Nitrogen family

The p-block elements

having five electrons in their
Valence shell and placed in 15th/orVA) group are

collectively known as
phicogens
ar
phictogens .

Element NP As Sha Bi
- - ~

Non-metals metalloids metal

A
2
Thes heavier members show
common of + 3
o .
s .
, +5

y saty fght
3+
.
2

BSAA
- physical state :
Nitrogen is
gas ,
phosphorus is

wax solid ,
while rests are solids

metallic listure
having -

and except N2 solid under room temp.

>
-
All are
polyatomic ,
all are

>
- Mp . .
increases from nitrogen to arsenic and then decreases -

much
>
- M .

p .

of phosphorus is heavier than that of nitrogen

due to atomicity and molecular .
mass

* Atomic radi : Atomic rade increases down the

group
& decreases down the
Ionisation energy
while It group
i P As Sh Bi

At .
radicts 0 .

70 1 10
.
1 : 20
1 - %
150

1
. E (Kymot's 1402 2012 947 834 703
 d-subshell in V S
..
of
.

*
xoxid state : due to absence

while
tots
N can not expand its o . S ,

but down
rest can show of to os.
dur
decreases
the stability of 5
group effect
inest pair
.

to

Oxyacids of Nap intermediate unstable and

* in o S are
undergo
. .

disproportionation .

+
1 +3
+3 +5

HPO2(aq) >
-
2
MP3
+
e
+
Phy
. 3HNO(ay)
g >MNOz + INO + H
.

+5 3 ↓ +5

L (aq)
=

-
HPO + By
As n00p
+
Phy

* god period elements show

exceptional behaviour from rest of the

-
elements
EN
is due to small siz & high
is d'orbitals valence shell
.
absence of in

Ny is considered to be an inest (non-reactive) due to

↑
gas very
high NEN bond energy , however
,

bond weaker than

single
N-N0-0 F-F is
single P-p/s s(a-a =

bond small size & Lop-L p . .

repulsion .

chemical properties :

1 . oxides :

ill
a the elements of group 15
form oxides
of the
type -

X 203 Y204 , X205,

b)Down the group ENI ,

hence acidic nature
of
oxide ↓ and
among
the oxides
of same element
acidic nature
.

higher the 0 S greater is the .

.
 down the
-) stability of oxide of higher 0 S decreases
.
.

to inext pair
gromp (due effect) .

9) Besides there three oxides , nitrogen forms two

more oxides N20 & NO
(Neutral oxides)
& Due to
pa-er multiple
bond oxides
of P As
, ,
56
,
ii

to their oxides
leads
cage structure
of oxides and

exist as dimers ErOb & Eg0 , o

② Hydrides :

9) All the elements of group-15 form volatile

hydride
of type EMs .

b) All the
hydrides are colourless gases Their smell .

becomes more and more

disagreeable from N to Bi

soluble in water due to rrbonding

> NU is
highly
,

,
while other hydrides are less soluble
.

↓ saria nature , I reducing

thermal stability nature
)
decreases from NU, to Billy
③ Halides of nitrogen family :

① Tribalides :
D
E
i All the elements of nitrogen family Y

is
towm
ill
trihalides
trihalides
.

of nitrogen family
elements have pyramidal
structur

ii) Except Bitz ,

all other trihalides are covalent and covalent
character decreases down the
group .
is Trihalides of nitrogen family elements (except NE &
Bits/get easily
hydrolysed by water
.

NN3 +
310 >
-
bH04 + Nhy
120 Sboc + 241
Sbiy >
-
+

pay + 3120 120 >

- Bioc Rus1
Hypoz
>
- + +
+ Tue
Bicy
Aszoy + Guat
CAsely +
3420 >
-

the order
vis Tendency towards
hydrolysis follows
N PJ As) Sb] Bi

vill Tribalides of P , As & Sh with fluoride (f) act as Levis ad.

SbE3 + 30 -> [SbF5]28

4
 NITROGEN FA MILY
1. NITROGEN (N 2 )

Preparation

(a) NH 4NO 2  N 2 + 2H 2 O

(b) (NH4)2Cr2O7  N2 + 4H2O + Cr2O3
(c)

Ba(N3) 2  Ba + 3N2  Purest N2 obtained
 
2NaN 3  2Na + 3N 2  by this method

(d) 2 NH 3 + 3NaOCl  N 2 + 3NaCl + 3H 2O

(e) 2NO  2Cu  2CuO  N 2

red over heated Black

(f) Cl2 passed into liquor NH3

3Cl 2 + 2NH 3  N 2 + 6HCl
6NH 3 + 6HCl  6NH 4 Cl
-----------------------------------------------------
3Cl2 + 8NH 3  N 2 + 6NH 4Cl
In this method NH3 conc. should not be lowered down beyond an particular limit.
3Cl2 + NH3  NCl3 + 3HCl
(Trimendously explosive)
P r op e r t i e s
(a) It is inert due to high bond energy.
(b) It is absorbed by hot metal like Ca, Mg, Al etc.
3Ca + N2  Ca3N2
2Al + N2  2AIN

Al2O3 + 3C + N2  2AIN + 3CO
Inorganic graphite (BN) x ! White slippery solid having 2D-sheet structure.
(BN) x   (BN) x
3000 ºC

3–D network structure similar to diamond (Borazon) which is harder than diamond and used for dimond cutting.

Na 2B 4O 7 + 2NH 4 Cl  2NaCl + 2NH 3 + 2B 2 O 3 + H 2 O

B 2O 3 + 2NH 3  2BN + 3H 2 O
(c) N2 can be absorbed by calcium carbide at the temp around 1000ºC

CaC 2  N 2 
1000 º C
 CaNCN
 (It is very good fertiliser)
nitrolim
Cyanamide ion 2
N – C N

N = C =N
(Ca(NCN)+ C) + 3H 2O CaCO 3 + 2NH 3 + C

Slowly decomposes
NH2–CO–NH2
(Intermidiate formed)
2. AMMONIA (NH 3 )
Preparation
–
Nitrate or nitrite reduction : NO 3 /NO 2 + Zn /Al + NaOH  NH3 + [Zn(OH)4]2–/ [Al(OH)4]–
–
(a)
(b) Metal nitride hydrolysis : N3– + 3H2O  NH3 +3OH –
(c) Haber's process : N2 + 3H2 
450 º C
200-1000atm
 2NH3
 catalyst Fe/Mo
No te : NH3 can't be dried by H2SO4, P2O5 and anhydrous CaCl2 because –
2NH3 + H2SO4  (NH4)2SO4
H2O + NH3 + P2O5  (NH4)3PO4
CaCl2 + 8NH3  CaCl2.8 NH3 (forms adduct)
Quick lime is used for this purpose
CaO + H2O  Ca(OH)2 (base) 
 Hence no interaction
NH3 (base) 

Properties
(a) It dissolves several electropositive metals like Li, Na, K, Rb, Cs, Sr, Ba etc.

Ex. K in liq NH3  (i) Blue in colour

(ii) Conducts electricity

(iii) Having reducing property

K K+ + e–

K+(NH3)n e (NH3)x It is the cause

solvated e
– for above property

K 2 [Ni(CN ) 4 ] 
K in liq
NH 3

 K 4 [Ni(CN ) 4 ]
Square planar Tetrahedral

(b) Ag(NO3) (aq) + BaCl2 (aq)   AgCl  + Ba(NO3)2

Filtrate Residue
Ba(NO3)2 AgCl
liq NH3 Ba(NO3)2
crystal –
Cl– + [Ag(NH3)2]+ BaCl2 +[Ag(NH3)2]++NO3

(c) CH3COOH is strong acid in liquid NH3 while in water is weak acid.
–


AcOH  AcO + H+



NH3 + H+  NH 4 and H2O + H+  H3O+
Basisity order NH3 > H2O
(d) Hydrolysis and Ammonolysis occurs is a same way.

SiCl4 + 4H2O  4HCl + Si(OH)4  Si3O2 + 2H2O

SiCl4 + 8NH3  4NH4Cl + Si(NH2)4  Si3N2 + NH3
Rate of hydrolysis and Ammonolysis will be affected by the presence of HCl vapour & NH4Cl vapour
respectively.
 (e) NH 4 – Salts Preparation
NaNO3
Gypsum suspension saturated CaCO3 + (NH4)2SO4 NH4NO3
with NH3 and CO2 passed
NaCl
NaNO2 CaCO3
NH4(NO2) NH4Cl (NH4)2CO3

3. OXIDES OF NITROGEN

Preparation and Properties of Oxides of Nitrogen

Formula Name Preparation & Structure Properties

N2O Dinitrogen monoxide NH4NO3  N2O + 2H2O Colourless gas, rather

(Nitrous oxide) N  N  O (sp, Linear polar molecule) unreactive, diamegnatic
Laughing gas neutral to litmus

NO Nitrogen monoxide (a) 3Cu + 8HNO3  3Cu(NO3) 2 + 2NO Colourless gas,

(b) 4NH3 + 5O2    4NO + 6H O

Pt
(Nitric oxide) 0 2
paramagnetic, Neutral to
900 C
litmus

NO2 Nitrogen dioxide Pb(NO3)2  2PbO + 4NO2 + O2 Brown gas, reactive,

Mixed anhydride N paramagnetic, angular

132º
O O and polar

2NO2 HNO2 + HNO3

N2O3 Dinitrogen trioxide NO + NO2 N 2O 3 Dark blue in liquid (–30ºC)

or solid state, unstable

O = N – O – N = O or in the gas phase
O
O=N–N N 2O 3   2HNO 2
H2O

N2O4 Dinitrogen tetroxide 2NO2 N 2O 4 Colourless, exists in

O O O equilibrium with NO 2
2N N– N both in the gaseous and
O O O liquid state, in solid state,
N2O 4 is unstable.

N2O 5 Dinitrogen pentoxide 2HNO3 + P 2O 5  H2O + N2O 5 No existance in gas phase,

H2O + P2O5  2HPO 3 in the solid state exists as
nitronium nitrate
O O
+
[NO 2] [NO 3] –
N N
O
O O
4. NITROUS ACID (HNO 2 )
Preparation
dil.acid
(a) M-nitrite 
HCl or H2 SO 4
 HNO
2

(b) N2O3 + H2O  2HNO2

Properties

(a) Oxidising property : Because of its easy oxidation to liberate nascent oxygen, it acts as a strong oxidant
2HNO2  H2O + 2NO + (O)

2KI + 2HNO2 + 2HCl  2KCl + 2H2O + 2NO + I2

SnCl2 + 2HNO2 + 2HCl  SnCl4 + 2NO + 2H2O
SO2 + 2HNO2  H2SO4 + 2NO
H2S + 2HNO2  2H2O + S  + 2NO
2FeSO4 + 2HNO2 + H2SO4  Fe2(SO4)3 + 2NO + 2H2O
Na3AsO3 + 2HNO2  Na3AsO4 + 2NO + H2O
(b) Reducing property : Nitrous acid also acts as a reducing agent as it can be oxidised into nitric acid.
HNO2 + (O)  HNO3
2KMnO4 + 5HNO2 + 3H2SO4  K2SO4 + 2MnSO4 + 5HNO3 + 3H2O
K2Cr2O7 + 3HNO2 + 4H2SO4  K2SO4 + Cr2 (SO4)3 + 3HNO3 + 4H2O
H2O2 + HNO2  H2O + HNO3
2HNO2 + NH2CONH2  2N2 + CO2 + 3H2O
Urea
HNO2 + NH3  NH4NO2  N 2 + 2H2O
HNO 2 + C 2H 5NH 2  C 2H 5OH + N 2 + H 2O
5 º C
HNO2 + C6H5 - NH2 · HCl  C6H5N = NCl + 2H2O
Benzene diazonium chloride

5. NITRIC ACID (HNO 3 )

It was named aqua fortis (means strong water) by alchemists.

Preparation

(a) Laboratory Method

KNO3 + conc. H2SO4  KHSO4 + HNO3 (vap)
vapours of nitric acid evolved are condensed in a glass receiver.
(b) Industrial Preparation
(i) Birkeland Eyde Process or arc process
3000 º C
Step 1 N2 + O2  

Electric Arc 2NO - heat
Step 2 NO + O2  NO2
Step 3 NO2 + H2O  HNO2 + HNO3
Step 4 HNO2  HNO3 + NO + H2O
(ii) Ostwald's Process
Pt.gauze
Step 1 NH3 + O2 
700 –800 º C

 2NO - heat

Step 2 NO + O2  NO2

Step 3 NO2 + H2O  HNO2 + HNO3
Step 4 HNO2  HNO3 + NO + H2O

Physical Properties

Nitric acid usually acquires yellow colour due to its decomposition by sunlight into NO2.
sunlight
4HNO3   4NO2 + 2H2O + O2

The yellow colour of the acid can be removed by warming it to 60-80ºC and bubbling dry air through it. it has
extremely corrosive action on the skin and causes painful sores.
Chemical Proper t ie s
It is very strong acid and it exhibits usual properties of acids. It reacts with basic oxides, carbonates, bicarbonates
and hydroxides forming corresponding salts.
CaO + 2HNO3  Ca(NO3)2 + H2O
Na2CO 3 + 2HNO3  2NaNO 3 + H 2O + CO 2
NaOH + HNO3  NaNO3 + H2O
Oxidising nature : Nitric acid acts as a strong oxidising agent as it decomposes to give nascent oxygen easily.
2HNO3  H2O + 2NO2 + O
or 2HNO3  H2O + 2NO + 3O
(a) Oxidation of non-metals : The nascent oxygen oxidises various non-metals to their corresponding
highest oxyacids.
(i) Sulphur is oxides to sulphuric acid

conc.and hot
S  6HNO 3   H2SO4 + 6NO2 + 2H2O

(ii) Carbon is oxidised to carbonic acid

C + 4HNO3   H2CO3 + 4NO2 + 2H2O

(iii) Phosphorus is oxidised to orthophosphoric acid.

conc.and hot
2P  10HNO 3   2H3PO4 + 10NO2 + 2H2O

(iv) Iodine is oxidised to iodic acid

conc.and hot
I 2  10HNO 3    2HIO3 + 10NO2 + 4H2O

(b) Oxidation of metalloids : Metalloids like non-metals also form highest oxyacids
(i) Arsenic is oxidised to arsenic acid

As + 5HNO3 
conc.and hot
 2H3AsO4 + 5NO2 + H2O
(ii) Antimony is oxidised to antimonic acid
conc.and hot
Sb + 5HNO3   2H3SbO4 + 5NO2 + H2O
(iii) Tin is oxidised to meta-stannic acid.
Sn + 2HNO3  H2SnO3 + 4NO2 + H2O
(c) Oxidiation of compounds
(i) Sulphur dioxide is oxidised to sulphuric acid
SO2 + 2HNO3  H2SO4 + 2NO2
(ii) Hydrogen sulphide is oxidised to sulphur
H2S + 2HNO3  2NO2 + 2H2O + S
(iii) Ferrous sulphate is oxidised to ferric sulphate in presence of H2SO4
6FeSO4 + 3H2SO4 + 2HNO3  3Fe2(SO4)3 + 2NO + 4H2O
(iv) Iodine is liberated from KI.
6KI + 8 HNO3  6KNO3 + 2NO + 3I2 + 4H2O
(v) HBr, HI are oxidised to Br2 and I2, respectively.
2HBr + 2HNO3  Br2 + 2NO2 + 2H2O Similarly
2HI + 2HNO3  I2 + 2NO2 + 2H2O
(vi) Ferrous sulphide is oxidised to ferric sulphate
FeS + 8HNO3  Fe2(SO4)3 + 8NO2 + 4H2O
(vii) Stannous chloride is oxidised to stannic chloride in presence of HCl
2HNO3 + 14H  NH2OH + NH3 + 5H2O
Hydroxylamine
NH3 + HNO3  NH4NO3
----------------------------------------------------------------------------------------------------------------------
7SnCl2 + 14 HCl + 3HNO 3  7SnCl 4 + NH2 OH + NH 4NO 3 + 5H 2O
(viii) Cane sugar is oxidised to oxalic acid
C 12H 22 O 11 + 36 HNO 3  6(COOH) 2 + 36NO 2 +23H 2 O
Action on Metals : Nitric acid reacts with most of the metals except noble metals like gold and platinum.
Towards its reaction with metals, HNO3 acts as an acid as well as an oxidising agent. Like Other acids, HNO3
liberate nascent H from metals which further reduces the nitric acid into number of products like NO, NO 2,
N2O, N2, NH2OH or NH3 according to the following reactions :
Metal + HNO3  Nitrate + H
2HNO3 + 2H  2NO + 2H2O
2HNO3 + 6H  2NO + 4H2O
2HNO3 + 10H  N 2 + 6H2O
2HNO 3 + 16H  2NH 3 + 6H 2O
The progress of the reaction is controlled by a number of factors :
(a) The nature of the metal
(b) The concentration of the acid,
(c) The temperature of the reaction
(d) The presence of other impurities
 C o n c en t r a t io n of n it r ic a c id M et a l M a in pr o d u c t s
Mg, Mn (2% ) H 2 + Metal nitrate
Very dilute HNO 3(6% )
Fe, Zn, Sn NH 4NO 3 + metal nitrate + H 2O
Pb, Cu, Ag, Hg NO + metal nitrate + H 2O
Dilute HN O 3 (20% ) Fe, Zn N 2O + metal nitrate + H 2O
Sn NH 4NO 3 + Sn(N O 3) 2
Zn, Fe, Pb, Cu, Ag, Hg NO 2 + metal nitrate + H 2O
Conc. HNO 3(70% )
Sn NO 2 + H 2SnO 3

Action on Proteins
(a) Nitric acid attacks proteins forming a yellow nitro compound called xanthoprotein. It, therefore, stains
skin and renders wool yellow. This property is utilized for the test of proteins.
(b) Oxidation : Number of organic compound are oxidised.
Sawdust catches fire when nitric acid is poured on it. Turpentine oil bursts into flames when treated with
fuming nitric acid. Toluene is oxidised to benzoic acid with dil. HNO3.
Structure
Nitric acid is a monobasic acid, i.e. the molecule consist of one hydroxyl group as it is formed by the hydrolysis
of nitryl chloride, NO2Cl. It may be structurally represented as below :

O
HO–N
O
Gaseous nitric acid is a planar molecule. The bond lengths and bond angles as present in the molecule are
represented in the figure :
H O
Å
22
6º 1.
0.

102º
11
96
Å

O N 130º
1.2
1.44Å 2Å
O
6. ALLOTROPIC MODIFICATIONS OF PHOSPHORUS
Phosphorus exists in a number of allotropic forms. These forms are :
(a) Yellow or white phosphorus (b) Red phosphorus (c) Black phosphorus

(a) White or yelllow phosphorus

Preparation
1200ºC
Bone ash or Apatite rock Ca3(PO4)2 + 3SiO2 3CaSiO3 + P2O5
(i) both have same formula 1500ºC
2P2O5 + 10C  P4 + 10CO
(Coke) white 'P'
conc.
(ii) Ca 3(PO4)2 + 3H2SO 4   3CaSO4 + 2H3PO 4
320ºC
H3PO4    HPO3
–H2O
meta phosphoric acid
1000ºC
12C + 4HPO3  2H2 + 12CO + P4
Coke white 'P'
Properties

(i) It has characteristic garlic smell and is poisonous in nature. Persons working with phosphorus develop a
disease in which the jaw bones decay. This disease is knwon as phossy jaw.
(ii) In contact w ith air, it undergoe s slow combustion and glows i n dark. This proper t y is called
p ho sp h or es c en c e .

(iii) Its ignition temperature is low (about 30° C). It readily catches fire giving dense fumes of phosphorus
pentoxide. It is, therfore, kept in water.

P4 + 5O2  P4O10 or 2P2O5

Structure

< P – P – P  60°

(b) Red phosphorus

Preparation

Red phosphorus is formed by heating yellow phosphorus, between 240–250° C, in presence of an inert gas.

240-250º C
White 'P'  Red 'P'
in an inert atm. like
N2 or CO2
I2 : catalyst

heated to 550ºC
Red 'P'  White 'P'
in an inert atm and then
rapid cooling to room temp.

Structure of red phosphorus :- It is regarded as a polymer consisting of chains of P 4 tetrahedral linked

together by covalent bond.
P P P P
P P P P P P P
P P P P
proposed molecular structue of red phosphorus

(c) Black P

Preparation : This is most stable form of Phosphorus

470 K
White(P)    Black P
at high P

Black P contain zig-zag & double layered structure.

Order of density & mp

 Black > Red > White

Comparison between White and Red Phosphorus

Property White phosphorus Red phosphorus

Physical state Soft waxy solid. Brittle powder.

Colour White when pure. Red.
Attains yellow colour
on standing.
Odour Garlic Odourless.
Solubility in water Insoluble. insoluble
Solubility in CS2 Soluble. Insoluble.
Physiological action Poisonous. Non-poisonous.
Chemical activity Very active. Less active.
Stability Unstable. Stable.
Phosphorescence Glows in dark Does not glow in dark.
Reaction with NaOH Evolves phosphine. No action.
Molecular formula P4 Complex polymer.

7. PHOSPHINE GAS (PH 3 )

Preparation
uses of Phy
(a) 
4H3PO3    PH3 + 3H3PO4
d . Holme's
Signal : containers
CaPe&cal ,
having
is pierced
(b) PH4I + KOH KI + PH3 + H2O  water which

and dropped in sea burns

(PH3 + HI)  purest PH 3 with flame & fumes giving signal

(c) 2AIP + 3H 2SO 4 Al 2(SO 4)3 + PH 3 
used
making smoke
in screen :
2
Physical proper it ie s
.

+ Calon) 2+ Po
(a) It is having 'rotten fish' smell. CP2 +
10-ph
↓
+
Br
(b) It is soluble in CS2 and insoluble in water. +
Oz(Air)
Pa0o(cloud)
–
PH3 + H2O PH + OH
in s-orbital, so donating capacity is less

Note : PH 4 is formed with acids.

(c) Like NH3, PH3 also can form addition product.

CaCl2 • 8NH3, Cu2Cl2 • 2PH3, AlCl3 • 2PH3, SnCl4 • 2PH3

PH3 can be absorbed by Ca(OCl)Cl.

PH3 + 3Ca(OCl)Cl + 3H2O  PCl3 + 3HCl + 3Ca(OH)2

2NH3 + 3Ca(OCl)Cl  N2 + 3CaCl2 + 3H2O

 Chemical properties

(a) PH3 + O3 

150 º
  P2O5 + H2O
(b) PH3 + 3Cl2  PCl3 + 3HCl
electrical
(c) PH3 + 4N2O 
sparking
  H3PO4 + 4N2

(d) 2PH3 + 3CuSO4 Cu3P2  + 3H2SO4

Detection of PH3 Black ppt.

(e) PH3 + 6AgNO3   Ag 3 P •3AgNO 3   + 3HNO3

Yellow ppt.

Ag3 P • 3AgNO3 + 3H2O  6 Ag  + 3HNO3 + H3PO3

Balck ppt.

(f) PH3 + 4HCHO + HCl  [P (CH 2 OH ) 4 ] Cl – (which is used for making fire-proof cotton fabrics)
white / colourless solid

8. OXIDES OF PHOSPHORUS

It forms three important oxides which exist in dimeric forms.

Phosphorus trioxide (P 4 O 6 )

Preparation

Phosphorus trioxides is formed when phosphorus is burnt in a limited supply of air.

P4 + 3O2 (limited)  P4O6

Properties

(a) Heating in air : On heating in air, it forms phosphorus pentoxide.

P4O6 + 2O2 P4O10
Phosphorus (V) oxide
(b) Action of water : It dissolves in cold water to give phosphorus acid.
P4O6 + 6H2O (cold)  4H3PO3
Phosphorus acid
It is, therefore, considered as anhydride of phosphorus acid.
No te : With hot water, it gives phosphoric acid and inflammable phosphine.

Structure ••
P

(a) Each atom of phosphorus in P4O6 is present at the corner of a tetrahedron O O

(b) Each phosphorus atom is covalently bonded to three oxygen atoms and O P
••

P
••

each oxygen atom is bonded to two phosphorus atoms.

O
O O
(c) It is clear from the structure that the six oxygen atoms lie along the edges
P
••
of the tetrahedron of P atoms. Structure of P4O6
Phosphorus (V) oxide (P 4 O 10 )

Preparation : It is prepared by heating white phosphorus in excess of air.


P4 + 5O2 (excess)  P4O10

Properties

(a) It is snowy white solid.

(b) Action with water : It readily dissolves in cold water forming metaphosphoric acid.
P4O10 + 2H2O (Cold)  4HPO3
Metaphosphoric acid.
With hot water it gives phosphoric acid.
P4O10 + 6H 2O (Hot)  4H3PO 4
Phosphoric acid
(c) Dehydrating nature : Phosphorus pentoxide has strong affinity for water and, therefore, acts as a
powerful dehydrating agent. It extracts water from many inorganic and organic compounds.
(d) P4O10 is a very strong dehydrating agent and extracts water from many compounds including sulphuric
acid and nitric acid.
P4O10
2HClO4   Cl2O7
– H2O
Chlorine (VII) oxide

P4O10
2CH 3 CONH 2  CH 3 CN
– H2O
Acetamide Methyl cyanide

Str uc tu re O
(a) Its structure is similar to that of P4O6.
P
(b) In addition, each phosphorus atom forms a double bond with oxygen
atom as shown in figure. O O

O P O P O
O
O O
P

O
Mus
>
- d - A 6 - 2 11 -
3 16 3
-

1 1
C -

7 -
3 12 -

17 - 4
3 - 4 8 -
3 13-2 18 - 3
* 2 g 4
14-419-3
-
-

5 -
310 -
3 15 4
-
2 20 -
 OXYGEN FA MILY
1. OXYGEN (O 2 )

Preparation

(a) From oxides

(i) By thermal decomposition of the oxides

3MnO 2  Mn3O4 + O2

3Pb 3O 4  6PbO + O2

2BaO 2  2BaO + O 2
2HgO 
450 º C
 2Hg + O2
2Ag 2 O 
350 ºC
 4Ag + O2
(ii) By the action of water on sodium peroxide (Oxone)
2Na2O2 + 2H2O  4NaOH + O2
(iii) By the action of conc. H2SO4 on MnO2

2MnO2 + 2H2SO4  2MnSO4 + 2H2O + O2

(b) From salts
(i) Alkali metal nitrates on heating give out oxygen
2NaNO3  2NaNO 2 + O 2
2KNO3  2KNO2 + O2
(ii) KClO3, K2Cr2O7 and KMnO4 decompose at high temperatures evolving oxygen.
2KClO3 
400 º C
 2KCl + 3O2
4K2Cr2O7 
400 º C
 4K2CrO4 + 2Cr2O3 + 3O 2
2KMnO4 
250 º C
 K2MnO4 + MnO2 + O2
(iii) By heating KMnO4 or K2Cr2O7 with concentrated H2SO4.
4KMnO4 + 6H2SO4  2K2SO 4 + 4MnSO4 + 6H2O + 5O2
2K2Cr2O7 + 8H2SO4  2K2SO4 + 2Cr2(SO4)3 + 8H2O + 3O2
(iv) By adding H2O2 to acidified KMnO4 solution.
2KMnO4 + 3H2SO 4 + 5H2O2  K2SO4 + 2MnSO4 + 8H2O + 5O2
(c) Laboratory method
In laboratory, oxygen is prepared by heating of a mixture of potassium chlorate and manganese dioxide
in 4 :1 ratio. (MnO2 used as a catalyst)

2KClO 3 
MnO 2


 2KCl  3O 2
Potassiumchlorate

(d) Electrolysis of water : Electrolysis of either acidified water using platinum electrodes or alkaline water
using nickel electrodes is made in an electrolytic cell for obtaining oxygen and hydrogen.



H 2 SO 4   2
 2H  SO 4
1
At cathode : 2H+ + 2e  H2 At anode : 2OH–  H2O + O + 2e
2 2
 Properties
It is non inflammable but a supporter of combustion.
Some typical reactions of dioxygen –

H2O(g)

2. OZONE (O 3 )

Preparation

(a) Unstable deep blue, diamagnetic gas, with fishy smell. Toxic enough (more toxic than KCN). It's intense
blue colour is due to the absorption of red light.

(b) Ozonised oxygen is separated by passing into spiral tube cooled by liquid air. Ozone condense at –
112.4ºC. [B.P. of O2 – 183ºC ; B.P. of liquid air is – 190ºC]

2F2 + 2H2O 4HF + O2

F2 + 3H2O 6HF + O3

Properties

(a) Oxidising property

It is one of best oxidising agent, in acid solution, its standard, reduction potential value is 2.07V.

O3 + 2H+ + 2e  O2 + H2O Eº = + 2.07 V

(i) Metal Sulphides to Sulphates.

MS + 4O3  MSO4 + 4O2 [M = Pb, Cu, Zn, Cd]

(ii) 2HX + O3 X2 + H2O + O2 [X= Cl, Br, I]

(iii) NaNO2 + O 3  NaNO3 + O 2

Na2SO3 + O3  Na2SO4 + O2

Na3AsO3 + O3  Na3AsO4 + O2

(iv) S + H2O + 3O3  H2SO4 + 3O2

2P + 3H2O + 5O3  2H3PO4 + 5O2

2As + 3H2O + 5O3  2H3AsO4 + 5O2

(v) Moist I2  HIO3 + 5O2

I2 + 5O3 + H2O  2HIO3 + 5O2

Dry I2  I4O9 (yellow)

2I2 + 9O3   I4O9 + 9O2

(vi) 2K2MnO4 + O3 + H2O  2KMnO4 + 2KOH +O2

2K4 [Fe(CN)6] + O3 + H2O  2K3 [Fe(CN)6] + 2KOH + O2

2FeSO4 + O3 + H2SO4  Fe2 (SO4)3 + O2 + H2O

(vii) 2KI (acidified) + O3 + 2HCl  I2 + 2KCI + H2O + O2

2KI(neutral)  O 3  2HCl  I2  2KOH  O 2 

 
KI  KOI  O estimated by this reaction.
KI  KOI  2HCl  2KCl  I2  H 2 O  3

I 2  2S 2 O 23   S 4 O 26   2I 

KI  3O 3  KIO 3  3O 2

alkaline 
KI  4O 3  KIO 4  4O 2

(viii) Hg loses its fluidity (tailing of Hg)

2Hg + O3  Hg2O + O2 Similarly

2Ag + O3  Ag 2 O + O2
Brown

(ix) BaO2 + O3  BaO + 2O2

H2O2 + O3  H2O + 2O2

Na2O2 + O3 + H2O  2NaOH + 2O2

(x) 2KOH + 5O3  2KO3 + 5O2 + H2O

Note: In all above reaction O3 gives up O2 but some reactions are there which consumes all O-atom.

 3SO2 + O3  3SO3

 3SnCl2 + 6HCl + O3  3SnCl4 + 3H2O

Absorbent

(a) Turpentine oil

(b) Oil of cinnamon

Uses

(a) Sterilizing water

(b) Detection of position of the double bond in the unsaturated compound.