i) White phosphorus, (ii) Red phosphorus, (iii) Black phosphorus
(i) White or yellow phosphorus : It is obtained from phosphate rock
or phosphorite as explained above. It exists as P4 units where four P
atoms lie at the corners of a regular tetrahedron with PPP  60 o . Each
P atom is linked to three other P atoms by covalent bonds. there are
total six bonds and four lone pairs of electrons present in a P4 molecule of
white phosphorus. ··
P It burns in oxygen at 565 K to give phosphorus pentoxide, reacts
60°
··
:P P
P at 470 K under high pressure (4000–12000atm) in an inert atmosphere.
··
Properties : White phosphorus is extremely reactive due to strain in
the P4 molecule, poisonous, soft, low melting (317 K) solid, soluble in
CS 2 , alcohols and ether. It has a garlic odour. Persons working with white
P develop a disease known as Phossy jaw in which jaw bones decay. It
turns yellow on exposure to light. Hence, it is also called yellow phosphorus.
It spontaneously catches fire in air with a greenish glow which is
visible in the dark (P4  3O2  P4 O6 ) . This phenomenon is called
phosphorescence. Because of its very low ignition temperature (303 K) , it
is always kept under water.
With sulphur it gives tetraphoshorus trisulphide with explosive
violence which is used in “strike anywhere matches”.
8 P4  3 S 8  8 P4 S 3
With metals phosphorus forms phosphides. For example,
P4  6 Mg  2 Mg3 P2
Due to its polymeric structure, red phosphorus is much less reactive
and has m.p. much higher than that of white phosphorus.
Properties : Red phosphorus is a hard, odourless, non poisonous
solid, insoluble in organic solvents such as CS 2 , alcohol and ether. Its
ignition temperature is much higher than that of white phosphorus and
thus does not catch fire easily. It does not show phosphorescence.
It sublimes on heating giving vapours which condense to give white
phosphorus. It is denser than white phosphorus and is a bad conductor of
electricity.
with halogens, sulphur and alkali metals only when heated forming their
corresponding salts.
It does not react with caustic alkalies and this property is made use
in separating red phosphorus from white phosphorus.
(iii) Black phosphorus : It is obtained by heating white phosphorus
White phosphorus 470
K Black phosphorus
4000 12000 atm. pressue
It has a double layered structure. Each layer is made up of zig-zag
chains with P  P  P bond angle of 99 o . Since it is highly polymeric, it
has high density. It is the most stable (inactive) form of phosphorus and has
a black metallic luster. It is a good conductor of heat and electricity.
(4) Compounds of phosphorus
(i) Oxides and oxyacids of phosphorus : Phosphorus is quite
reactive and forms number of compounds in oxidation states of –3 , +3 and
+5. Phosphorus forms two common oxides namely, (a) phosphorus trioxide
( P4 O6 ) and (b) phosphorus penta oxide (P4 O10 ) .
(a) Phosphorus (III) oxide ( P4 O6 ) :
.P.
.. ..
O O
..
.. ..
127
o

With aqueous alkalies, on heating, white phosphorus gives phosphine

O
..
0 3 1
P4  3 NaOH  3 H 2 O  PH3  3 NaH 2 PO2 ..
(Phosphine ) Sod. hypophosph ite .P. O .P.
..
It is an example of a disproportionation reaction where the oxidation
state of P decreases from 0 to –3 (in PH 3 ) and increases to +1 (in .. .P. ..
O
.. 166 pm O
..
NaH 2 PO2 )
White phosphorus acts as a strong reducing agent. It reduces It is formed when P Phosphorus
is burnttrioxide
in a limited supply of air,
HNO 3 to NO 2 and H 2 SO 4 to SO 2 . It also reduces solutions of P4  3O2  P4 O6 .
(limited)
Cu, Ag and Au salts to their corresponding metals. For examples,
It is a crystalline solid with garlic odour. It dissolves in cold water
P4  8 CuSO 4  14 H 2 O  8 Cu  8 H 2 SO 4  4 H 3 PO4 to give phosphorous acid,

P4  20 AgNO3  16 H 2 O  20 Ag  4 H 3 PO4  20 HNO 3 P4 O6 + 6 H 2 O  4 H 3 PO3 , It is therefore, considered as

cold Phosphorou s acid
(ii) Red phosphorus : It is obtained by heating white phosphorus at anhydride of phosphorus acid.
540  570 K out of contact with air in an inert atmosphere ( CO 2 or
With hot water, it gives phosphoric acid and inflammable phosphine,
coal gas) for several hours.
P4 O6  6 H 2 O (hot)  3 H 3 PO4  PH3
540  570 K
White phosphorus   Red phosphorus Phosphoric acid
CO 2 or coal gas
It reacts vigorously with Cl 2 to form a mixture of phosphoryl
Red phosphorus exists as chains of P4 tetrahedra linked together
chloride and meta phosphoryl chloride.
through covalent bonds to give a polymeric structure as shown.
P4 O6  4 Cl 2  2 POCl3  2 PO2 Cl
P P P Phosphoryl chloride Metaphosph oryl chloride

P P P P P P (b) Phosphorus (V) oxide P4 O10  :

P P P
 736 s and p-Block Elements
..
: O:

143 pm
P O
.. 102 o .. Metaphosphoric acid +5
.O. 123o
.O. (HPO3 )n Monobasic P
..

160 pm
.O. O
HO
.. P .. P .. Pyrophospric acid O O
: .O. O
.. . .:
O
(Diphosphoric acid).
+5

.. P Tetrabasic P P
.. H 4 P2 O7 OH
.O. .O. HO OH
O
OH
:O
. .: (5) Chemical Fertilizers : The chemical substances which are added
It is prepared by heating white phosphorus in excess of air, to the soil to keep up the fertility of soil are called fertilizers.
Phosphorus pentoxide
P4  5 O2 (excess )  P4 O10 . It is snowy white solid. It readily dissolves in Types of fertilizers : Chemical fertilizers are mainly of four types,
cold water forming metaphosphoric acid. (i) Nitrogenous fertilizers : e.g. Ammonium sulphate (NH 4 )2 SO 4 ,
P4 O10  2 H 2 O  4 HPO3 . With hot water, it gives Calcium cyanamide CaCN 2 , Urea NH 2 CONH 2 etc.
(Cold) Metaphosph oric acid
(ii) Phosphatic fertilizers : e.g. Ca(H 2 PO4 )2 .H 2 O (Triple super
phosphoric acid, P4 O10  6 H 2 O  4 H 3 PO4 .
Hot Phosphoric acid phosphate), Phosphatic slag etc.
(iii) Potash fertilizers : e.g. Potassium nitrate (KNO 3 ), Potassium
P4 O10 is a very strong dehydrating agent. It extracts water from many
sulphate (K 2 SO 4 ) etc.
compounds including H 2 SO 4 and HNO 3 ,
(iv) Mixed fertilizers : These are made by mixing two or more
H 2 SO 4  SO 3 ; 2 HNO 3 4 
 N 2 O5
P O P O
4 10 10 fertilizers in suitable proportion. e.g. NPK (contains nitrogen, phosphorus
 H 2O  H 2O
and potassium).
CH 3 CONH 2 
 CH 3 CN
P4 O10 NPK is formed by mixing ammonium phosphate, super phosphate
Acetamide H 2O Methyl cyanide and some potassium salts.
(ii) Oxyacids of phosphorus : Phosphorus forms a number of oxyacids Oxygen Family
which differs in their structure and oxidation state of phosphorus. These are
H 3 PO2 , H 3 PO3 , H 4 P2 O6 , H 3 PO4 , Oxygen is the first member of group 16 or VIA of the periodic table.
It consists of five elements Oxygen (O), sulphur (S), selenium (Se),
(HPO3 )n , H 4 P2 O5 , H 4 P2 O7 . From these H 3 PO2 , H 3 PO3 are tellurium (Te) and polonium (Po). These (except polonium) are the ore
reducing agents. H 4 P2 O 5 (pyrophosphoric acid) is dibasic acid. forming elements and thus called chalcogens.
(1) Electronic configuration
(HPO3 )n is formed by dehydration of H 3 PO4 at 316 o C .
Elements Electronic configuration ( ns 2 np 4 )
Table : 18.6 Oxyacids of phosphorus
Oxidation 8 O [He] 2 s 2 2 p 4
Name state of P Structure
and Basicity 16 S [ Ne ] 3 s 2 3 p 4
O 34 Se [ Ar] 3d 10 4 s 2 4 p 4
Hypophosphorous +1
P 52 Te [Kr] 4 d 10 5 s 2 5 p 4
acid H 3 PO2 Monobasic H
84 Po [ Xe] 4 f 14 5 d 10 6 s 2 6 p 4
H OH
O
Physical properties
Phosphorous acid +3 (1) Physical state : Oxygen is gas while all other are solids.
P
H 3 PO3 Dibasic (2) Atomic radii : Down the group atomic radii increases because
OH
H the increases in the number of inner shells overweighs the increase in
OH nuclear charge.
O O
(3) Ionisaion energy : Down the group the ionisation energy
Hypophosphoric acid +4 decrease due to increase in their atomic radii and shielding effect.
H 4 P2 O 6 Tetrabasic
P P
(4) Electronegativity : Down the group electronegativity decreases
OH
due to increase in atomic size.
HO OH OH (5) Electron affinity : Element of this group have high electron
Orthophosphoric acid +5 O affinity, electron affinity decreases down the group.
H 3 PO4 Tribasic (6) Non – metallic and metallic character : These have very little
P metallic character because of their higher ionisation energies.
OH
HO OH
 s and p-Block Elements 737

(7) Nature of bonding : Compound of oxygen with non metals are H 2 O  H 2 S  H 2 Se  H 2 Te

predominantly covalent. S, Se, and Te because of low electronegativities
show more covalent character. (2) Oxides : These elements form monoxides (MO), dioxides
(8) Melting and boiling points : The melting point and boiling points ( MO2 ) and trioxides (MO3 ) .
increases on moving down the group. (i) Dioxides : Sulphur, selenium and tellurium burn in air to form
(9) Catenation : Oxygen has some but sulphur has greater tendency SO 2 , SeO 2 and TeO 2 . The dioxide molecules contain p  p bonds
for catenation. which become weaker with increase in atomic number because of the
H  O  O  H, H  S  S  H, increase in the bond length.
(H 2 O 2 ) (H 2 S 2 ) (a) Sulphur dioxide, SO 2 is a gas at room temperature and exists as
H  S  S  S  H, H S S S S H individual molecules even in the solid state. Its molecule has bent structure and is a
(H 2 S 3 ) (H 2 S 4 ) resonance hybrid of the following canonical structures.
(10) Allotropy
S S S
Oxygen – O 2 and O 3
Sulphur – Rhombic , monoclinic, plastic sulphur O O O O O O
Selenium – Red (non-metallic) grey (metallic) SO 2 is acidic in nature and also called the anhydride of
Tellurium – Non-metallic and metallic (more stable)
sulphurous acid. It can act as reducing and oxidising agent. SO 2 also acts
Polonium –  and  (both metallic)
as a beleaching agent in the presence of moisture, but in contrast to Cl 2 ,
(11) Oxidation states : Oxygen shows – 2, + 2 and –1 oxidation
states. Other elements show +2 ,+4 and +6 oxidation states. its bleaching action is temporary.
Chemical properties SO 2  2 H 2 O  H 2 SO 4  2[H ]
(1) Hydrides : The elements of this group form hydrides such as
Colouring matter 2[H ] ⇌ Colourless compound
H 2 O, H 2 S , H 2 Se , H 2 Te an H 2 Po . Following are their characteristics.
(i) Physical states : Water is colourless and odourless while hydrides Hence, SO 2 bleaches due to reduction and the bleaching action is
of the rest of the elements of this group are colourless, unpleasant smelling temporary.
poisonous gases. (b) Selenium dioxide, SeO 2 is a solid with polymeric zig-zag
(ii) Volatile nature : Volatility increases from H 2 O to H 2 S and structure at room temperature however it exist as discrete molecules in the
then decreases. The low volatility and abnormally high boiling point of gaseous phase.
water is due to the association of water molecules on account of hydrogen O O O
bonding because of strongly electronegative oxygen atom linked to hydrogen
=

=
Se Se Se
atom. thus, water is liquid while H 2 S and other hydrides are gases under
normal condition of temperature and pressure. O O O O
(iii) Acidic character : The hydrides of this group behave as weak (c) Tellurium dioxide, TeO 2 is also a solid with polymeric zig-zag
diprotic acids in aqueous solution, the acidic character increasing from structure at room temperature very similar to that of selenium dioxide.
H 2 S to H 2 Te when H 2 O is neutral. (ii) Trioxides : Sulphur, selenium and tellurium can form trioxides
(iv) Thermal stability : The thermal stability decreases from H 2 O also.
(a) Sulphur trioxide, SO 3 : In the gaseous state monomeric SO 3
to H 2 Po because the size of the central atom (from O to Po )
has a planar structure with S  O bond distance of 143 pm and
increases resulting in longer and weaker M  H bond consequently the
bond strength decreases. This results in the decrease of the thermal O  S  O bond angle of 120 o . SO 3 molecule is a resonance hybrid of
stability. following structures.
(v) Reducing character : The reducing power of the hydrides
increases from H 2 O to H 2 Po due to the decreasing bond strength from O O O O

H 2 O to H 2 Po . S S S S
143 pm
(vi) Bond angle : All these hydrides are angular molecules and the 120°
bond angle H  X  H ( X is O, S , Se , Te ) decreases from H 2 O to O O O O O O O O

H 2 Te . Canonical structures Resonance hybrid

In the solid phase sulphur trioxide polymerises to cyclic trimer or to
Increasing order of reducing power of hydrides : a stable linear chain structure. SO 3 is the anhydride of H 2 SO 4 . It is
H 2 O  H 2 S  H 2 Se  H 2 Te acidic in nature and acts as oxidising agent.
Increasing order of bond angles in hydrides : (b) Selenium trioxide, SeO 3 : it is a solid substance which exists
H 2 Te  H 2 Se  H 2 S  H 2 O as a cyclic tetramer, however in the vapour phase it exists as a monomer
The order of stability of hydrides : (c) Tellurium trioxide, TeO 3 : It is a solid at room temperature
H 2 O  H 2 S  H 2 Se  H 2 Te existing as a polymer.
The order of increasing acidic nature of hydrides : The increasing order of acidic nature of oxides is
TeO 3  SeO 3  SO 3 .
 738 s and p-Block Elements
(3) Oxyacids : (3) Laboratory Method : In the laboratory, O 2 is prepared by thermal
H 2 SO 3 , H 2 SO 4 , H 2 S 2 O3 , H 2 SO 5 , H 2 S 2 O8 , H 2 S 2 O7 , H 2 S 2 O6 decomposition of potassium chlorate.
2 KClO3   2 KCl  3O2
420 K
(4) Halides : Oxygen : OF2 , Cl 2 O, Br2 O MnO 2

Sulphur : S 2 F2 , S 2 Cl 2 , SF2 , SCl 2 , SBr2 , SF4 , SCl 4 and SF6 In the absence of MnO2 catalyst, the decomposition takes place at
670-720 K. Therefore, MnO2 acts as a catalyst and also lowers the
Selenium and tellurium : SeF6 and TeF6
temperature for the decomposition of KClO3 .
Anamolous Behaviour of Oxygen
(4) O 2 can also be prepared by the action of water on sodium peroxide
Oxygen is the first member of the group 16 family and differs from
the other members of the family because of as, 2 Na 2 O2  2 H 2 O  4 NaOH  O2 .
(1) Its small size (5) Industrial preparation : The main sources for the industrial
preparation of dioxygen are air and water.
(2) Its high electronegativity
(i) From air : O 2 is prepared by fractional distillation of air. During
(3) Its high ionisation energy
this process, N 2 with less boiling point (78 K) distills as vapour while O 2
(4) Absence of d -orbitals in the valence shell with higher boiling point (90 K) remains in the liquid state and can be
It differs from the other members of the family as follows separated.
(1) Elemental state : Oxygen is a diatomic gas while others are octa- (ii) From water : O 2 can also be obtained by the electrolysis of
atomic solids with eight membered puckered ring structure. water containing a small amount of acid or alkali,
Electrolysis
(2) Oxidation states : Oxygen shows O.S. of –2 in most of its
2H 2O 2 H 2 (g)  O2 (g) .
compounds. It also shows an O. S. of +2 in F2 O and –1 in H 2 O 2 or
Physical properties of O : It is a colourless, tasteless and odourless
other peroxides. It cannot show O.S. beyond 2. Other elements show 2

gas. It is slightly soluble in water and its solubility is about

oxidation states of +2, +4 and +6 because these elements have vacant d -
orbitals so that their valence shell can expand. 30 cm 3 per litre of water at 298 K.

(3) Hydrogen-bonding : Oxygen atom is very small and has quite Table : 18.7 Physical properties of atomic and molecular oxygen
high nuclear charge. therefore, it has high value of electronegativity and is Atomic properties Molecular properties
able to form H -bonds. the other elements, because of their large size, Atomic radius (pm) – 73 Bond length (pm) – 120.7
cannot form H -bonds. As a result, H 2 O is liquid while H 2 S is a gas Ionic radius O (pm) – 140
2–
Bond energy (kJ mol ) – 493
–1

and H 2 Se etc., are solids. Electronegativity – 3.5 Density at S.T.P. (gcm )– 1.429
–3

Ionisation energy (kJ mol ) – 1310

–1
Melting point (K) – 54.4
(4) Maximum covalency : Oxygen has a maxium covalency of two
Electron affinity (kJ mol ) – 140
–1
Boiling point (K) – 90.2
while other elements can show a maximum covalency of six. This is because
these elements have vacant d -orbitals while oxygen has not. Chemical properties of O : It does not burn itself but helps in
2

burning. It is quite stable in nature and its bond dissociation energy is very
(5) Types of compounds : The compounds of oxygen are mainly
ionic and polar covalent due to high electronegativity of oxygen while those high. Therefore, it is not very reactive as such, O2  O  O .
of others are not. Therefore, dioxygen reacts at higher temperatures. However, once
(6) Magnetic character : Oxygen is paramagnetic while others are the reaction starts, it proceeds of its own. This is because the chemical
not. reactions of dioxygen are exothermic and the heat produced during the
reaction is sufficient to sustain the reactions.
Oxygen and its compounds
(1) Action with litmus : Like dihydrogen, it is also neutral and has
Oxygen is the most abundant element in the earth crust (46.5%). It no action on blue or red litmus.
was discovered by Karl Scheele and Joseph Priestley. It occurs in three (2) Reaction with metals : Active metals like Na, Ca react at room
isotopic forms : temp. to form their respective oxides.
16 17 18
8O 8O 8O 4 Na  O2  2 Na 2 O ; 2Ca  O2  2CaO
( Abundance : 99 .76 %) ( Abundance : 0 .037 %) ( Abundance : 0 .204 %)
It reacts with Fe, Al, Cu etc. metals at high temperature
18
Out of the three isotopes, 8O is radioactive. 4 Al  3O2  2 Al2 O3 ; 4 Fe  3O2  2 Fe2 O3
Occurrence : In free state, it occurs in air and constitutes 21% by (3) Action with Non-metals : It form oxides.
volume of air. 1073 K
Preparation of Dioxygen : Oxygen is prepared by the following 2 H 2  O 2     2 H 2 O ;
Electricdischarge
methods.
(1) By the decomposition of oxygen rich compounds : e.g. N 2  O 2   2 NO
3273 K
Nitricoxide
2 KNO 3   2 KNO 2  O2 ; 2 KClO3 
Heat
 2 KCl  3 O 2
Heat

Pot. Nitrate Pot. Chlorate MnO 2 S  O2  SO 2 ; Heat

C  O2   CO 2
Heat

(2) By heating dioxides, Peroxides and higher oxides : e.g. (4) Reaction with compounds : Dioxygen is an oxidising agent and
2 Ag 2 O   4 Ag  O 2 ;
Heat
3 MnO2   Mn3 O4  O 2
Heat it oxidises many compounds under specific conditions. e.g.
Silver oxide Manganese dioxide 700 K
4 HCl  O2   2 H 2 O  2Cl 2 ;
 2 BaO  O 2
Heat CuCl 2
2 BaO2
Barium peroxide Barium oxide
 s and p-Block Elements 739

4 NH 3  5 O2   4 NO  6 H 2 O
1073 K Suboxides : These oxides contain less oxygen than expected from
Pt the normal valency. For example, N 2 O.
CS 2  3O2   CO 2  2SO 2 ;
Heat
Mixed oxides : These oxides are made up of two simple oxides. For
example, red lead Pb3 O4 (2 PbO2  PbO2 ), magnetic oxide of iron,
CH 4  2O2  CO 2  2 H 2 O
Fe3 O4 (FeO  Fe2 O3 ) and mixed oxide of manganese,
Uses of dioxygen
Mn3 O4 (MnO2  2 MnO).
(1) It is used in the oxy-hydrogen or oxy-acetylene torches which are
used for welding and cutting of metals. Ozone or trioxygen
Ozone is an allotrope of oxygen. It is present in the upper
(2) It is used as an oxidising and bleaching agent,
atmosphere, where it is formed by the action of U. V. radiations on O 2 ,
(3) Liquid O 2 is used as rocket fuel.
3 O 2    2O 3 .
U. V . radiation
(4) It is used in metallurgical processes to remove the impurities of Ozone
metals by oxidation. O 3 protects us from the harmful U. V. radiations which causes
Compounds of Oxygen skin cancer. Now a days, ozone layer in the atmosphere is depleting due to
(1) Oxides : A binary compound of oxygen with another element is NO released by supersonic aircrafts and chlorofluoro carbons (CFC’S) i.e.
called oxide. On the basis of acid-base characteristics, the oxides may be freon which is increasingly being used in aerosols and as a refrigerant.
classified into the following four types, Preparation : Ozone is prepared by passing silent electric discharge
(i) Basic oxides : Alkali, alkaline earth and transition metals form through pure, cold and dry oxygen in a specially designed apparatus called
ozoniser. The formation of ozone from oxygen is an endothermic reaction.
basic oxides - Na 2 O, MgO, Fe2 O3 etc. their relative basic character
Silent electric
decreases in the order : alkali metal oxides>alkaline earth metal 3O2 2O 3 H  285.4 kJ
oxides>transition metal oxides. discharge

(ii) Acidic oxides : Non-metal oxides are generally acidic - Ozone is prepared in the laboratory by the following two types of
CO 2 , SO 2 , SO 3 , NO 2 , N 2 O5 , P4 O10 , Cl 2 O7 etc. ozonisers,
(a) Siemen’s ozoniser, (b) Brodie’s ozoniser
(iii) Amphoteric oxides : Al2 O3 , SnO 2 etc. For the better yield of ozone : (a) Only pure and dry oxygen should
be used. (b) The ozoniser must be perfectly dry. (c) A fairly low
(iv) Neutral oxides : H 2 O, CO, N 2 O, NO etc.
temperature ( 273 K) must be maintained. (d) The electric discharge
Trends of oxides in the periodic Table : On moving from left to the must be sparkless.
right in periodic table, the nature of the oxides change from basic to Physical properties : Ozone is a light blue coloured gas, having
amphoteric and then to acidic. For example, the oxides of third period has pungent odour. It is heavier than air. Its vapour density is 24. It is slightly
the following behaviour, soluble in water.
Cl 2 O7 Chemical properties : The important chemical properties of ozone
Na 2 O Al2 O 3 SiO2 P4 O10 SO 2 are discussed below,
MgO very
strongly amphoter weakly strongly (1) Decomposition : Pure ozone decomposes on heating above 475
basic acidic strongly
basic ic acidic acidic
acidic K to form O 2 gas.
Basic to acidic character increases 2O 3   3O2 H  285.4 kJ
475 K

However, on moving down a group, acidic character of the oxides (2) Oxidising agent : Ozone is one of the most powerful oxidising
decreases. For example in the third group, the acidic character of oxides agent with the liberation of dioxygen. In fact, ozone is a stronger oxidising
decreases as: agent than molecular oxygen because ozone has higher energy content and
decomposes to give atomic oxygen as:
B 2 O 3 acidic Al2 O 3 Ga 2 O 3 (weakly In2 O 3 , Tl 2 O 3
O3  O2  O
amphoteric basic) basic Atomic oxygen
Therefore, ozone oxidises a number of non-metals and other
Acidic to basic character increases reducing agents. e.g.
On the basis of oxygen content the oxides may be classified into the 2 Ag  O3  Ag 2 O  O 2 ; S  3O 3  SO 3  3O 2
Metal Silver oxide Non metal
following types,
Normal oxides : These contain oxygen atoms according to the PbS  4 O 3  PbSO 4  4 O 2
Compound
normal oxidation number i.e. – 2. For example, MgO, H 2 O,
Mercury is oxidised to mercurous oxide,
CaO, Li 2 O, Al2 O3 etc. 2 Hg  O3  Hg 2 O  O 2
Polyoxides : These contain oxygens atoms more than permitted by Mercurous oxide

the normal valency. Therefore, these contain oxygen atoms in oxidation state
different than –2.
Peroxides : These contains O 22  ion having oxidation number of
oxygen as –1. For example,
H 2 O2 , Na 2 O2 , BaO2 , PbO2 etc.
Superoxides : These contains O 2 ion having oxidation number of
oxygen as –1/2. For example, KO 2 , PbO2 , etc.
During this reaction mercury loses its meniscus and starts sticking
to the sides of the glass. This is known as tailing of mercury. Mercurous
oxide formed in this reaction dissolves in mercury and starts sticking to the
glass surface.
(3) Bleaching agent : Due to the oxidising action of ozone, it acts as
a mild bleaching agent as well as a sterilizing agent. It acts as a bleaching
agent for vegetable colouring matter.
Vegetable colouring matter  O3  Oxidised coloured matter O2
(Colourless )
 740 s and p-Block Elements
For example, ozone bleaches indigo, ivory, litmus, delicate fabrics
etc.
(4) Formation of ozonides : Ozone reacts with alkenes in the
presence of CCl 4 to form an ozonide. e.g.
O

CH 2  CH 2  O 3   H 2 C
CCl 4
CH 2
Ethylene
(4) Colloidal or  -sulphur : It is prepared by passing H 2 S
O O through a solution of an oxidizing agent or water or by treating sodium
Ethylene ozonide
thiosulphate with dil. HCl.
Structure of O : The structure of O 3 molecule is angular as shown
3 Properties of sulphur : It burns in air with, a blue flame forming
in fig. The O  O  O bond angle is 116.8° and O  O bond length is 128 SO 2 , gives sulphur hexafluoride with F2 and sulphur mono chloride
pm. with Cl 2 , sulphides with metals like Na, Ca, Zn, Hg, Fe, Cu etc., reduces
O HNO 3 to NO 2 and H 2 SO 4 to SO 2 . With NaOH solution on heating,
12816.8°pm 12816.8°pm
116.8° S 8  12 NaOH  4 Na 2 S  2 Na 2 S 2 O3  6 H 2 O .
O O It gives sodium sulphide and sodium thiosulphate, with excess of
Uses of ozone
sulphur, 2 Na 2 S  S 8  2 Na 2 S 5 .
(1) O 3 is used for disinfecting water for drinking purposes because
Uses of sulphur : It is used in the manufacture of matches, gun
ozone has germicidal properties. powder (mixture of charcoal, sulphur and potassium nitrate), explosives and
(2) It is used for purifying air of crowded places such as cinemas,
fire works SO 2 , H 2 SO 4 , CS 2 and dyes, sulpha drugs and ointment for
under ground railway, auditoriums, tunnels, mines etc.
curing skin diseases and in the vulcanization of rubber.
(3) It is used in industry for the manufacture of KMnO4 , artificial Compounds of Sulphur
silk, synthetic camphor etc. (1) Hydrogen Sulphide : It is prepared in the laboratory by the
Sulphur and its compounds action of dil. H 2 SO 4 on ferrous sulphide in kipp’s apparatus,
Sulphur is the second member of oxygen family and belongs to
group-16 (VI A) of the periodic table. FeS  H 2 SO 4  FeSO 4  H 2 S . It is colourless gas having foul smell
Occurrence : Sulphur occurs in the earth’s crust to the extent of resembling that of rotten eggs. It reacts with many cations (of group II and
0.05%. It occurs in the free state as well as in combined state. Sulphur IV) to give coloured sulphides,
occurs mainly as sulphides and sulphates. eg. Cu 2  S 2  CuS ; Cd 2  S 2  CdS ;
Black ( Yellow)
Table 18.8
2 2 2 2
Sulphide Ores Sulphate Ores Ni S  NiS ; Co S  CoS
(Black) (Black)

Iron pyrites (fool’s gold) – FeS 2 Gypsum – CaSO 4 .2 H 2 O The solubility of sulphides can be controlled by the H  ions
Galena – PbS Epsom salt – MgSO4 .7 H 2 O concentration and therefore, H 2 S finds extensive use in qualitative
analysis of cation radicals.
Copper pyrites – CuFeS 2 Barytes – BaSO 4
: :
Cinnabar – HgS Zinc blende – ZnS S
Extraction of sulphur (Frasch process) : Sulphur is generally 93.3O
extracted from underground deposits by drilling three concentric pipes upto
the beds of sulphur (700 – 1200 feet deep). H H
(2) Halides of sulphur : Two important halides of sulphur are SF4
Allotropy in sulphur : Sulphur exists in four allotropic forms,
(1) Rhombic or octahedral or -sulphur : It is a bright yellow solid, and SF6 .
soluble in CS 2 and stable at room temp. All other varieties of sulphur (i) Sulphur tetrafluoride : SF4 is formed by the reaction of
gradually change into this form on standing. sulphur with CoF3 .
(2) Monoclinic sulphur or prismatic or -sulphur: It is prepared by S  4 CoF3  SF4  4 CoF2
melting the sulphur and then cooling it till a crust is formed. On removing
the crust, needle shaped crystals of monoclinic sulphur separate out. It is It is a colour gas which is quite reactive. It is hydrolysed with water.
dull yellow in colour, soluble in CS 2 and stable only above 369K. Below SF4  2 H 2 O  SO 2  4 HF
this temperature it changes into rhombic form. It is used for fluorinating inorganic and organic compounds.
Thus, at 369K both these varities co-exist. This temperature is Structure : It has see-saw structure with sp 3 d -hybrdization and is
called transition temperature and the two sulphurs are called enantiotropic derived from triogonal bipyramid geometry in which an equatorial position
substances. It also exist as molecules similar to that of rhombic sulphur but is occupied by a lone pair of electrons.
the symmetry of the crystals is different. F
(3) Plastic or amorphous or  -sulphur : It is a super cooled liquid F
insoluble in CS 2 , soft and amorphous. It consists of long zig-zag chains of : S
S-atoms.
F
F
.. .. ..
:S ..S S:
.. O
105 C ..
..S .. ..S
..S
.. ..
S S
 s and p-Block Elements 741

(ii) Sulphur hexafluoride : SF6 is prepared by burning sulphur in a SO 2 molecule has a bent structure with a O – S – O bond angle
stream of fluorine. OF is not known though sulphur forms SF . This is because
6 6
of 119 . Sulphur is sp 2 hybridized.
o

oxygen has no d -orbitals in its valence shell. ..

SF6 is a colourless gas. It is extremely inert substance even at red
heat. It does not react with water. on account of its chemical inertness and
S
p – d
dielectric strength, it is used as an insulator in high voltage generators and p – d
119O
switch-gears.  

Structure : It has an octahedral structure with sp 3 d 2 - O O

(ii) Sulphur trioxide (SO ): It is formed by the oxidation of SO 2 .
3

hybridisation around the central sulphur atom.

Therefore, all S  F bond distances are equal in its structure. 2SO 2  O2  2SO 3700 K , 2 atm.
V2O5
F F
F In the gaseous phase, it exists as planar triangular molecular species
S involving hybridization of the S-atom. It has three S–O  bonds and three
F F S–O  bonds. The O–S–O bond angle is of 120 .
F o

(3) Oxides of sulphur : Sulphur forms several oxides of which O

sulphur dioxide (SO 2 ) and sulphur trioxide (SO 3 ) are most important.
p – 
(i) Sulphur dioxide (SO ) : It is prepared by burning sulphur or iron d
S
2

pyrites in air. p – p –
S 8  8 O2  8 SO 2 ; 4 FeS 2  11O2  2 Fe2 O3  8 SO 2 d

120O

d

In laboratory, it is prepared by heating copper turnings with conc. O O

(4) Oxyacids of sulphur : Sulphur forms many oxyacids. Some of
H 2 SO 4 these are,
Cu  2 H 2 SO 4  CuSO 4  SO 2  2 H 2 O
It is a colourless gas with irritating and suffocating smell.
Table : 18.9 Oxyacids of sulphur
Formula Name Important properties Structural formula
H 2 SO 3 (+4) Sulphurous acid Free acid does not exist diprotic, ..
strong reducing agent O  S  OH
|
OH
H 2 SO 4 (+6) Sulphuric acid Stable diprotic, dehydrating agent O
||
(Oil of vitriol) O  S  OH
|
OH
H 2 S 2 O 3 (–2 and +6) Thiosulphuric acid Free acid does not exist but its salts S
e.g. Na 2 S 2 O 3 All quite stable ||

reducing agent O  S  OH
|
OH
H 2 S 2O4 (+3) Dithionous acid O O
|| ||
HO  S  S  OH
H 2 S 2 O 6 (+5) Dithionic acid Free acid is moderately stable but its O O
salts are quite stable. || ||
OS— S O
| |
OH OH
H 2 S 2 O7 (+6) Disulphuric acid Strong oxidising agent O O
(Pyrosulphuric acid) || ||
(Oleum) O  S O S  O
| |
OH OH
H 2 SO 5 (+6) Peroxomonosulphuric acid Stable crystalline solid, powerfull O
(Its salts known as persulphates) oxidising agent ||
(Caro's acid) HO  S — OOH
||
O
H 2 S 2 O 8 (+6) Peroxodisulphuric acid Strong oxidising agent. O O
(its salts are known as disulphates) || ||
(Marshals acid) O  S  OO S  O
| |

OH OH