S-BLOCK

Hydrogen peroxide
Laboratory Preparation:
(i) From Sodium peroxide: It is prepared in the laboratory by adding small amounts of sodium peroxide
to ice cold water.
Na
2
O
2
+ 2H
2
O 2NaOH + H
2
O
2
In place of cold water, dilute sulphuric acid (20%) can be used. Sodium peroxide in small amounts at a time
is added to cold 20% sulphuric acid.
Na
2
O
2
+ H
2
SO
4
Na
2
SO
4
+ H
2
O
2
The crystals of hydrated sodium sulphate (Na
2
SO
4
10H
2
O) are removed by cooling the solution. The
solution of hydrogen peroxide obtained always consists some dissolved sodium sulphate. The concentration
of H
2
O
2
is about 3%.
BaO
2
8H
2
O + H
2
SO
4
= BaSO
4
+ H
2
O
2
+ 8H
2
O
The barium sulphate formed is filtered off and a solution of H
2
O
2
is obtained.
The use of sulphuric acid has a disadvantage as it catalyses the decomposition of hydrogen peroxide
formed. In place of sulphuric acid, weak acids like orthophosphoric acid, carbonic acid are preferred.
Barium peroxide on treatment with orthophosphoric acid gives a precipitate of barium phosphate and
H
2
O
2
which goes into the solution.
3BaO
2
+ 2H
3
PO
4
Ba
3
(PO
4
)
2
+ 3H
2
O
2
ppt.
Insoluble barium phosphate is filtered off. The filterate consists of hydrogen peroxide.
The barium phosphate is decomposed by dilute sulphuric acid.
Ba
3
(PO
4
)
2
+ 3H
2
SO
4
3BaSO
4
+ 2H
3
PO
4
BaSO
4
is removed by filtration and orthophosphoric acid is used again.
Mercks process: H
2
O
2
can be obtained by passing a current of CO
2
through a cold pasty solution of
barium peroxide in water.
BaO
2
+ CO
2
+ H
2
O BaCO
3
+ H
2
O
2
Barium carbonate being insoluble is filtered off.
Manufacture of Hydrogen Peroxide
(i) Auto oxidation of 2-butyl anthraquinol
(ii) By Oxidation of isopropyl alcohol
(iii) Electrolytic process: In this process, the electrolysis of 50% sulphuric acid is carried out at low
temperature using platinum electrodes and a current of high density. Proxy disulphuric acid is formed.
2H
2
SO
4
2H
+
+ 2HSO
4

2HSO
4

H
2
S
2
O
8
+ 2e (anode)
peroxy
disulphuric acid
Peroxy disulphuric acid is distilled. Hydrolysis occurs and a distillate containing about 30% H
2
O
2
is obtained.
H
2
S
2
O
8
+ 2H
2
O 2H
2
SO
4
+ H
2
O
2
In place of 50% H
2
SO
4
, ammonium hydrogen sulphate dissolved in excess of sulphuric acid can be used
for electrolysis.
NH
4
HSO
4
NH
4
SO
4

+ H
+
At anode 2NH
4
SO
4

(NH
4
)S
2
O
8
+ 2e
Ammonium peroxy
disulphate
At cathode 2H
+
+ 2e H
2
(g)
The solution containing ammonium peroxy disulphate is heated at 43 mm pressure when its hydrolysis
occurs forming hydrogen peroxide.
(NH
4
)
2
S
2
O
8
+ 2H
2
O 2NH
4
HSO
4
+ H
2
O
2
Hydrogen peroxide along with water distils over. Ammonium bisulphate can be used again. This method
gives 3040% aq. solution of hydrogen peroxide.
Properties of H
2
O
2
Physical Properties: (i) Pure anhydrous hydrogen peroxide is a syrupy liquid. It is colourless but gives a
bluish tinge in thick layers. It is odourless.
(ii) It is soluble in water, alcohol and ether.
(iii) It has bitter taste. It is injurious to skin (blisters are formed).
Chemical Properties: (i) Stability: It is unstable in nature. It decomposes on standing and heating. It is
an example of auto oxidation-reduction reaction.
2H
2
O
2
= 2H
2
O + O
2
(ii) Acidic nature: The pure liquid has weak acidic nature but its aqueous solution is neutral towards
litmus. It reacts with alkalies and carbonates to give their corresponding peroxides.
H
2
O
2
+ 2NaOH = Na
2
O
2
+ 2H
2
O
H
2
O
2
+ Ba(OH)
2
= BaO
2
+ 2H
2
O
H
2
O
2
+ Na
2
CO
3
= Na
2
O
2
+ CO
2
+ H
2
O
(iii) Oxidising nature: It is a powerful oxidising agent. It is a electron acceptor in acidic and alkaline
solutions.
H
2
O
2
+ 2H
+
+ 2e = 2H
2
O (In acidic solutions)
H
2
O
2
+ 2e = 2OH
-
(In alkaline solutions)
The reactions are generally slow in acid solutions but fast in alkaline solution.
Oxidising nature of hydrogen peroxide can be interpreted on account of the possession of label oxygen
atom. The potential equation for its oxidising nature can be written as,
H
2
O
2
H
2
O + O
the following examples show the oxidising nature of H
2
O
2
:
(a) It oxidises black lead sulphide (PbS) to which lead sulphate (PbSO
4
).
PbS + 4H
2
O
2
PbSO
4
+ 4H
2
O
(b) It oxidises nitrites to nitrates.
NaNO
2
+ H
2
O
2
NaNO
3
+ H
2
O
(c) It oxidises sulphites into sulphates.
Na
2
SO
3
+ H
2
O
2
Na
2
SO
4
+ H
2
O
(d) It oxidises arsenites into arsenates
Na
3
AsO
3
+ H
2
O
2
Na
3
AsO
4
+ H
2
O
(e) It liberates iodine from potassium iodide
2KI + H
2
O
2
2KOH + I
2
(f) It oxidises H
2
S into sulphur
H
2
S + H
2
O
2
2H
2
O + S
(g) It oxidises acidified ferrous sulphate to ferric sulphate
2FeSO
4
+ H
2
SO
4
+ H
2
O
2
Fe
2
(SO
4
)
3
+ 2H
2
O
(h) It oxidises acidified potassium ferrocyanide to potassium ferricyanide
2K
4
Fe(CN)
6
+ H
2
SO
4
+ H
2
O
2
2K
3
Fe(CN)
6
+ K
2
SO
4
+ 2H
2
O
(i) It oxidises formaldehyde to formic acid. This oxidation occurs in presence of pyrogallol and in alkaline
medium.
HCHO + H
2
O
2
HCOOH + H
2
O
or HCHO + H
2
O
2
2HCOOH + H
2
(j) Benzene in presence of ferrous sulphate is oxidised to phenol.
(k) It dissolves the chromic hydroxide precipitate present in NaOH solution forming a yellow solution of
sodium chromate.
2Cr(OH)
3
+ 4NaOH + 3H
2
O
2
2Na
2
CrO
4
+ 8H
2
O
(l) A solution of chromic acid in sulphuric acid or acidified potassium dichromate is oxidised to blue peroxide
of chromium (CrO
5
) which is unstable, however, it is soluble in ether and produces blue coloured solution.
K
2
Cr
2
O
7
+ H
2
SO
4
+ 4H
2
O
2
2CrO
5
+ K
2
SO
4
+ 5H
2
O
Peroxide of chromium decomposes to form chromic sulphate and oxygen.
4CrO
5
+ 6H
2
SO
4
2Cr
2
(SO
4
)
3
+ 6H
2
O + 7O
2
Peroxide of chromium is represented as
(m) In acidic solution, mercury is oxidised to mercuric oxide.
Hg + H
2
O
2
H SO
2 4

HgO + H
2
O
(n) Bleaching action: Due to its oxidising nature, it acts as a bleaching agent.
Coloured material + O Colourless
It bleaches materials like silk, hair, ivory, cotton, wool, etc.
(iv) Reducing nature: It can also act as a reducing agent towards powerful oxidising agents.
H
2
O
2
2H
+
+ O
2
+ 2e

In alkaline solution, however, its reducing action is more effective.

H
2
O
2
+ 2OH

2H
2
O + O
2
+ 2e

The potential equation when H

2
O
2
acts as a reducing agent can be expressed as,
H
2
O
2
+ O H
2
O + O
2
(a) Ag
2
O is reduced to silver
Ag
2
O + H
2
O
2
2Ag + H
2
O + O
2
(b) It reduces ozone to oxygen.
H
2
O
2
+ O
3
H
2
O + 2O
2
(c) Manganese dioxide in acidic medium is reduced to manganous salt.
MnO
2
+ H
2
SO
4
PbO + H
2
O + O
2
(e) Red lead in presence of HNO
3
is reduced to plumbous salt.
Pb
3
O
4
+ 6HNO
3
+ H
2
O
2
3Pb(NO
3
)
2
+ 4H
2
O + O
2
(f) Chlorine and bromine are reduced to corresponding hydracids.
Cl
2
+ H
2
O
2
2HCl + O
2
This reaction can be shown in following steps:
Cl
2
+ H
2
O
2
2HCl + O
2
Similarly, Br
2
+
2
O
2
2HBr + O
2
(g) It reduces acidified KMnO
4
solution, i.e., acidified KMnO
4
is decolorised by H
2
O
2
.
2KMnO
4
+ 3H
2
SO
4
+ 5H
2
O
2
K
2
SO
4
+ 2MnSO
4
+ 8H
2
O + 5O
2
(h) Potassium ferricyanide (alk. solution) is reduced to potassium ferrocyanide.
2K
3
Fe(CN)
6
+ 2KOH + H
2
O
2
2K
4
Fe(CN)
6
+ 2H
2
O + O
2
(i) Hypohalites are reduced to halides
NaOCl + H
2
O
2
NaCl + H
2
O + O
2
(j) KIO
4
is reduced to KIO
3
KIO
4
+ H
2
O
2
KIO
3
+ H
2
O + O
2
Uses:
(a) for restoring colour of old paintings.
(b) as antichlor to remove traces of chlorine and hypochlorite.
(c) Highly concentrated solution (about 40%) of H
2
O
2
is used to oxidise petrol, alcohol, and hydrozine
hydrate for the propelling of rockets and torpedoes.
NH
2
NH
2
+ 2H
2
O
2
N
2
+ 4H
2
O
Compounds of Sodium
1. Sodium Oxide, Na
2
O :
It is prepared by heating sodium nitrate or sodium nitrite with sodium.
2NaNO
3
+ 10Na 6Na
2
O + N
2
2NaNO
2
+ 6Na 4Na
2
O + N
2
Pure sodium oxide is formed when the mixture of sodium azide and sodium nitrite is heated.
3NaN
2
+ NaNO
2
2Na
2
O + 5N
2
Na
2
O + H
2
O 2NaOH + heat
On heating at 400
0
C, it disproportionates forming sodium peroxide and metallic sodium vapour.
2Na
2
O
400
0
C

Na
2
O
2
+ 2Na
Sodamide is formed when it reacts with liquid ammonia
Na
2
O + NH
3
NaNH
2
+ NaOH
It is used as dehydrating and polymerising agent in organic chemistry.
2. Sodium Peroxide, Na
2
O
2
:
It is formed by heating sodium in excess of air free from moisture and carbon dioxide or in excess of pure
oxygen .
2Na + O
2
(excess)
350
0
C

Na
2
O
2
It is a pale yellow powder. On exposure, it becomes white moisture and carbon dioxide
2Na
2
O
2
+ 2H
2
O 4NaOH + O
2
2Na
2
O
2
+ 2CO
2
2Na
2
CO
3
+ O
2
At low temperature, it forms H
2
O
2
with water and acids.
It combines with CO and CO
2
Na
2
O
2
+ CO Na
2
CO
3
2Na
2
O
2
+ 2CO
2
2Na
2
CO
3
+ O
2
It acts as a powerful oxidising agent.
(a) Chromic compounds are oxidised to chromates
2Cr(OH)
3
+ 3Na
2
O
2
2Na
2
CrO
4
+ 2NaOH + 2H
2
O
(b) Manganous salt is oxidised to sodium manganate.
MnSO
4
+ 2Na
2
O
2
Na
2
NO
4
+ Na
2
SO
4
(c) Sulphides are oxidised to corresponding sulphates
Na
2
S + 4O Na
2
SO
4
Benzoyl peroxide (bleaching agent) is formed when C
6
H
5
COCl reacts with Na
2
O
2
2C
6
H
5
COCl + Na
2
O
2
(C
6
H
5
CO)
2
O
2
+ 2NaCl
Benzoyl peroxide
3. Sodium Hydroxide (Caustic Soda), NaOH :
(a) Methods involving sodium carbonate as a starting material: Two methods are used. These are:
(i) Causticisation process (Gossage process): This process depends on the reaction between suspension
of lime (milk of lime, calcium hydroxide) and sodium carbonate. This reaction is reversible.
Na
2
CO
3
+ Ca(OH)
2
CaCO
3
+ 2NaOH
Na
2
CO
3
+ Fe
2
O
3
2NaFeO
2
+ CO
2
The sodium ferrite is cooled and thrown into hot water. The hydrolysis of sodium ferric occurs forming a
solution of sodium hydroxide and insoluble ferric oxide.
2Na
2
FeO
2
+ H
2
O 2NaOH + Fe
2
O
3
The solution is filtered and evaporated to dryness to get flakes of sodium hydroxide.
(b) Methods involving sodium chloride as starting material: Methods used are electrolytic as the
electrolysis of sodium chloride solution is carried out in an electrolytic cell.
Principle: A sodium chloride solution contains Na
+
, H
+
, Cl

and OH

ions.
NaCl Na
+
+ Cl

H
2
O H
+
+ OH

Hydrogen is liberated at cathode, Cl

2
gas is liberated.
The solution on electrolysis becomes richer in Na
+
and OH

ions.
Since chlorine reacts with sodium hydroxide solution even in cold forming sodium chloride and sodium
hypochlorite, it is necessary that chlorine should not come in contact with sodium hydroxide during
electrolysis.
2NaOH + Cl
2
NaCl + NaClO + H
2
O
To overcome this problem, the anode is separated from the cathode in the electrolytic cell either by using
a porous diphragm or by using a mercury cathode.
(i) Porous diaphragm process (Nelson cell process): Nelson cell consists of a perforated steel tube
lined inside with asbestos. The tube acts as a cathode. A graphite rod dipped in sodium chloride solution
serves as anode.
(ii) Castner-Kellner cell: This is the common cell in which mercury is used as cathode. Two graphite
electrodes act as anodes and a series of iron rods fitted in the inner compartment act as cathode. Mercury
in the outer compartments acts as cathode while in the inner compartment it acts as anode by induction.
The cell is kept rocking with help of an eccentric wheel.
When electricity is circulated, sodium chloride in the outer compartments is electrolysed. Chlorine is evolved
at the graphite anode while Na
+
ions are discharged at the Hg cathode. The liberated sodium forms amalgam
with mercury.
NaCl Na
+
+ Cl

At Anode 2Cl

2Cl + 2e Cl
2
At Cathode Na
+
+ e Na
Na + Hg Amalgam
The sodium amalgam thus formed comes in the inner compartment due to rocking. Here, the sodium amalgam
acts as the anode and iron rods act as cathode.
At Anode Na-amalgam Na
+
+ Hg + e
At Cathode 2H
2
O + 2e H
2
- + 2OH

The concentrated solution of sodium hydroxide (about 20%) is taken out from inner compartment and
evaporated to dryness to get solid NaOH.
(iii)Kellner-Solvay cell: This is the modified cell. The flowing mercury acts as cathode. A number of
graphite rods dipping in sodium chloride solution acts as anode.
Chemical Properties:
(a) Action of atmosphere: 2NaOH + CO
2
Na
2
CO
3
+ H
2
O
(b) Strong alkali: Sodium hydroxide is a strong alkali as it dissociates completely in water furnishing OH

ions.
NaOH Na
+
+ OH

(i) It reacts with acids forming corresponding salts.

NaOH + HCl NaCl + H
2
O
2NaOH + H
2
SO
4
Na
2
SO
4
+ 2H
2
O
NaOH + HNO
3
NaNO
3
+ H
2
O
3NaOH + H
3
PO
4
Na
3
PO
4
+ 3H
2
O
NaOH + CH
3
COOH CH
3
COONa + H
2
O
(ii) It combines with acidic oxides to form salts.
2NaOH + CO
2
Na
2
CO
3
+ H
2
O
Sodium
carbonate
2NaOH + SO
2
Na
2
SO
3
+ H
2
O
Sodium
sulphide
2NaOH + 2NO
2
NaNO
3
+ NaNO
2
+ H
2
O
Sodium Sodium
Nitrate Nitrite
(iii) Amphoteric oxides of aluminium, zinc, tin and lead dissolve in sodium hydroxide forming corresponding
salts.
Al
2
O
3
+ 2NaOH 2NaAlO
2
+ H
2
O
Sodium meta
aluminate
ZnO + 2NaOH Na
2
ZnO
2
+ H
2
O
Sodium zincate
SnO + 2NaOH NaSnO
2
+ H
2
O
Sodium stannite
SnO
2
+ 2NaOH NaSnO
3
+ H
2
O
Sodium stannate
PbO + 2NaOH NaPbO
2
+ H
2
O
Sodium plumbite
PbO
2
+ 2NaOH NaPbO
3
+ H
2
O
Sodium plumbate
(c) Action on non-metals: Non metals like halogens, P(yellow), S, Si, B, etc. are attacked by NaOH.
(i) Halogens: Hypohalites and halides are formed with cold and dilute solution of NaOH.
Cl
2
+ 2NaOH NaCl + NaClO + H
2
O
(cold and dilute) Sodium
hypo chlorite
Br
2
+ 2NaOH NaBr + NaBrO + H
2
O
(cold and dilute) Sodium
hypo bromite
I
2
+ 2NaOH NaI + NaIO + H
2
O
(cold and dilute) Sodium
hypo iodate
Halogens form helates and halides with hot and concentrated solution of NaOH.
3Cl
2
+ 6NaOH 5NaCl + NaClO
3
+ 3H
2
O
(hot and conc.) Sodium chlorate
3r
2
+ 6NaOH 5NaBr + NabrO
3
+ 3H
2
O
(hot and conc.) Sodium bromate
3I
2
+ 6NaOH 5NaI + NaIO
3
+ 3H
2
O
(hot and conc.) Sodium iodate
(ii) Yellow phosphorus (white) when heated with NaOH solution evolves phosphine gas (PH
3
) alongwith
the formation of sodium hypophosphite.
P
4
+ 3NaOH + 3H
2
O 3NaH
2
PO
2
+ PH
3
Sodium Phosphine
hypophosphite
(iii) Sulphur on heating with sodium hydroxide solution forms sodium thiosulphate
4S + 6NaOH Na
2
S
2
O
3
+ 2Na
2
S + 3H
2
O
Sodium sodium
thio sulphate sulphide
(iv) Silicon evolves hydrogen when heated with NaOH solution
2NaOH + Si + H
2
O Na
2
SiO
3
+ 2H
2
Sodium silicate
(v) Boron also evolves hydrogen when fused with NaOH.
2B + 6NaOH 2Na
3
BO
3
+ 3H
2
Sodium borate
(d) Action on metals: Metals like Zn, Al, Sn, Pb react with sodium hydroxide solution and evolve hydrogen.
Zn + 2NaOH Na
2
ZnO
2
+ H
2
2Al + 2NaOH + 2H
2
O 2NaAlO
2
+ 3H
2
Sn + 2NaOH + H
2
O Na
2
SnO
3
+ 2H
2
Pb + 2NaOH + H
2
O Na
2
PbO
3
+ 2H
2
[However, Sn and Pb when fused with NaOH form Na
2
SnO
2
and Na
2
PbO
2
, respectively.
Sn + 2NaOH Na
2
SnO
2
+ H
2
Pb + 2NaOH Na
2
PbO
2
+ H
2
]
(e) Action on salts: Sodium hydroxide reacts with metallic salts to form hydroxides which may be insoluble
or dissolve in excess of NaOH to form salts of oxyacids. Some of the hydroxides decompose its insoluble
oxides.
(i) Insoluble hydroxides: Salts of nickel, iron, manganese, copper, etc., form insoluble hydroxides.
Ni(NO
3
)
2
+ 2NaOH Ni(OH)
2
+ 2NaNO
3
FeSO
4
+ 2NaOH Fe(OH)
2
+ Na
2
SO
4
FeCl
3
+ 3NaOH Fe(OH)
3
+ 3NaCl
Red ppt.
CrCl
3
+ 3NaOH Cr(OH)
3
+ 3NaCl
Green ppt.
MnSO
4
+ 2NaOH Mn(OH)
2
+ Na
2
SO
4
Buff coloured ppt.
CuSO
4
+ 2NaOH Cu(OH)
2
+ Na
2
SO
4
Blue coloured ppt.
(ii) Insoluble hydroxides which dissolve in excess of NaOH.
ZnSO
4
+ 2NaOH Zn(OH)
2
+ Na
2
SO
4
White insoluble
Zn(OH)
2
+ 2NaOH Na
2
ZnO
2
+ 2H
2
O
Sodium zincate
(soluble)
AlCl
3
+ 3NaOH Al(OH)
3
+ 3NaCl
White ppt.
Al(OH)
3
+ NaOH NaAlO
2
+ 2H
2
O
Sodium meta
aluminate(soluble)
SnCl
2
+ 2NaOH Sn(OH)
2
+ 2NaCl
White ppt.
Sn(OH)
2
+ 2NaOH Na
2
SnO
2
+ 2H
2
O
Sodium stannite
(Soluble)
(iii) Unstable hydroxides
2AgNO
3
+ 2NaOH 2AgOH + 2NaNO
3
2AgOH Ag
2
O + H
2
O
(Brown)
HgCl
2
+ 2NaOH Hg(OH)
2
+ 2NaCl
Hg(OH)
2
HgO + H
2
O
(Yellow)
(f) Action of ammonium salts: Ammonium salts are decomposed on heating with sodium hydroxide
solution with the evolution of ammonia gas.
NH
4
Cl + NaOH NH
3
- + NaCl + H
2
O
(NH
4
)
2
SO
4
+ 2NaOH Na
2
SO
4
+ 2NH
3
- + H
2
O
(g) Action of carbon monoxide:
NaOH reacts with carbon monoxide under pressure at 150200
0
C to form sodium formate.
NaOH + CO
150 200
5 10
0

C
atm
HCOONa
Sodium formate
(h) Caustic property: Sodium hydroxide bereaks down the proteins of skin to a pasty mass. On account
of this property, it is commonly called as Caustic soda.
4.Sodium Carbonate or Washing Soda (Na
2
CO
3
.10H
2
O)
The most important one is Solvay process. The following are the three main processes for the manufacture
of sodium carbonate.
(a) Le-Blanc process, (b) Solvay, ammonia soda process, and (c) Electrolytic process.
(a) Le- Blanc process: The raw materials of this process are common salt (NaCl), sulphuric acid, coke
and calcium carbonate (CaCO
3
). It involves the following steps:
(i) Conversion of NaCl into Na
2
SO
4
: The common salt a heated with calculated quantity of sulphuric
acid (concentrated) in the furnace.
NaCl + H
2
SO
4
NaHSO
4
+ HCl
Sodium hydrogen
sulphate
The paste is heated at higher temperature when sodium hydrogen sulphate is converted into sodium sulphate.
NaHSO
4
+ NaCl Na
2
SO
4
+ HCl
Sodium sulphate, thus formed is technically called salt cake. The HCl evolved is dissolved in water to form
hydrochloric acid.
(ii) Conversion of salt-cake into black ash:
The solid residue is called black ash. This contains about 45% sodium carbonate.
(iii) Recovery of Na
2
CO
3
: The black ash is crushed and extracted with water. The sodium carbonate
dissolves and the insoluble impurities mainly consisting CaS are left behind. The insoluble material is called
sludge or alkali waste. The solution consisting sodium carbonate is evaporated to gen solid sodium carbonate.
(b) Solvay ammonia soda process: This is the modern process used for the manufacture of sodium
carbonate.The raw materials required in this process are the common salt, ammonia and limestone.
NH
3
+ H
2
O + CO
2
NH
4
HCO
3
Ammonium bicarbonate
NaCl + NH
4
HCO
3
NaHCO
3
+ NH
4
Cl
Sodium
bicarbonate
2NaHCO
3

Na
2
CO
3
+ H
2
O + CO
2
(c) Electrolytic process: In this process sodium chloride is first converted into sodium hydroxide by
electrolysis. In the Nelson cell used for the manufacture of sodium hydroxide, carbon dioxide number
pressure is blown along with steam. The sodium hydroxide produced will then react with carbon dioxide to
form sodium carbonate. The solution is concentrated and crystallised.
2NaOH + CO
2
Na
2
CO
3
+ H
2
O
Physical Properties: The common form is decahydrate, Na
2
CO
3
.10H
2
O. This form is called washing
soda. The decahydrate form on standing in air effloresces and crumbles to powder. It is the monohydrate
form,
Na
2
CO
3
.H
2
O. It also forms a heptahydrate, Na
2
CO
3
.7H
2
O.
Chemical Properties: (a) Action of acids: It is readily decomposed by acids with evolution of carbon
dioxide. The reaction occurs in two steps.
Na
2
CO
3
+ HCl NaHCO
3
+ NaCl
NaHCO
3
+ HCl NaCl + H
2
O + CO
2
(b) Action of CO
2
: On passing CO
2
through the concentrated solution of sodium carbonate, sodium
bicarbonate gets precipitated.
Na
2
CO
3
+ H
2
O + CO
2
2NaHCO
3
(c) Action of silica: When the mixture of sodium carbonate and silica is fused, sodium silicate is formed.
Sodium silicate is called soluble glass or water glass as it is soluble in water.
Na
2
CO
3
+ SiO
2
Na
2
SiO
3
+ CO
2
-
(d) Action of slaked lime: Sodium hydroxide is formed when the solution of sodium carbonate and
slaked lime is heated.
Na
2
CO
3
+ Ca(OH)
2
2NaOH + CaCO
3
(e) Action with sulphur and sulphur dioxide: When aqueous solution of sodium carbonate containing
sulphur is treated with sulphur dioxide, sodium thiosulphate (Na
2
S
2
O
3
) is formed.
Na
2
CO
3
+ SO
2

H O
2

Na
2
SO
3
+ CO
2
-
Na
2
SO
3
+ S Na
2
S
2
O
3
(f) Action on salts of non-alkali metals: Sodium carbonate reacts with metal salts (except alkali metal
salts) to form insoluble or basic carbonates.
CaCl
2
+ Na
2
CO
3
CaCO
3
+ 2NaCl
BaCl
2
+ Na
2
CO
3
BaCO
3
+ 2NaCl
2MgCl
2
+ 2Na
2
CO
3
+ H
2
O MgCO
3
Mg(OH) + 4NaCl + CO
2
Basic Magnesium Carbonate
5ZnSO
4
+ 5Na
2
CO
3
+ 4H
2
O [2ZnCO
3
3Zn(OH)
2
]H
2
O + 5Na
2
SO
4
+ 3CO
2
Basic zinc Carbonate
CuSO
4
+ Na
2
CO
3
CuCO
3
+ Na
2
SO
4
2CuSO
4
+ 2Na
2
CO
3
+ H
2
O Cu(OH)
2
CuCO
3
+ CO
2
+ Na
2
SO
4
Basic copper Carbonate
3(CH
3
COO)
2
Pb + 3Na
2
CO
3
+ H
2
O 2PbCO
3
Pb(OH)
2
+ CO
2
+ 6CH
3
COONa
Basic lead Carbonate
2AgNO
3
+ Na
2
CO
3
Ag
2
CO
3
+ 2NaNO
3
Carbonates of metals like Fe, Al, Sn, etc., When formed are immediately hydrolysed to hydroxides.
Fe
2
(SO
4
)
3
+ 3Na
2
CO
3
Fe
2
(CO
3
)
3
+ 3Na
2
SO
4
Fe
2
(CO
3
)
3
+ 3H
2
O

2Fe(OH)
3
+ 3CO
2
Uses: As a laboratory reagent. The mixture of Na
2
CO
3
and K
2
CO
3
is used as a fusion mixture.
5. Sodium Bicarbonate (Baking Soda), NaHCO
3
It is obtained as the intermediate product in the solvay ammonia soda process. Normal carbonated can be
changed to bicarbonate by passing carbon dioxide through its saturated solution.
Na
2
CO
3
+ CO
2
+ H
2
O

2NaHCO
3
Sparingly soluble
Properties: It is a white crystalline solid, sparingly soluble in water. The solution is alkaline in nature due
to hydrolysis. The solution is weakly basic.
NaHCO
3
+ H
2
O

NaOH + H
2
CO
3
The solution gives yellow colour with methyl orange but no colour with phenolphthalein.
On heating, it loses carbon dioxide and water forming sodium carbonate.
2NaHCO
3
Na
2
CO
3
+ H
2
O+ CO
2
The metal salt which forms basic carbonate with sodium carbonate, gives normal carbonate with sodium
bicarbonate
ZnSO
4
+ 2NaHCO
3
ZnCO
3
+ Na
2
CO
3
+ H
2
O+ CO
2
6. Sodium Thiosulphate, Na
2
S
2
O
3
.5H
2
O
It is the sodium salt of an unstable acid, thiosulphuric acid (H
2
S
2
O
3
). It is also known as hypo. The following
methods can be used for its preparation.
(i) It is obtained by boiling sodium sulphite solution with flowers of sulphur.
Na
2
SO
3
+ S Na
2
S
2
O
3
The unreacted sulphur is filtered off and the filtrate is evaporated to crystallization.
(ii) Springs reaction: The mixture of sodium sulphite and sodium sulphide is treated with calculated
quantity of iodine.
Na
2
S + I
2
+ Na
2
SO
3
Na
2
S
2
O
3
+ 2NaI
The resulting solution is concentrated and allowed to crystallise when crystals of sodium thiosulphate being
less soluble separate out first.
(iii) When the solution containing sodium carbonate and sodium sulphide is treated with sulphur dioxide,
sodium thiosulphate is formed with evolution of carbon dioxide.
2Na
2
S + Na
2
CO
3
+ 4SO
2
3Na
2
S
2
O
3
+ CO
2
-
(iv) Sodium thiosulphate is formed when sulphur is heated with caustic soda solution.
4S + 6NaOH Na
2
S
2
O
3
+ 2Na
2
S + 3H
2
O
With excess of sulphur, sodium pentasulphide is formed,
Na
2
S + 4S Na
2
S
5
(v) On passing SO
2
gas through the solution of Na
2
CO
3
in presence of sulphur we get sodium thiosulphate.
Na
2
CO
3
+ SO
2
Na
2
SO
3
+ CO
2
Na
2
SO
3
+ S Na
2
S
2
O
3
Properties: (i) It is a colourless crystalline solid consisting of 5 molecules of water as water of crystallization.
It has the formula, Na
2
S
2
O
3
5H
2
O. It is soluble in water. It melts at 48
0
C.
(ii) Action of heat: It is efflorescent substance. The water molecules are completely lost when heated at
215
0
C.
Na
2
S
2
O
3
5H
2
O
215
0
C

Na
2
S
2
O
3
+ 5H
2
O
When strongly heated above 223
0
C, it decomposes forming sodium sulphate and sodium pentasulphide.
4Na
2
S
2
O
3
3Na
2
SO
4
+ Na
2
S
5
(iii)Action of acids: Dilute acids decompose it with evolution of SO
2
and precipitation of sulphur.
Na
2
S
2
O
3
+ 2HCl 2NaCl + SO
2
+ S + H
2
O
Na
2
S
2
O
3
+ H
2
SO
4
Na
2
SO
4
+ SO
2
+ S + H
2
O
(iv) Oxidation : It is oxidised by iodine quantitatively
2Na
2
S
2
O
3
+ I
2
2NaI + Na
2
S
4
O
6
Sodium tetrathionate
Colour of iodine disappears.
(v) Reducing action: It is oxidised by chlorine and bromine water. Sulphur is precipiated.
Na
2
S
2
O
3
+ Cl
2
+ H
2
O Na
2
SO
4
+ 2HCl + S
It reduces FeCl
3
to FeCl
2
2Na
2
S
2
O
3
+ 2FeCl
3
Na
2
S
4
O
6
+ 2FeCl
2
+ 2NaCl
(vi) Action of AgNO
3
: A white precipitate of silver thiosulphate is obtained which changes to yellow,
brown and finally black due to the formation of silver sulphide.
2AgNO
3
+ Na
2
S
2
O
3
Ag
2
S
2
O
3
+ 2NaNO
3
Ag
2
S
2
O
3
+ H
2
O Ag
2
S + H
2
SO
4
(vii) Action of silver halides: Halides form complexes with sodium thiosulphate. Silver bromide forms
argento thiosulphate complex.
AgBr + 2Na
2
S
2
O
3
Na
3
[Ag(S
2
O
3
)
2
] + NaBr
Sodium argentothiosulphate
(colourless)
Similar reactions are observed with AgCl and AgI.
This property is utilised in photography for fixing the negative and positive of black and white photography.
It removes undecomposed AgBr present on the film.
(viii) Action on copper sulphate: Cuprous thiosulphate is formed which dissolves in excess of sodium
thiosulphate to form a complex.
CuSO
4
+ Na
2
S
2
O
3
CuS
2
O
3
+ Na
2
SO
4
Cupric thiosulphate
2Cu
2
S
2
O
3
+ Na
2
S
2
O
3
Cu
2
S
2
O
3
+ Na
2
S
4
O
6
Cuprous thiosulphate
3Cu
2
S
2
O
3
+ 2Na
2
S
2
O
3
Na
4
[Cu
6
(S
2
O
3
)
5
]
Sodium cupro thiosulphate
Uses: Sodium thiosulphate is used :
(a) as an antichlor to remove excess of chlorine from bleached fabrics.
Sodium Chloride (Common salt), NaCl
Sodium chloride is the most common of the salts of sodium. It is also called common salt or table salt or
rock salt or sea salt.
Manufacture from sea water: The sea water is allowed to dry up under summer heat in small tanks or
pits. The solid crust so formed is collected.
Potassium:
Compounds of potassium: Potassium chloride is the starting material for the preparation of various
potassium compounds. It is obtained from carnallite, KClMgCl
2
6H
2
O, by fractional crystallisation. The
carnalities ground and extracted with a 20 percent solution of MgCl
2
. The carnallite dissolves while NaCl
and MgSO
4
remain undissolved. The clear solution is put to crystalline when crystals of KCl separate out.
Oxides: Three oxides of potassium are known:
(a) Potassium monoxide, K
2
O
(b) Potassium dioxide (tetraoxide or superoxide), KO
2
or K
2
O
4
(c) Potassium sesquioxide, K
2
O
3
KO
2
is prepared by burning potassium in excess of oxygen free from moisture.
K + O
2
KO
2
It is also obtained by reacting dry potassium hydroxide with ozone.
2KOH + O
3
2KO
2
+ H
2
O
K
2
O
3
is obtained when oxygen is passed through liquid ammonia containing potassium.
4K (dissolved in liquid NH
3
)
3
2
O

2K
2
O
3
Potassium superoxide, KO
2
, is a chrome yellow powder. it dissolves in water giving H
2
O
2
and O
2
.
2KO
2
+ 2H
2
O 2KOH + H
2
O
2
+ O
2
It reacts directly with CO and CO
2
.
2KO
2
+ CO K
2
CO
3
+ O
2
2KO
2
+ CO
2
K
2
CO
3
+ (3/2)O
2
On heating with sulphur, it forms potassium sulphate.
2KO
2
+ S K
2
SO
4
KO
2
is used as an oxidising agent. It is used as air purifier in space capsules, submarines and breathing
masks as it both produces oxygen and removes carbon dioxide.
Potassium Hydroxide, KOH
It is manufactured like sodium hydroxide, i.e. by electrolysis of KCl solution.
It is used for the absorption of gases like CO
2
, SO
2
, etc. It is often called as caustic potash and its aq.
solution is knwon as potash Iye. It is used for making soft soaps.
Alcoholic caustic potash is a useful reagent in organic chemistry as it eliminates hydrogen halides from alkyl
halides.
C
2
H
5
Br + KOH(alc.) C
2
H
4
+ KBr + H
2
O
Potassium carbonate, K
2
CO
3
It is also called Potash or Pearl ash. It cannot be made by the use of Solvay process as potassium bicarbonate
is more soluble than sodiumbicarbonate. However, it can be prepared by Le-Blanc process. KCl is first
converted into K
2
SO
4
K
2
SO
4
is then heated with CaCO
3
and carbon.
KCl + K
2
SO
4
KHSO
4
+ HCl
KHSO
4
+ KCl K
2
SO
4
+ HCl
K
2
SO
4
+ CaCO
3
+ 2C K
2
CO
3
+ CaS + 2CO
2
It is a white powder, deliquescent in nature. It is highly soluble in water.
It is used in the maufacture of hard glass. The mixture of K
2
Co
3
adn Na
2
CO
3
is used as a fusion mixture in
laboratory.
COMPOUNDS OF MAGNESIUM
Magnesium Oxide, MgO, (Magnesia)
Preparation: It can be prepared by following reactions.
2Mg + O
2
Burning

2MgO
Mg(OH)
2

Heated

MgO + H
2
O
2Mg(NO
3
)
2

Heated

2MgO + 4NO
2
+ O
2
MgCO
3

Heated

MgO + CO
2
Properties: It is a light infusible white powder. It fuses at 2800
o
C. It is slightly soluble in water and forms
magnesium hydroxide.
MgO + H
2
O

Mg(OH)
2
It is basic in nature. It reacts with acids to form corresponding salts.
MgO + 2HCl

MgCl
2
+ H
2
O
MgO + H
2
SO
4

MgSO
4
+ H
2
O
It is reduced by carbon at very high temperature.
MgO + C

Mg + CO
Magnesium oxide when mixed with a saturated solution of magnesium chloride sets to a hard mass like
cement known as magnesia cement or sorels cement. The composition is MgCl
2
.5MgO.xH
2
O.
Magnesium Hydroxide, Mg(OH)
2
Preparation: It is prepared by dissolving magnesium oxide in water or by treating magnesium salt with an
alkali.
MgO + H
2
O

Mg(OH)
2
MgCl
2
+ Ca(OH)
2

Mg(OH)
2
+ CaCl
2
MgCl
2
+ 2NaOH

Mg(OH)
2
+ 2NaCl
Properties: It is a white powder. It is sparingly soluble in water. It is basic in nature and forms salts with
acids. It decomposes on heating. It readily dissolves in strong solution of NH
4
Cl.
Mg(OH)
2
+ 2NH
4
Cl

MgCl
2
+ 2NH
4
OH
Uses: A suspension of Mg(OH)
2
in water is used in medicine as an antacid under the name, milk of
magnesia.
Magnesium Carbonate, MgCO
3
It is found in nature as magnesite (MgCO
3
) and dolomite (MgCO
3
.CaCO
3
).
Preparation: It can be prepared by adding sodium bicarbonate to a hot solution of magnesium salt.
MgSO
4
+ 2NaHCO
3

MgCO
3
+ Na
2
SO
4
+ H
2
O + CO
2
The magnesium carbonate cannot be obtained by the addition of sodium carbonate to the solution of
magnesium salt. A white precipitate of a basic acarbonate of composition 3MgCO
3
.Mg(OH)
2
.2H
2
O is
obtained. It is known as magnesia alva. It is suspended in water and CO
2
is passed when magnesium
bicarbonates known as fluid imagines is formed. The solution is boiled when normal magnesium carbonate
separates out.
2MgSO
4
+ 2Na
2
CO
3
+ H
2
O

MgCO
3
.Mg(OH)
2
+ 2Na
2
SO
4
+ CO
2
MgCO
3
.Mg(OH)
2
+ 3CO
2
+ H
2
O

2Mg(HCO
3
)
2
Mg(HCO
3
)
2

MgCO
3
+ CO
2
+ H
2
O
Properties: It is a white powder, insoluble in water. It dissolves readily in water containing excess of
carbon dioxide.
MgCO
3
+ CO
2
+ H
2
O

Mg(HCO
3
)
2
It dissolves in acids foming salts with evolution of CO
2
.
MgCO
3
+ 2HCl

MgCl
2
+ H
2
O + CO
2
MgCO
3
+ H
2
SO
4

MgSO
4
+ H
2
O + CO
2
On heating, it decomposes with evolution of CO
2
.
MgCO
3

MgO + CO
2
It forms double carbonates with alkali carbonates.
MgCO
3
+ Na
2
CO
3

Na Mg CO
So le
2 3 2
( )
lub
Magnesium chloride, MgCl
2
.6H
2
O
It occurs as mineral carnallite, KCl.MgCl
2
.6H
2
O and bischrofite, MgCl
2
.H
2
O. It is found in sea water,
mineral springs, etc.
Preparation: (a) It is extracted from carnallite mineral. The mineral is fused and cooled to 176
o
C when
whole of KCl is deposited while MgCl
2
.6H
2
O remains in the fused state.
(b) It can also be obtained by dissolving Mg, MgO, Mg(OH)
2
or MgCO
3
in dilute hydrochloric acid.
The preparation of anhydrous magnesium chloride has already been described in the extraction of magnesium.
Properties: It is a colourless crystalline solid, highly deliquescent and highly soluble in water. It is the
starting material for various magnesium compounds.
Magnesium Sulphate, MgSO
4
.7H
2
O
It occurs in nature as minerals kiesserite (MgSO
4
.H
2
O), epsom salt (MgSO
4
.7H
2
O) and kainite
(KCl.MgSO
4
.3H
2
O).
Preparation: It is formed by reacting magnesite (MgCO
3
) or dolomite with dilute sulphuric acid.
MgCO
3
+ H
2
SO
4
MgSO
4
+ H
2
O + CO
2
MgCO
3
.CaCO
Dolomite
3
+ 2H
2
SO
4
MgSO
4
+
CaSO
Ino le
4
( lub )
+ 2CO
2
+ 2H
2
O
It is commercially prepared by boiling kiesserite mineral in water. The crystals are obtained when the
solution is cooled.
MgSO
4
.H
2
O + 6H
2
O

MgSO
4
.7H
2
O
Properties: It is a colourless crystalline compound, soluble in water. The crystals are efflorescent and
bitter in taste. It is isomorphous with ZnSO
4
.7H
2
O. It forms double sulphates with alkali metal sulphates,
K
2
SO
4
.MgSO
4
.6H
2
O (Schonite).
Heating effect: When heated to 150
o
C, it changes to monohydrate. On further heating, it becomes anhdrous
at 200
o
C. On strong heating, it decomposes into MgO.
MgSO
4
.7H
2
O
150
o
C

MgSO
4
.H
2
O
200
o
C

MgSO
4

Strong
!eating

MgO + SO
2
+
1
2
2
O
Magnesium sulphate is reduced by lampblack at 800
o
C.
2MgSO
4
+ C 2MgO + 2SO
2
+ CO
2
CALCIUM
COMPOUND OF CALCIUM
Quick Lime, Slaked Lime and Lime Water
Preparation: CaCO
3
CaO + CO
2
.
The reaction moves towards right hand direction if CO
2
formed is immediately removed from the kiln by
allowing a blast of air to enter the kiln through fire boxes. The temperature for the decomposition of
limestone should be near about 1000
o
C otherwise at higher temperature, the clay present in the limestone
as impurity will react with it to form silicate.
When water is added to lime, a hissing sound is produced along with clouds of steam. In this process a
large amount of heat energy is given out. The lime cracks with the formation of a powder called slaked lime
[Ca(OH)
2
].
CaO
"ui#$ e lim
+ H
2
O
Ca OH
Sla$ed e
( )
lim
2
+ Heat energy
The process is known as slaking of lime. The paste of lime in water is called milk of lime while the filtered
and clear solution is known as lime water. Chemically both are Ca(OH)
2
.
%imetone
CaCO ( )
3
1000
0
C

"ui#$ %ime
CaO ( )

H O
2

Sla$ed %ime
Ca OH & ( ) '
2

Su(enion
Mil$ o) %ime
Ca OH
( )
( )
2
Suspended in water
Filter

Clear Solution
%ime *ater
Ca OH
( )
( )
2
Mortar
Slaked lime is mixed with three to four times its weight of sand. The mixture is made into a thick paste with
gradual addition of water. This paste is called mortar and is used in building construction.
Ca(OH)
2
+ CO
2
CaCO
3
+ H
2
O
CaCl
2
+ Na
2
CO
3
CaCO
3
+ 2NaCl
The precipitate of CaCO
3
thus obtained is known as precipitated chalk.
It is a white powder, insoluble in water. It dissolves in presence of CO
2
due to formation of calcium
bicarbonate.
CaCO
3
+ H
2
O + CO
2
Ca(HCO
3
)
2
Calcium Sulphate, CaSO
4
2H
2
O (Gypsum)
It is found in nature as anhydride (CaSO
4
) and gypsum (CaSO
4
2H
2
O).
It can be prepared by reacting any calcium salt with either sulphuric acid or a soluble sulphate.
CaCl
2
+ H
2
SO
4
CaSO
4
+ 2HCl
CaCl
2
+ Na
2
SO
4
CaSO
4
+ 2NaCl
Plaster of Paris, 2CaSO
4
H
2
O (Calcium sulphate hemihydrate)
Preparation:
(i) Plaster of paris is a white powder.
(ii) It has the property of setting to a hard mass when a paste with water is allowed to stand aside for
sometime. Slight expansion occurs during the setting as water is absorbed to reform CaSO
4
2H
2
O (gypsum).
the setting process is exothermic. The process of setting takes place in two stages. In the first stage, there
is conversion of Plaster of Paris into ortho-rhombic form of gypsum (setting step) and in the second stage
ortho-rhombic form changes into monoclinic form (hardening step).
2
4 2
CaSO H O
+later o) +ari

Setting
H O

2

CaSO H O
Ot!o r bi#
4 2
2
!om

Hardening
CaSO H O
Mono#lini#
4 2
2
The setting of plaster of paris may be catalysed by sodium chloride while it is retarded by borax or alum.
Addition of alum to Plaster of Paris makes the setting very hard. The mixture is known as Keenes cement.
(iii) When Plaster of Paris is heated at 200
0
C, it forms anhydrous calcium sulphate which is known as dead
plaster. It has no setting property as it takes up water only very slowly.
BORON FAMILY
Boron
Occurence: Boron is not found free in nature. In the combined state, it is found as the salts of boric acid.
The important minerals of boron are:
(i) Borax (Tincal) : Na
2
B
4
O
7
10H
2
O It is found in Tibet, Ceylon, California and Kashmir.
(ii) Colemanite: Ca
2
B
6
O
11
5H
2
O It is found in Asia Minor and America.
Panderinite: Ca
2
B
6
O
11
3H
2
O
(iii) Boracite: 2Mg
3
B
8
O
15
MgCl
2
It is found in Stass-furt, Germany.
(iv) Boronatro calcite: CaB
4
O
7
NaBO
2
8H
2
OIt is found in Chile.
(v) Kernite (Rasorite): Na
2
B
4
O
7
4H
2
OIt is found in Mojave dessert in America.
(vi) Boric acid: H
3
BO
3
It occurs in the jets of steam called soffioni escaping from ground in the
volcanic regions of Tuscany.
Boron is also present to some extent in plants and sometimes in coal ash.
Extraction: Boron is extracted from borax and colemanite minerals. The extraction involves two steps:
(i) Preparation of boric anhydride, B
2
O
3
, from one of the minerals.
(ii) Reduction of B
2
O
3
.
1st Step
(a) Preparation of B
2
O
3
from borax:
The finely ground borax is heated with concentrated hydrochloric acid or concentrated sulphuric
acid when sparingly soluble orthoboric acid separates out.
Na
2
B
4
O
7
+ 2HCl 2NaCl + H
2
B
4
O
7
Borax Tetraboric acid
Na
2
B
4
O
7
+ H
2
SO
4
Na
2
SO
4
+ H
2
B
4
O
7
H
2
B
4
O
7
+ 5H
2
O 4H
3
BO
3
Orthoboric acid
Orthoboric acid is strongly heated to get B
2
O
3
2H
3
BO
3
B
2
O
3
+ 3H
2
O
(b) Preparation of B
2
O
3
from colemanite:
(i) The powdered mineral is fused with sodium carbonate.
Ca
2
B
6
O
11
+ 2Na
2
CO
3
2CaCO
3
+ Na
2
B
4
O
7
+ 2NaBO
2
Colemanite
The fused mass is extracted with hot water. CaCO
3
remains as insoluble. The fiterate containing
Sborax and sodium metaborate is put to crystallisation when borax is obtained. The remaining
solution is treated wth carbon dioxide which converts sodium metaborate into borax.
4NaBO
2
+ CO
2
Na
2
B
4
O
7
+ Na
2
CO
3
The borax is then converted into B
2
O
3
in the manner described above.
(ii) The other method of conversion of colemanite into B
2
O
3
involves the suspension of mineral
in water and passing of sulphur dioxide gas into the suspension.
Ca
2
B
6
O
11
+ 4SO
2
+ 4 H
2
O 2Ca(HSO
3
)
2
+ H
4
B
6
O
11
H
4
B
6
O
11
+ 7 H
2
O 6H
3
BO
3

Ca
2
B
6
O
11
+ 11 H
2
O + 4SO
2
2Ca(HSO
3
)
2
+ 6H
3
BO
3
On concentration and cooling, crystals of boric acid separate out. These crystals from B
2
O
3
on
strong heating.
2H
3
BO
3
B
2
O
3
+ 3H
2
O
2nd step
Reduction of B
2
O
3
: The reduction of boric anhydride (B
2
O
3
), can be done with sodium, potassium or
magnesium. The boric anhydride is mixed with sodium, potassium or magnesium
powder and heated in a covered crucible.
B
2
O
3
+ 6Na 2B + 3 Na
2
O
B
2
O
3
+ 6K 2B + 3K
2
O
B
2
O
3
+ 3Mg 2B + 3MgO
The fused mass is stirred with iron rod as to oxidise the unreacted sodium or potassium. T h e
mass is then boiled with dil. HCl when insoluble boron powder is obtained. It is washed with water
and made dry. This is the amorphous variety of boron.
Modern method (Electrolyte method):
Boron is obtained these days by the electrolysis of a fused mixture containing boric anhydride,
magnesium oxide and magnesium fluoride at 1100
0
C. The electrolysis is done in carbon crucible
which acts as anode and iron rod is used as cathode. The magnesium discharged at cathode
reduces B
2
O
3
to boron.
2MgO 2Mg + O
2
B
2
O
3
+ 3Mg 2B + 3MgO
Boron thus obtained is heated electrically in vacuum at 1100
0
C when the impurities are volatilised
off and pure boron is obtained.
Crystalline variety of boron is obtained by the reduction of B
2
O
3
with aluminium powder.
B
2
O
3
+ 2Al 2B + Al
2
O
3
Aluminium is removed by heating the fused mass with NaOH solution.
Physical Properties:
Boron exists in two allotropic forms, (a) crystalline and (b) amorphous. Crystalline boron is black
and chemically inert in nature. It is very hard in nature. It is very hard in nature.
Amorphous boron is brown and chemically active. It melts at 2300
0
C and boils at 2550
0
C.
It is difficult to fuse it. It is bad conductor of heat and electricity. Its density is 2.4 g mL
1
.
Chemical Properties:
(i) Action of air and oxygen:
Amorphous form when heated in air or oxygen at 700
0
C, burns Amorphous form when heated in
air or oxygen at 700
0
C, burns with a reddish flame forming a mixture of oxide and nitride.
4B + 3O
2
2B
2
O
3
2B + N
2
2BN
(ii) Action of water:
Boron is not affected by water under ordinary conditions, however, when steam is passed over red
hot boron, hydrogen is liberated.
2B + 3H
2
O B
2
O
3
+ 3H
2
-
(iii) Action of acids:
Boron is not affected by non-oxidising acids. It is attacked by oxidising acids like conc. H
2
SO
4
and
HNO
3
.
B + 3HNO
3
H
3
BO
3
+ 3NO
2
-
2B + 3H
2
SO
4
2H
3
BO
3
+ 2SO
2
-
(iv) Action of alkalies:
Boron dissolves in fused alkalies, liberating hydrogen.
2 + 6NaOH 2Na
3
BO
3
+ 3H
2
-
(v) Action of metals:
Boron combines with strongly electropositive metals at high temperatures to form borides.
3Mg + B
2
Mg
3
B
2
(vi) Action of non-metals:
Boron forms B
2
S
3
when heated with sulphur. It forms extremely hard substance boron carbide(B
4
C),
when heated with carbon in an electric furnace. Boron combines directly with chlorine and bromine
at higher temperatures.
(vii) Reducing nature:
It is a powerful reducing agent.
3CO
2
+ 4B 2B
2
O
3
+ 3C
3SiO
2
+ 4B 2B
2
O
3
+ 3Si
Uses: Boron is used :
(i) as a deoxidiser in the casting of copper.
(ii) for making boron steels which are very hard and are used as control rods in atomic reactors.
(iii) as a catalytic agent.
Boron steel or boron carbide rods are used to control the nuclear reactions. Boron has a very high
cross-section to capture the neutrons. According to another concept boron absorbs neutron to
make the boron having even number of neutrons.
5
B
10
+
0
n
1

5
B
11
Compounds of Boron
1. Boron Trioxide, B
2
O
3
It is also called sesquioxide. It is an anhydride of orthoboric acid.
It is prepared by burning boron in oxygen,
4B + 3O
2
2B
2
O
3
or heating orthoboric acid to redness,
2H
3
BO
3
B
2
O
3
+ 3H
2
O
It is a white hygroscopic solid. It absorbs moisture (becoming opaque from transparent galssy
mass) and finally converted into boric acid.
B
2
O
3
+ H
2
O 2HBO
2
(Metaboric acid)
HBO
2
+ H
2
O H
3
BO
3
(Orthoboric acid)
(B
2
O
3
is, thus, the anhydride of orthoboric acid)
It is an acidic oxide. It combines with metal oxides when fused and forms metaborates.
Some of the metaborates have characterstic colours (This is the basis of borax bead test.)
CuO + B
2
O
3
Cu(BO
2
)
2
[The volatile part of the salt is displaced by B
2
O
3
CuOSO
3
+ B
2
O
3
CuOB
2
O
3
+ SO
3
(CuSO
4
) blue bead
[Cu(BO
2
)
2
]
Cr
2
O
3
3SO
3
+ 3B
2
O
3
Cr
2
O
3
3B
2
O
3
+ 3SO
3
]
[Cr
2
(SO
4
)
3
] Green bead
[2Cr(BO
2
)
3
]
It is reduced by magnesium.
B
2
O
3
+ 3Mg

Heated
2B + 3MgO
When reacted with strongly acidic oxides, it behaves as a base.
2B
2
O
3
+ P
4
O
10
4BPO
4
2. Borax (Sodium Tetraborate)Na
2
B
4
O
7
.10H
2
O
(i) It is also called Tincal or Suhaga. Tincal conatins about 45% of borax. Advantage is taken of its
higher solubility in hot water and purification. The natural tincal is dissolved in hot water and insoluble
impurities are filtered off. The solution is concentrated and cooled when crystals of borax are
obtained.
(ii) Borax can be obtained from colemanite mineral
(iii) From boric acid:
Small quantities of borax are obatined from boric acid by neutralising it with soda ash.
4H
3
BO
3
+ Na
2
CO
3
Na
2
B
4
O
7
+ 6H
2
O + CO
2
Properties : Borax is known in three forms: (i) Prismatic borax which is the common form and is the
decahydrate form, Na
2
B
4
O
7
10H
2
O. It is obtained by crystallising the solution at ordinary
temperature. It is less soluble in hot water. (ii) Octahedral form, which is the pentahydrate, Na
2
B
4
O
7
5H
2
O, is obtained by crystallising solution at 60
0
C. This is jewellers borax. (ii) Borax glass is the
anhydrous form, Na
2
B
4
O
7
. It is obtained by heating the common from above its melting point. It is
a colourless glassy mass and is not stable in moist air as it absorbs moisture and is gradually converted
into decahydrate form.
Basic nature: The solution of borax is alkaline in nature. This is due to its hydrolysis (salt of strong alkali
and weak acid). Na
2
B
4
O
7
+ 7H
2
O 2NaOH + 4H
3
BO
3
strong alkali weak acid
Action of heat:
On heating, borax first swells up due to elimination of water molecules. On further heating, it melts
to a liquid which then solidifies to a transparent glassy mass.
Na
2
B
4
O
7
10H
2
O
O H 10
Heat
2

Anhydrous
7 4 2
O B Na

C 740
0

meta Sodium
2
NaBO 2 +
Boric
3 2
O B


mass Glassy
anhydride borate
When hot glassy mass is brought in contact with a coloured salt and heated again in the flame, B
2
O
3
displaces the volatile oxides and combines with basic oxides to form metaborates.
Metaborates of basic radicals have characterstic colours.
CuSO
4
+ B
2
O
3
CuOB
2
O
3
+ SO
3

Cu(BO
2
)
2
Blue
This is the chemistry of borax bead test.
(iv) Various compounds of boron can be obtained from borax.
(v) Aqueous solution of borax acts as a buffer because it contains weak acid and its salt with
strong base.
Na
2
B
4
O
7
+ 7H
2
O 2Na[B(OH)
4
] + 2H
3
BO
3
Structure of borax:
Borax can be represented as Na
2
[B
4
O
5
(OH)
4
]8H
2
O. It has two tetrahedral and two trianglular
units joined together as shown in the following figure.
Uses: Borax is used:
(i) for the borax bead test in qualitative analysis.
(ii) as a flux. [This is based on its property to dissolve many metal oxides to form borates of
low melting points.]
(iii) as an antiseptic.
(iv) in water softening as it forms insoluble calcium and magnesium borates (CaB
4
O
7
, MgB
4
O
7
).
(v) in the manufacture of enamels and glazes for pottery and tiles.
(vi) in making optical glasses and also borosilicate glass which is very resistant to heat and
shock.
(vii) in leather industry for cleaning hides and skins.
(viii) for impregnating match-sticks to prevent after glow.
(ix) for stiffening of candles.
3. Orthoboric acid, H
3
BO
3
Preparation : (i) From borax:
A hot concentrated solution of borax is treated with calculated quantity of concentrated sulphuric
acid. When the solution is cooled, crystals of boric acid are obtained.
Na
2
B
4
O
7
+ H
2
SO
4
+ 5H
2
O Na
2
SO
4
+ 4H
3
BO
3
(ii) From colemanite:
A large quantity of boric aicd is made from colemanite mineral. The mineral is powdered and mixed
with boiling water. Sulphur dioxide is circulated through the suspension when boric acid is formed.
Ca
2
B
6
O
11
+ 2SO
2
+ 11H
2
O 2Ca(HSO
3
)
2
+ 6H
3
BO
3
on cooling, boric and crystalline out.
(iii) From Tuscany soffioni:
Boric acid occurs in the jets of steam called soffioni issuing from the ground in the volcanic regions
of Tuscany. The jets are caught in large tanks of water. The resulting liquid is concentrated by
steam. On allowing the hot solution to cool, crystals of boric acid separate out.
Properties:(i) It forms soft , white, needle like crystals having a soapy touch.
(ii) It is less soluble in cold water but more soluble in hot water. It is steam volatile.
(iii) It is a weak acid and ionises mainly as monobasic acid.
H
3
BO
3
+ H
2
O H
3
O
+
+ H
2
BO
3

(iv) When heated at 100

0
C, it loses water and converted into metaboric acid.
H
3
BO
3

100
0
C

HBO
2
+ H
2
O
When metaboric acid is heated at 160
0
C, tetraboric acid results.
H
2
B
4
O
7
2B
2
O
3
+ H
2
O
(v) A mixture of ethyl alcohol with boric acid burns with greed edged flame due to the formation
of volatile ethyl borate.
H
3
BO
3
+ 3C
2
H
5
OH B(OC
2
H
5
)
3
+ 3H
2
O
Ethyl borate
Uses: Orthoboric acid is used:
(i) as an antiseptic and eye wash under the name boric lotion.
(ii) in the manufacture of enamels and glazes for pottery.
(iii) as food preservative.
(iv) in glass industry.
4. Halides of boron :
Boron combines with halogens anf forms the halides of type BX
3
, (X = F, Cl, Br, I).
Except BF
3
, other trihalides can be prepared by the treatment of halogens on a mixture of B
2
O
3
and carbon at high temperature.
B
2
O
3
+ 3C + 3X
2
2BX
3
+ 3CO
(X
2
= Cl
2
, Br
2
, I
2
)
BF
3
may be obtained by heating CaF
2
with concentrated sulphuric acid and boric anhydride.
3CaF
2
+ B
2
O
3
+ 3H
2
SO
4
2BF
3
+ 3CaSO
4
+ 3H
2
O
Boron trihalides are also obtained by direct combination of boron and halogens under suitable
conditions.
2B + 3X
2
3BX
3
Properties:
(i) These are covalent in nature due to small size and high charge density on B
3+
ion.
(ii) These are non-electrolyses as in liquid state do not conduct electricity.
(iii) The boiling points are very low. The boiling points increase as the atomic number of halogens
increases. BF
3
is a colourless gas, BCl
3
is a colourless fuming liquid (b. pt. = 13
0
C), BBr
3
is also a colourless fuming liquid (b. pt. = 90
0
C) while BI
3
is a white fusible solid (m. pt.
310
0
C)
(iv) The trihalides are electron deficient compounds. Boron atom acquires six electrons on account
of three B X bonds, i.e., 2 electrons short of an octet. Thus, the boron atom in BX
3
molecule can
accept two more electrons, i.e., an electron pair from the donor atoms like N, P, O, S, F etc., in
NH
3
, PH
3
, H
2
O, H
2
S, HF, F

, etc., respectively to form addition compounds (donor-acceptor

compounds).
H
3
N : + BF
3
[H
3
N BF
3
]
Donor Acceptor
(Lewis base) (Lewis acid)
The relative Lewis acid character of boron trihalides is found to follow the following order.
BI
3
> BBr
3
> BCl
3
> BF
3
but the expected order on the basis of electronegativity of the halogens (electronegativity of halogens
decreases from F to I should be,
BF
3
> BCl
3
> BBr
3
> BI
3
This anomaly is expalined on the basis of the relative tendency of the halogen atom to back donate
its unutilised electrons to vacant p-orbital of boron atom. In BF
3
, boron has a vacant 2p orbital and
each fluorine has fully filled unutilised 2p-orbitals. Fluorine transfers two electrons to vacant 2p-
orbital of boron, thus forming pp-pp bond.
This type of bond has some double bond character and is known as dative or back bonding. All the
three bond lengths are same. It is possible when double bond is delocalized. The delocalization
may be represented as:
-
This bond reduces the electron deficieny of boron atom hence its Lewis acid character decreases.
The tendency to form back bonding its maximum in BF
3
and decreases from BF
3
to BI
3
. Thus,
BCl
3
, BBr
3
and BI
3
are stronger Lewis acids then BF
3
.
(v) All boron trihalides, except boron trifluoride, are hydrolysed to boric acid.
BCl
3
+ 3H
2
O H
3
BO
3
+ 3HCl
The degree of hydrolysis increases from BCl
3
to BI
3
. Due to resistance of BF
3
to hydrolysis and its
tendency to act as Lewis acid, BF
3
is used as a catalyst in organic reaction.
5. Hydrides of Boron:
Boron forms a number of hydrides. These are called boranes by analogy with alkanes.
These belong to one of the two series, viz., B
n
H
n+4
and B
n
H
n+6
. The members of B
n
H
n+6
are less
stable.
B
n
H
n+4
B
n
H
n+6
B
2
H
6
B
4
H
10
B
5
H
9
B
5
H
11
B
6
H
10
B
6
H
12
B
10
H
14
B
9
H
15
The simplest boron hydride, BH
3
, in unknown. The most important hydride is dibornae(B
2
H
6
) which
has been extensibely studied.
Diborane , B
2
H
6
: It is prepared:
(i) By the action of lithium aluminium hydride on boron trichloride in the presnce of ether.
4BCl
3
+ 3LiAlH
4

Ether

2B
2
H
6
+ 3LiCl + 3AlCl
3
(ii) By passing silent electric discharge at low pressure through a mixture of boron trichloride
or tribromide and excess of hydrogen.
2BCl
3
+ 6H
2

Silent electric
disch e

ar
B
2
H
6
+ 6HCl
(iii) By reacting lithium hydride with boron trifluoride
8BF
3
+ 6LiH B
2
H
6
+ 6LiBF
4
Properties:
(i) It is a colourless gas which is stable at low temperature in the absence of moisture and grease. At
higher temperatures in the absence of moisture and grease. At higher temperatures, it changes to
higher boranes and at red heat it decomposes to boron and hydrogen. It has disagreeable odour
and causes headache.
B
2
H
6

!ed heat

2B + 3H
2
(ii) It burns in oxygen. The reaction is highly exothermic.
B
2
H
6
+ 3O
2
B
2
O
3
+ 3H
2
O + heat
(iii) It readily reacts with water liberating hydrogen.
B
2
H
6
+ 6H
2
O 2H
3
BO
3
+ 6H
2
(iv) It reacts with strong alkalies to form metaborates and hydrogen.
B
2
H
6
+ 2KOH + 2H
2
O 2KBO
2
+ 6H
2
(v) It reacts with chlorine forming boron trichloride.
B
2
H
6
+ 3Cl
2
2BCl
3
+ 3HCl
(vi) In presence of anhydrous aluminium chloride, it reacts with dry HCl.
B
2
H
6
+ HCl B
2
H
5
Cl + H
2
Chlorodiborane
(vii) Lithium borohydride is formed when dibornae reacts with LiH in presence of ether.
2LiH + B
2
H
6

Ether

2LiBH
4
(viii) It reacts with carbon monoxide under pressure to form carbonyl, BH
3
CO.
B
2
H
6
+ 2CO 2BH
3
CO
(ix) It reacts with sodium amalgam forming an addition compound.
B
2
H
6
+ 2Na (amalgam) B
2
H
6
Na
2
(x) At low temperatures, an addition product, B
2
H
6
2NH
3
, is obtained with ammonia.
B
2
H
6
+ 2NH
3

"o# tem$%

B
2
H
6
2NH
3
When the addition product is heated at 200
0
C, a volatile compound borazole or inorganic benzene
is formed.
2B
2
H
6
2NH
3
2B
3
N
3
H
6
+ 12 H
2
Borazole
Borazole has a ring structure like benzene.
Uses: The important uses of diborane are:
(i) as a catalyst in polymerization reactions.
(ii) as a reducing agent in organic reactions
(iii) for making high energy fuels and propellants
(iv) for preparing ydrcarbons, alcohols, ketones and acids through hydroboration method.
Structure:Diborane is an example of electron deficient compound. Boron atom has three half filled orbitals
in excited state, i.e., it can link with three hydrogen atoms. Thus, while each boron atom in diborane
can link to itself three hydrogen atoms, there are no electrons left to form a bond between two
boron atoms as shown below:
Diethyl in 1921 proposed a bridge structure for diborane. Four hydrogen atoms, two on the left
and two on the right, known as terminal hydrogens and two boron atoms lie in the same plane. Two
hydrogen atoms forming bridges, one aboveand other below, lie in a plane
perpendicular to the rest of molecule. This structure shows that there are two types of hydrogen
atoms Terminal and bridging. 4terminal hydrogen atoms can easily be replaced by methyl groups
but when two bridging hydrogen atoms are attacked, the molecule is ruptured.
According to molecular orbital theory, each of the two boron atoms is sp
3
hybrid state. Of t h e
four hybrid orbitals, three have one electron each while the fourth is empty. Two of the four orbitals
of each of the boron atom overlap with two terminal hydrogen atoms forming two normal BH s-
bonds.One of the remaining hybrid orbital (either filled or empty) of one of the boron atoms, 1s
orbital of hydrogen atom (bridge atom and one of the hybrid orbitals of the other boron atom
overlap to form a delocalized orbital covering the three nuclei with a pair of electrons. Such a bond
is known as three centre two electron bonds.

Formation of three centre bond (BHB)
Similar overlapping occurs in one hydrogen atom (bridging and fourth hybrid orbital of each boron
atom. Thus, the formation of diborane molecule can be depicted as shown in the following figure.
Structure of diborane
On account of repulsion between the two hydrogen nuclei, the delocalized orbitals of bridges are
drifted away from each other giving the shape of a banana. The three centre two electron bonds are
also known as banana bonds.
ALUMINIUM
Occurence:Aluminium is a third most abundant element forming 8.3% of earths crust. It is a constituent
of clay, slate and many types of silicate rocks. It is found only in the combined state, the important
minerals are:
(i) Oxides:(a) Corundum, ruby, sapphire, emerald, Al
2
O
3
.
(b) Diaspore, Al
2
O
3
H
2
O
(c) Gibbsite, Al
2
O
3
3H
2
O.
(d) Bauxite, Al
2
O
3
2H
2
O, it is the chief ore of aluminium from which extraction of aluminium is
made. It is usually associated with varying amounts of ferric oxide and silica.
(ii)Fluoride: Cryolite, Na
3
AlF
6
. It is the second important ore of aluminium.
(iii) Basic Sulphate:
Alunite or alum stone, K
2
SO
4
Al
2
(SO
4
)
3
4Al(OH)
3
(iv) Basic Phosphate:
Turquoise, AlPO
4
Al(OH)
3
H
2
O. It is usually blue coloured due to presence of copper phosphate.
(v) Silicates: Felspar, KAlSi
3
O
8
, kaolin, porcelain, mica, china clay, slate, etc. Al
2
O
3
2SiO
2
2H
2
O
Extraction: Aluminium is mainly isolated from bauxite ore which is generally contaminated with ferric
oxide and silica. The removal of ferric oxide and silica from bauxite ore is essential before it is
subjected to electrolysis because it is rather difficult to remove iron and silicon from aluminium
metal, the presence of these elements makes the aluminium metal brittle and liable to corrosion.
Thus, the extraction of aluminium from bauxite ore involves the following three steps. m
(i) Purification of bauxite ore, i.e. removal of ferric oxide and silica.
(ii) Electrolytic reduction of Al
2
O
3
.
(iii) Electrolytic purification of aluminium.
Purification of bauxite ore:
The following methods are used for purifying the bauxite ore.
(a)Baeyers process:
This process is mainly applied to bauxite ore containing ferric oxide as chief impurity. The colour of
such ore is usually red and hence called red bauxite. The powdered ore is first roasted at a low
temperature as to convert any ferrous oxide, if present, into ferric oxide. It is then digested with a
concentrated solution of sodium hydroxide (density 1.45 g mL
1
) in an autoclave under pressure at
150
0
C for several hours. The aluminium oxide dissolves in caustic soda forming soluble sodium
meta aluminate and settle down. These are removed by filteration.
Al
2
O
3
2H
2
O + 2NaOH 2NaAlO
2
+ 3H
2
O
Sodium meta aluminate
(soluble)
The precipitate is washed and dried.
The soluble of NaOH is concentrated and used again.
(b)Halls process:
Bauxite is fused with sodium carbonate. Al
2
O
3
combines with sodium carbonate forming sodium
meta aluminate. The fused mass is extracted with water where Fe
2
O
3
and SiO
2
remain as insoluble
in the residue.
Al
2
O
3
+ Na
2
CO
3
2NaAlO
2
+ CO
2
The solution containing sodium meta aluminate is warmed to 50-60
0
C and carbon dioxide is circulated
through it. Al(OH)
3
separates out as precipitates.
2NaAlO
2
+ CO
2
+ 3H
2
O 2Al(OH)
3
+ Na
2
CO
3
The precipitate is filtered, washed and dried.
The solution of Na
2
CO
3
is concentrated and used again.
(c) Serpecks process:
This process is used when silica is present in considerable amounts in bauxite ore. The ore is mixed
with coke and heated at 1800
0
C in presence of nitrogen, where AIN (Aluminium nitride) is formed.
Al
2
O
3
+ 3C + N
2
2AIN + 3CO
Silica is reduced to silicon which violatilises off at this temperature.
SiO
2
+ 2C Si + 2CO
AIN is hydrolysed with water into aluminium hydroxide.
This process has one distinct advantage that ammonia is obtained as a valuable by product.
Calcination of aluminium hydroxide:
The aluminium hydroxidem precipitate obtained in the above processes is calcined at 1500
0
C in a
rotary kiln to obtain pure alumina (Al
2
O
3
)
2Al(OH)
3

1&00
0
C

Al
2
O
3
+ 3H
2
O
Electrolytic reduction of pure alumina:
The electrolysis of pure alumina faces two difficulties: (i) Pure alumina is a bad conductor of electricity,
(ii) The fusion temperature of pure alumina is about 2000
0
C and at this temperature when t he
electrolysis is carried of fused mass, the metal formed vapourises as the boiling point of aluminium
is 1800
0
C. The above difficulties are overcome by using a mixture containing alumina, cryolite
(Na
3
AlF
6
) and fluorspar (CaF
2
) in the ratio of 20:24:20. The fusion temperature of this mixture is
900
0
C and it is a good conductor of electricity. The electrolysis is carried out in an iron box
lined inside with gas carbon which acts as cathode. The anode consists of carbon rods which dip
in the fused mixture of the electrolyte from above. The fused electrolyte is covered with a layer of
coke.
The current passed through the cell serves two purposes (i) heating of the electrolyteThe
temperature of the cell is automatically maintained at 900950
0
C, (ii) electrolysis. On passing current
current, aluminium is discharged at cathode. Aluminium being heavier than electrolyte sinks to
the bottom and is atpped out periodically from tapping hole. Oxygen is liberated at anode. It attacks
carbon rods forming CO and CO
2
. The process is continuous. When the concentration of the
electrolyte decreases, the resistance of the cell increases. This is indicated by the glowing of a lamp
placed in parallel. AT this stage more of alumina is added.
The exact mechanism of the electrolysis is not yet known. Two concepts have been proposed.
First concept:
AlF
3
Al
3+
+ 3F

Al
3+
ions are discharged at cathode and F

ions at anode.
Al
3+
+ 3e Al (at cathode)
2F

F
2
+ 2e (at anode)
The liberated fluorine reacts with alumina to form AlF
3
and O
2
. The oxygen attacks the carbon
anodes to form CO and CO
2
.
Al
2
O
3
+ 3F
2
2AlF
3
+ 3/2 O
2
2C + O
2
2CO
C + O
2
CO
2
Anodes are replaced frequently.
Second concept:
Alumina (Al
2
O
3
) ionises as
Al
2
O
3
Al
3+
+ AlO
3
3
Cathode Anode
Al
3+
+ 3e Al(at cathode)
At anode AlO
3

is oxidised.
4AlO
3
3
2Al
2
O
3
+ 3O
2
+ 12 e (at anode)
Thus, the overall chemical reaction taking place during electrolysis is,
2Al
2
O
3
4Al + 3O
2
Aluminium of 99.8% purity is obatined from this process.
Refining of aluminium by Hoopes electrolytic method:
Aluminium is further purified by Hoopes process. The electrolytic cell consists of an iron box lined
inside with carbon. The cell consists of three layers which differ in specific gravities. The upper
layer is of pure aluminium which acts as cathode. The middle layer consists of a mixture of the
fluorides of Al, Ba and Na. The lowest layer consists of impure aluminium which acts as anode. The
middle layer works as electrolyte.
The graphite rods dipped in pure aluminium and Cu-Al alloy rod at the bottom in the impure
aluminium work as conductors. One electrolysis, aluminium is deposited at cathode from the middle
layer and an equminium is taken up by the middle layer from the bottom layer (impure aluminium).
Therefore, aluminium is transferred form bottom to the top layer through middle layer while the
impurities are left behind. Aluminium thus obtained is 99.98% pure.
Physical Properties:
(a) Aluminium is a bluish white lustre metal. The lustre is destroyed on long exposure to air
due to formation of a thin film of oxide on the surface.
(b) The density of aluminium is 2.7 g mL
-1
(light metal). It is malleable and ductile.
(c) It is a good conductor of heat and electricity.
(d) It melts at 660
o
C and boils at 1800
o
C.
(e) It can be welded and cast but difficult to solder.
FLOWSHEET FOR THE EXTRACTION OF ALUMINIUM
Aluminium ore, Al
2
O
3
2H
2
O(Bauxite)

REFINING OF BAUXITE
(a) Baeyers Process:
Bauxite ore
!oasted

as to convert FeO into Fe
2
O
3
Roasted ore + NaOH
solution

1&0
'0
0
C
atm

%
NaAlO
2

Hydrolysis
in $resence
o( little Al OH

) *
3
Al OH
$$t
) *
%
3
+ NaOH
(b) Halls Process:
Bauxite ore + Na
2
CO
3

+used

NaAlO
2
Extracted with water
Solution
Warmed 5060
0
C
CO
2
is circulated

Al OH
$$t
) *
%
3
+ Na
2
CO
3
(c) Serpecks Process:
Bau,ite ore
nitroen
+ Coke
1'00
0
C

AIN
H O
2

Al OH
$$t
) *
%
3
+ NH
by $roduct
3

CALCINATION
Al(OH)
3

1&00
0
C

Al
2
O
3
Anhydrous alumina

ELECTROLYTIC REDUCTION
Electrolyte Al
2
O
3
dissolved in Na
3
AlF
6
and CaF
2
CathodeCarbon lining Anode Graphite rods
Al
2
O
3

Electrolysis
C

-&0
0

Al
$ure -- '. %
+ O
2
ELECTROLYTIC REFINING
(Hoopes process) Pure Al (99.98% pure)
Chemical Properties:
(a) Action of air: Aluminium is not affected by dry air but in moist air a thin film of oxide is formed
over its surface. It burns in oxygen producing brilliant light.
4Al + 3O
2
2Al
2
O
3
The reaction is highly exothermic and the heat evolved is used in the thermite process for the
reduction of oxides of Cr, Fe, Mn, etc.
(b) Action of water: Pure aluminium is not affected by pure water. The impure aluminium is readily
corroded by water containing salts (sea water). Aluminium decomposes boiling water evolving
hydrogen.
-
-
2Al + 6H
2
O 2Al(OH)
3
+ 3H
2
-
(c) Action of acids: The oxidation potential of aluminium is 1.66 volts thus, it is strongly electropositive,
very reactive and a powerful reducing agent. It dissolves in HCl(dil. and conc.) and dilute sulphuric
acid, evolving hydrogen.
2Al + 6HCl 2AlCl
3
+ 3H
2
-
2Al + 3H
2
SO
4
Al
2
(SO
4
)
3
+ 3H
2
-
The reaction with dil. H
2
SO
4
is very slow probably on account of the insolubility of the oxide film in this acid.
Hot concentrated sulphuric aicd dissolves Al with evolution of SO
2
.
2Al+6H
2
SO
4
Al
2
(SO
4
)
3
+ 3SO
2
+ 6H
2
O
Dilute and concentrated HNO
3
has no effect on Al, i.e., Al is rendered passive by nitric acid. This
is due to surface oxidation and formation of a thin film of oxide on its surface. Organic acids have
little action on Al at ordinary temperatures.
(d) Action of alkalies:
Aluminium is attacked by caustic alkalies with the evolution of hydrogen.
2Al +
2 2
2
NaOH H O
solution
+


2
2
NaAlO
Sodium meta
alu ate so le min ) lub *
+ 3H
2
-
2Al + 6NaOH
+used

2
3 3
Na AlO
Sodium alu ate min
+ 3H
2
-
(e) Action of non-metals:
Besides oxygen, aluminium reacts with non-metals directly to form corresponding compounds.
Aluminium when heated in the atmosphere of nitrogen, forms aluminium nitride.
2Al + N
2
2AIN
Aluminium powder when fused with sulphur forms aluminium sulphide.
2Al + 3S Al
2
S
3
Finely powdered heated aluminium combines with halogens to form corresponding halides.
2Al + 3X
2
2AlX
3
(X
2
= F
2
, Cl
2
, Br
2
, I
2
)
All these compounds are hydrolysed with water.
AlN + 3H
2
O Al(OH)
3
+ NH
3
Al
2
S
3
+ 6H
2
O 2Al(OH)
3
+ 3H
2
S
AlX
3
+ 3H
2
O Al(OH)
3
+ 3HX
(f) Reducing agent:
It is a good reducing agent and reduces oxides of metals like Cr, Fe, Mn etc.
Cr
2
O
3
+ 2Al 2Cr + Al
2
O
3
+ heat
Fe
2
O
3
+ 2Al 2Fe + Al
2
O
3
+ heat
3Mn
3
O
4
+ 8Al 9Mn + 4Al
2
O
3
+ heat
It reduces oxides of non-metals also
3CO
2
+ 4Al 2Al
2
O
3
+ 3C
3SiO
2
+ 4Al 2Al
2
O
3
+ 3Si
(g) Displacement of other metals:
Being more electropositive it displaces copper, zinc and lead from the solution of their salts.
3ZnSO
4
+ 2Al Al
2
(SO
4
)
3
+ 3Zn
3CuSO
4
+ 2Al Al
2
(SO
4
)
3
+ 3Cu
Uses: (i) Aluminium being cheap and light metal is largely used for making household utensils, trays,
frames, etc. Bodies of autmobiles, aircraft and roofing are made of aluminium sheet.
(ii) Thin foils of Al are used in wrapping soaps, cigarettes and confectionary.
(iii) Al wire is used in transmission lines and coils for dynamos and motors.
(iv) It is used for making silvery paints for covering iron and other materials.
(v) It is used in thermic process for tyhe extraction of Cr, Mn, etc.
(vi) Since it is not attacked by nitric acid, it is used in chemical plants and for transporting nitric
acid.
(vii) Because of its lightness, good conductivity and resistance to corrosion, it is used for making
alloys which find applications in industries and arts.
(viii) Aluminium amalgam is used as a reducing agent.
(ix) Aluminium powder is used in fire works, flash light powder and in thermite welding.
Compounds of aluminium
1. Aluminium Oxide or Alumina, Al
2
O
3
It occurs in nature as colourless corundum and tinted with metallic oxides as ruby (red), sapphire
(blue), amethyst (violet), emery (green), etc. These coloured oxides are precious stones. Hydrated
oxide (Al
2
O
3
.2H
2
O) occurs as Bauxite.
It is prepared by igniting aluminium hydroxide, aluminium sulphate or ammonium alum.
2Al(OH)
3
Al
2
O
3
+ 3H
2
O
Al
2
(SO
4
)
3
AL
2
O
3
+ 3SO
3
(NH
4
)
2
SO
4
.Al
2
(SO
4
)
3
.24H
2
O Al
2
O
3
+ 2NH
3
+ 4SO
3
+ 25H
2
O
It is obtained in crystalline form by strongly heating a mixture of aluminium fluoride and boric oxide.
2AlF
3
+ B
2
O
3
Al
2
O
3
+ 2BF
3
It is a white solid, insoluble in water. It is a stable and unreactive substance. It begins to volatilise at
1750
o
C. It boils at 2250
o
C.
It shows amphoteric nature. When it is fused with oxides of chromium, iron and cobalt, synthetic
semi-precious stones are obtained.
It is widely used for making bauxite bricks which are used for lining furnaces. Fused alumina is used
as refractory material. When heated in an electric arc at 3000
o
C, a hard powder known as alundun
is obtained which is used as abrasive. With lime, it is used as bauxitecement which is not affected
by sea water. It is used in chromatography, in extraction of aluminium and in preparing precious
stones.
2. Aluminium chloride, AlCl
3
(i) Anhydrous aluminium chloride:
It is prepared by passing dry HCl gas or chlorine gas over heated aluminium turnings in absence of
air. The vapours of aluminium chloride are condensed when solid anhydrous aluminium chloride is
obtained.
2Al + 6HCl 2AlCl
3
+ 3H
2
2Al + 3Cl
2
2AlCl
3
It can also be obtained by heating a mixture of alumina and caubon in an atmosphere of chlorine.
Al
2
O
3
+ 3C + 3Cl
2

1000
0
C

2AlCl
3
+ 3CO
Vapours

B
Cooled
Solid anhydrous aluminium chloride
(ii) Hydrated aluminium chloride:
AlCl
3
.6H
2
O, is formed when aluminium metal or aluminium hydroxide is dissolved in dilute
hydrochloric acid.
2Al + 6HCl AlCl
3
+ 3H
2
Al(OH)
3
+ 3HCl AlCl
3
+ 3H
2
O
HCl gas is circulated through the solution to obtain crystals of hydrated aluminium chloride.
Properties:(a)Anhydrous aluminium chloride is a white solid. It is deliquescent and fumes in air. On heating
it sublimes a 180
o
C and the vapour density corresponds to the formula Al
2
Cl
6
. It is covalent when
anhydrous as it does not conduct current in fused state. It is soluble in organic solvents such as
alcohol, ether, benzene, etc. The dimeric formula is retained in non-polar sovents but is broken into
[Al(H
2
O)
6
]Cl
3
on dissolution in water on account of high heat of hydration. The molecular (dimer)
is an autocomplex and is represented as,
(b) Anhydrous aluminium chloride fumes in moist air due to evolution of HCl.
Al
2
Cl
6
+ 6H
2
O 2Al(OH)
3
+ 6HCl
When dissolved in water, it changes into hydrated aluminium chloride which is ionic in nature.
Al
2
Cl
6
+ 12H
2
O 2AlCl
3
.6H
2
O
AlCl
3
Al
3+
+ 3Cl
-
(c) Anhydrous aluminium chloride forms an addition product with ammonia gas.
Al
2
Cl
6
+ 12NH
3
2[AlCl
3
.6NH
3
]
(d) The solution of aluminium chloride in water is acidic in nature due to hydrolysis.
AlCl
3
+ 3H
2
O Al(OH)
3
+ 3HCl
Weak base Strong acid
(e) When ammonium hydroxide is added to the solution of aluminium chloride, a gelatinous
precipitate of aluminium hydroxide appears which does not dissolve in excess of NH
4
OH.
AlCl
3
+ 3NH
4
OH Al(OH)
3
+ 3NH
4
Cl
(f) When sodium hydroxide is added to the solution of aluminium chloride drop by drop, a
white gelatinous precipitate appears which dissolves in excess of sodium hydroxide forming
sodium meta-aluminate.
AlCl
3
+ 3NaOH Al(OH)
3
+ 3NaCl
Al(OH)
3
+ NaOH NaAlO
2
+ 2H
2
O
Uses: (i) It is used as a catalyst in FriedelCrafts reaction.
(ii) It is also used in the manufacture of gasoline by cracking of high boiling fractions of petroleum.
(iii) It finds extensive use in the manufacture of dyes, drugs and perfumes.
3. Alums : Formerly, the term alum was used to describe only one double sulphate with 24 molecules of
water of crystallisation, potassium aluminium sulphate, K
2
SO
4
Al
2
(SO
4
)
3
24H
2
O, but now this term
is used for all the double sulphates having the composition,
M
2
SO
4
M
2
(SO
4
)
3
24H
2
O
where M stands for molecular basic radicals such as Na
+
, K
+
, Rb
+
, Cs
+
, Ag
+
, Ti
+
, NH
4
+
and M for
a trivalent basic radicals such as Al
3+
, Cr
3+
, Fe
3+
, Mn
3+
, Co
3+
, etc.
Some examples of alums are:
Potash alum K
2
SO
4
Al
2
(SO
4
)
3
24H
2
O (Commonly called alum)
Ammonium alum (NH
4
)
2
SO
4
Al
2
(SO
4
)
3
24H
2
O
Sodium alum Na
2
SO
4
Al
2
(SO
4
)
3
24H
2
O
Chrome alum K
2
SO
4
Cr
2
(SO
4
)
3
24H
2
O
Ferric alum (NH
4
)
2
SO
4
Fe
2
(SO
4
)
3
24H
2
O
Alums are generally obtained when hot solutions of equimolar quantities of their constituent sulphates
are mixed and the resulting solution is subjected to crystallisation.
Alums are crystalline compounds. In alums each metal ion is surrounded by six water molecules
and the crystals of alums consist of [M(H
2
O)
6
]
+
, [M(H
2
O)
6
]
3+
and SO
4
2
ions.
Alums are fairly soluble in hot water but less soluble in cold water. The solutions are acidic
and have strigent taste.The solutions show the properties of ions of the constituent salts. The alums
are isomorphous to each other and form mixed crystals.
Each alum has different melting point. Alums lose water of crystallisation when heated. If rapidly
heated to a high temperature,the alum swells up and a porous mass called burnt alum is left behind.
The alums are effective in precipitating colloids, i.e., act as coagulants. The alums have germicide
properties. Alums are thus used in the purification of water, tanning of leather, as modrants in
dyeing and as antiseptics.
Potash alum, K
2
SO
4
Al
2
(SO
4
)
3
24H
2
O
It is commonly known as alum.
Preparation:
(i) From bauxite or aluminium sulphate:
Bauxite is boiled with sulphuric acid to form aluminium sulphate. To this solution calculated quantity
of K
2
SO
4
is added. The solution is concentrated and cooled. After some time crystals of potash
alum are obtained.
Al
2
O
3
+ 3H
2
SO
4
Al
2
(SO
4
)
3
+ 3H
2
O
Al
2
(SO
4
)
3
+ K
2
SO
4
+ 24H
2
O K
2
SO
4
Al
2
(SO
4
)
3
24H
2
O
Potash Alum
(ii) From alum stone or alunite:
Alum stone is treated with dilute sulphuric aicd and the solution is boiled. A calculated quantity of
K
2
SO
4
is added to the solution. The solution on cooling yields crystals of potash.
K
2
SO
4
Al
2
(SO
4
)
3
4A;(OH)
3
+ 6H
2
SO
4
K
2
(SO
4
)
3
+ 3Al
2
(SO
4
)
3
+ 12H
2
O
alum stone
K
2
SO
4
Al
2
(SO
4
)
3
+ 24H
2
O K
2
(SO
4
)
3
Al
2
(SO
4
)
3
24H
2
O
Properties:(a)It is a white crystalline compound.
(b) It is soluble in water and its aquoeus solution is acidic due to hydrolysis of Al
2
(SO
4
)
3
.
(c) On heating it swells up on account of elimination of water molecules.
K
2
SO
4
Al
2
(SO
4
)
3
24H
2
O
200
0
C

K
2
SO
4
Al
2
(SO
4
)
3
+ 24 H
2
O
K
2
SO
4
Al
2
(SO
4
)
3

!ed Heat

K
2
SO
4
+ Al
2
O
3
+ 3SO
3
(d) Its aqueous solution contains K
+
, Al
3+
and SO
4
2
ions and their usual tests can be performed.
Uses: It is used:
(i) as a modrant in dyeing and calico printing.
(ii) in sizing of cheap quality of paper.
(iii) in purification of water.
(iv) as antiseptic and in stopping bleeding from cuts.
(v) in leather tanning.
* * * * *
GROUP -IV
Types of Carbide
(i) Ionic and salt like:
Classification on basis of (a) C
1
unit
no. of carbon atoms

(b) C
2
unit
present in hydrocarbon (c) C
3
unit
found on their hydrolysis
C
1
unit: Al
4
C
8
, Be
2
C
Be
2
C + H
2
O Be(OH)
2
+ CH
4
Al
4
C
3
+ 12H
2
O 4Al(OH)
3
+ 3CH
4
C
2
unit: CaC
2
, BaC
2
CaC
2
+ 12H
2
O Ca(OH)
2
+ CHCH
C
3
unit: Mg
2
C
3
Proposed struc. Mg
2
C
3
+ H
2
O 2Mg(OH)
2
+ CH
3
C

C: Propyne

2 2
C C C

= = +

H 4
CH
2
=C=CH
2

Dual show tautomerism

Acetelene
(ii) Covalent carbide : SiC & B
4
C
(iii) Interstitial carbide : MC (Transition element or inner transitional elements forms this kind of carbide)
Interstitial carbide formation doesn't affect the metalic lusture and electrical conductivity.(Q no chemical
bond is present, no change in property)
Fe
3
C: Cementite
SiC
Preparation
SiO
2
+ 2C(coke)
C 2500
to 2000

Si + 2CO-
Si + C
C 2500
to 2000

SiC diamond like structure colourless to yellow solid in room temp.

when impurity is present
Properties
(i) It is very hard and is used in cutting tools and abrassive powder(polishing material)
(ii) It is very much inert
(iii) It is not being affected by any acid except H
3
PO
4
(iv) It reacts with NaOH in presence of air
SiC + 2NaOH + O
2
Na
2
SiO
3
+ CO
2
+ H
2
O
CO
How to detect
How to estimate
What are its absorbers
(i) How to detect
(a) burns with blue flame
(b) CO is passed through PdCl
2
solution giving rise to black ppt.
CO + PdCl
2
+ H
2
O CO
2
- + Pd + 2HCl
Black metallic
deposition
(ii) How to estimate
I
2
O
5
+ 5CO I
2
+ 5CO
2
I
2
+
2
3 2
O S 2I

+
2
6 4
O S
(iii) What are its absorbers
(a) Cu
2
Cl
2
: CuCl + CO + 2H
2
O [CuCl(CO)(H
2
O)
2
]
Uses:
In the Mond's process of Ni - extraction
CO is the purifying agent for Ni
Impure Ni + CO
C 50
Ni(CO)
4

C 150
Ni + 4CO
recycled
Producer gas: CO + N
2
+ H
2
Water gas: CO + H
2
Water gas is having higher calorific value than producer gas. Q in water gas, both CO & H
2
burns while
in producer gas N
2
doesn't burn.
Teflon ) CF CF (
n 2 2

CHCl
3
+ HF
catalyst
SbFCl
with heated
4

CF
2
HCl
HCl
again
heated

CF
2
=CF
2

pess and ! te"p high
at tion #oly"eisa

) CF CF (
n 2 2

Purpose
Temp. withstanding capacity upto 500550C (1
st
organic compound withstand this .......... of high
temp.)
SILICON
Occurrence
Silicon is the second most abundant (27.2%) element after oxygen (45.5%) in the earth's crust. It does
not occur free in nature but in the combined state, it occurs widely in form of silica and silicates. All
mineral rocks, clays and soils are built of silicates of magnesium, aluminium, potassium or iron. Aluminium
silicate is however the most common constituent of rocks and clays.
Silica is found in the free state in sand, flint and quartz and in the combined state as silicates like
(i) Feldspar K
2
O. Al
2
O
3
. 6SiO
2
(ii) Kaolinite Al
2
O
3
. 2SiO
2
. 2H
2
O
(iii) Asbestos CaO. 3MgO. 4SiO
2
Preparation
(i) From silica (sand): Elemental silicon is obtained by the reduction of silica (SiO
2
) with high purity coke in
an electric furnace.
SiO
2
(s) + 2C(s) Si(s) + 2CO(g)
(ii) From silicon tetrachloride (SiCl
4
) or silicon chloroform (SiHCl
3
) : Silicon of very high purity required for
making semiconductors is obtained by reduction of highly purified silicon tetrachloride or silicon chloroform
with dihydrogen followed by purification by zone refining.
SiCl
4
(l) + 2H
2
(g) Si(s) + 4HCl(g)
SiHCl
3
(s) + H
2
(g) Si(s) + 3HCl (g)
PHYSICAL PROPERTIES :
(i) Elemental silicon is very hard having diamond like structure.
(ii) It has shining luster with a melting point of 1793 K and boiling point of about 3550 K.
(iii) Silicon exists in three isotopes, i.e. Si
2$
14
, Si
2%
14
and Si
30
14
but Si
2$
14
is the most common isotope.
CHEMICAL PROPERTIES:
Silicon is particularly unreactive at room temperature towards most of the elements except fluorine.
Some important chemical reactions of silicon are discussed below.
(i) Action of air : Silicon reacts with oxygen of air at 1173 K to form silicon dioxide and with nitrogen of
air at 1673 K to form silicon nitride,.
Si(s) + O
2
(g)

& 11'3
SiO
2
(s)
Silicon dioxide
3Si(s) + 2N
2
(g)

& 16'3
Si
3
N
4
(s)
Silicon nitride
(ii) Action of steam : It is slowly attacked by steam when heated to redness liberating dihydrogen gas.
Si(s) + 2H
2
O(g)

edness
SiO
2
(s) + 2H
2
(g)
(iii) Reaction with halogens: It burns spontaneously in fluorine gas at room temperature to form silicon
tetrafluoride (SiF
4
).
Si(s) + 2F
2
(g)

e (e"peat) *oo"
SiF
4
(l)
However, with other halogens, it combines at high temperatures forming tetrahalides.
(iv) Reaction with carbon : Silicon combines with carbon at 2500 K forming silicon carbide (SiC) known
as carborundum.
Si(s) + C(s)

& 2500
SiC(s)
Carborundum is an extremely hard substance next only to diamond. It is mainly used as an abrasive and
as a refractory material.
USES:
(i) Silicon is added to steel as such or more usually in form of ferrosilicon (an alloy of Fr and Si) to make it
acid-resistant.
(ii) High purity silicon is used as semiconductors in electronic devices such as transistors.
(iii) It is used in the preparation of alloys such as silicon-bronze, magnesium silicon bronze and ferrosilicon.
COMPOUNDS OF SILICON:
Silicates: Details about silicates are given in the topic " Solid State".
What is silane. Si
n
H
2n+2
(SiH
4
) & Si
2
H
6
Only these two are found
Higher molecules are not formed. Q Si can't show catanetion property
Hot Mg + Sivap Mg
2
Si
4 2
SO H ! dil
MgSO
4
+ SiH
4
+ Si
2
H
6
+ ...
Ques. SiH
4
is more reactive than CH
4
. Explain
Reasons
(i)
+
H Si in
+
H C
C - electro-ve than H
Si less electro-ve than H
So bond polarity is reversed when Nu

attacks, it faces repulsion in C but not in Si
(ii) Silicon is having vacant d orbital which is not in case of carbon
(iii) Silicon is larger in size compared to C. By which the incoming Nu

doesn't face any steric hindrance to

attack at Si whereas CH
4
is lightly held from all sides.
Silicones
It is organs silicon polymer
CCl
4
+ H
2
O no hydrolysis
but CCl
4
+ H
2
O COCl
2
+ 2HCl
super heated
steam
SiCl
4
+ H
2
O Si(OH)
4
+ 4HCl
SiO
2
R
2
SiCl
2
+ H
2
O

HCl 2
R
2
Si(OH)
2

O H
2

* * *
+ + +
O Si O Si O Si O
+ + +
* * *

silicon
R
2
CCl
2
+ H
2
O
eadily
O H looses
HCl 2
2

R
2
C(OH)
2


O H
2
* C *
++
O

Silicones may have the cyclic structure also having 3, 4, 5 and 6 nos. of silicon atoms within the ring.
Alcohol analoge of silicon is known as silanol
* *
+ +
* Si O Si *
O O
* Si O Si *
+ +
* *
+ +
+ +


not planar
R
3
SiCl
O H
2
R
3
SiOH

O H
2
R
3
Si-O-SiR
Silanol
R
2
SiCl
2
+ R
3
SiCl
hydolysis
O H
2


on condensati
heating
O H
2

* *
+ +
Si O Si
+ +
* *

This end of the chain can't lie extended hence
* R
3
SiCl is called as chain stopping unit
* Using R
3
SiCl in a certain proportion we can control the chain length of the polymer
RSiCl
3
+ H
2
O R-Si(OH)
3

+ +
* O O
+ + +
O Si O Si O Si *
+ + +
O * O
+ +

sp
3
3 dimensional network
It provides the crosslinking among the chain making the polymer more hard and hence controling the
proportion of RSiCl
3
we can control the hardness of polymer.
Uses
(1) It can be used as electrical insulator (due to inertness of SiOSi bonds)
(2) It is used as water repellant (Q surface is covered) eg. car polish, shoe polish, massonary works in
buildings
(3) It is used as antifoaming agent in sewage disposal, beer making and in cooling oil used to prepare potato chips.
(4) As a lubricant in the gear boxes.
SILICA
Occurrence:
Silica or silicon dioxide occurs in nature in the free state as sand, quartz and flint and in the combined
state as silicates like, Feldspar : K
2
O.Al
2
O
3
.6SiO
2
, Kaolinite : Al
2
O
3
. 2SiO
2
. 2H
2
O etc.
PROPERTIES:
(i) Pure silica is colourless, but sand is usually coloured yellow or brown due to the presence of ferric oxide
as an impurity.
(ii) Silicon dioxide is insoluble in water and all acids except hydrofluoric acid.
SiO
2
(s) + 4HF(l) SiF
4
(l) + 2H
2
O(l)
(iii) It also combines with metallic oxides at high temperature giving silicates e.g.
SiO
2
(s) + CaO(s)

CaSiO
3
(s)
(iv) When silica is heated strongly with metallic salts, silicates are formed and the volatile oxides are driven
off as vapours.
SiO
2
(s) + Na
2
CO
3
(s) Na
2
SiO
3
(s) + CO
2
(g)
SiO
2
(s) + Na
2
SO
4
(s) Na
2
SiO
3
(s) + SO
3
(g)
3SiO
2
(s) + Ca
3
(PO
4
)
2
(s) 3CaSiO
3
(s) + P
2
O
5
(g)
The first two examples quoted here are important in glass making.
STRUCTURES OF SILICA :
Silica has a three-dimensional network structure. In silica, silicon is sp
3
-hybridized and is thus linked to
four oxygen atoms and each oxygen atom is linked to two silicon atoms forming a three-dimensional
giant molecule as shown in figure. This three-dimensional network structure imparts stability to SiO
2
crystal and hence a large amount of energy is required to break the crystal resulting in high melting point.
+ + +
Si O Si O Si
+ + +
O O O
+ + +
Si O Si O Si
+ + +
O O O
+ + +
Si O Si O Si
+ + +
USES:
(i) Sand is used in large quantities to make mortar and cement.
(ii) Being transparent to ultraviolet light, large crystal of quartz are used for making lenses for optical instruments
and for controlling the frequency of radio-transmitters.
(iii) Powdered quartz is used for making silica bricks.
(iv) Silica gel (SiO
2
.xH
2
O) is used as a desiccant (for absorbing moisture) and as an adsorbent in
chromatography.
TIN & ITS COMPOUND
(i) Sn
2
O
C 1500
+

SnO
2
[Burns with a bright flame]

(ii) Sn + 2H
2
O
(iii) Reaction with acid.
Sn
(iv) Sn + 2NaOH + H
2
O Na
2
SnO
3
+ 2H
2
-.
or
KOH [In absence of air Na
2
SnO
2
forms and in contact with air it readity converts into Na
2
SnO
3
]
Oxides:
white gey
SnO , SnO
2

heated
stongly
C 1500


Sn + O
2
SnC
2
O
4

ai
o- contact
o- o)t

SnO (grey) + CO + CO
2

SnCl
2

&OH
Sn(OH)
2
Both are amphoteric in nature :
SnO + H
2
SO
4
SnSO
4
+ H
2
O
SnO + 2HCl SnCl
2
+ H
2
O
SnO + 2NaOH or KOH

cold
Na
2
SnO
2
or K
2
SnO
2
+H
2
O
But conc. hot alkali behaves differently.
2SnO + 2KOH or NaOH K
2
SnO
3
or Na
2
SnO
3
+ Sn + H
2
O
Bi(OH)
3
+ [Sn(OH)
4
]
2
Bi + [Sn(OH)
6
]
2
(black)
SnO
2
+ 2H
2
SO
4
Sn(SO
4
)
2
+ 2H
2
O
(Soluble only in hot conc. H
2
SO
4
)
SnO
2
+ 2NaOH

Na
2
SnO
3
+ H
2
O
SnO
2
+ 4S + 2Na
2
CO
3
Na
2
SnS
3
+ Na
2
SO
4
+ 2CO
2
(Insoluble in all acids even if in aq. rigia)
SnCl
2
& SnCl
4
:
(1) Sn + 2HCl (hot conc.) SnCl
2
+ H
2
-
SnCl
2
.2H
2
O

Sn(OH)Cl + HCl - + H
2
O- Hence anh. SnCl
2
cannot be obtained.

SnO + HCl - {SnCl

4
+ 4H
2
O Sn(OH)
4
+ 4HCl- fumes comes out}
(2) A piece of Sn is always added to presence a solution of SnCl
2
. Explain.
6SnCl
2
+ 2H
2
O + O
2
2SnCl
4
+ 4Sn(OH)Cl (white ppt)
SnCl
4
+ Sn 2SnCl
2
SnCl
4
+ 4H
2
O Sn(OH)
4
(white ppt.) + 4HCl
(3) SnCl
2
+ HCl HSnCl
3

HCl
H
2
SnCl
4

SnCl
4
+ 2HCl H
2
SnCl
6
(Hexachloro stannic (IV) acid)
SnCl
4
+ 2NH
4
Cl (NH
4
)
2
SnCl
6
(colourless crystalline compound known as " pink salt ")
(4) Red Prop. of SnCl
2
:
Sn
+2
+ 2Fe
+3
2Fe
+2
+ Sn
+4
2Cu
+2
+ Sn
+2
2Cu
+
+ Sn
+4
Hg
+2
+ Sn
+2
Hg +Sn
+4
PhNO
2
+ SnCl
2
/ HCl PhNH
2
+ Sn
+4
K
2
Cr
2
O
7
+ SnCl
2
+ HCl Cr
+3
+ Sn
+4
+ KCl + H
2
O
(5) Readily combines with I
2
SnCl
2
I
2
This reaction is used to estimate tin.
Formation of SnCl
4
:
(i)
) "olten (
Sn +
) dy (
) ./cess ( Cl
2
SnCl
4
(ii) 2HgCl
2
+ Sn 2Hg + SnCl
4
(iii) Sn + Aq. rigia SnCl
4
+ NO + H
2
O
* SnCl
4
. 5H
2
O is known as butter of tin used as mordant.
(NH
4
)
2
SnCl
6
is known as 'pink salt' used as calico printing.
Mosaic gold : SnS
2
yellow crystalline substance :
Sn + 4NH
4
Cl (NH
4
)
2
SnCl
4
+ 2NH
3
+ H
2
2(NH
4
)
2
SnCl
4
+ 2S SnS
2
+ 2NH
4
Cl + (NH
4
)
2
SnCl
6
* Distinction of Sn
+2
/ Sn
+4
:
(i) H
2
S (ii) Hg
+2
(iii) Fe
+3
+ [K
3
Fe(CN)
6
]

+2
Sn
Blue ppt.
COMPOUNDS OF LEAD
Oxides of lead :
(i) PbO (ii) Pb
3
O
4
(Red) (iii) Pb
2
O
3
(reddish yellow) (Sesquioxide)
(iv) PbO
2
(dark brown)
(1) PbO
Laboratory Prep
n
. :
Pb(NO
3
)
2
2PbO + 4NO
2
+ O
2
PbO
2

C 600 abo0e
Pb
3
O
4

Pb
2
O
3

! C o H
by #b to ed)ced easily
o/ide hot 1 O #b
2

Preparation of Pb
2
O
3
:
2aOH in it o-
!
n
sol hot
#bO 2 +
a"o)nt
3i"ited
2aOCl Pb
2
O
3
+ NaCl
Pb
2
O
3
+ 2HNO
3
PbO
2
+ Pb(NO
3
)
2
+ H
2
O
This reaction suggests that Pb
2
O
3
contains PbO
2
.
(2) Pb
3
O
4
: 6PbO + O
2
2Pb
3
O
4
{In the same way, prove that its formula is 2PbO. PbO
2
}
Pb
3
O
4
+ 4HNO
3
(cold.conc) or (hot dil.) 2Pb(NO
3
)
2
+ PbO
2
+ 2H
2
O
But 2Pb
3
O
4
+ 6H
2
SO
4
6PbSO
4
+ 6H
2
O + O
2
Pb
3
O
4
+ 8HCl 3PbCl
2
+ 4H
2
O + Cl
2
(3) PbO
2
: Insoluble in water. HNO
3
, But reacts with HCl + H
2
SO
4
(hot conc.) and in hot NaOH / KOH.
(i) Pb
3
O
4
+ HNO
3

(ii) Pb(OAc)
2
+ Ca(OCl)Cl + H
2
O PbO
2
[Brown(dark)] + CaCl
2
+ 2CH
3
CO
2
H

Excess bleaching powder

is being removed by stirring with
HNO
3
Reaction : PbO
2
+ 4HCl PbCl
2
+ Cl
2
+ 2H
2
O
2PbO
2
+ 2H
2
SO
4
2PbSO
4
+ 2H
2
O + O
2
PbO
2
+ 2NaOH Na
2
PbO
3
+ H
2
O
Q. What happens when electrolysis is performed for hot NaCl solution containing PbO with stirring.
Sol. NaCl l Na
+
+ Cl

. H
2
O l H
+
+ OH

At cathode : 2H
+
+ 2e H
2
-
At anode : 2Cl

Cl
2
+ 2e
Cl
2
+ 2OH

l Cl

+ OCl

+ H
2
O
PbO + OCl

(excess formed due to electrolysis) PbO

2
+ Cl

PbO
2
: Powerful oxidising agent :
(i) PbO
2
+ SO
2
PbSO
4
[spontaneously]

PbS + O
3
PbSO
4
+ 4O
2
PbS + 4H
2
O
2
PbSO
4
+ 4H
2
O

(ii) PbO
2
+ 2HNO
3
+ (COOH)
2
Pb(NO
3
)
2
+ 2CO
2
+ 2H
2
O
(iii) 2MnSO
4
+ 5PbO
2
+ 6HNO
3
3Pb(NO
3
)
2
+ 2PbSO
4

+ 2HMnO
4
+ 2H
2
O
PbCl
4
: Exists as H
2
[PbCl
6
]
PbO
2
+ 4HCl PbCl
4
+ 2H
2
O
{ice cold conc. saturated with Cl
2
}
PbCl
4
+ 2HCl H
2
PbCl
6
Lead Tetraacetate :
Pb
3
O
4
+ 8AcOH(hot glacial) Pb(OAc)
4
+ 2Pb(OAc)
2
+ 4H
2
O
Pb(OAc)
2
is also converted into Pb(OAc)
4
by passing into Cl
2
2Pb(OAc)
2
+ Cl
2
Pb(OAc)
4
+ PbCl
2

It is used as oxidising agent in org. chemistry to oxidise 1,2-diol to aldehydes and ketones.
) OH ( *CH
+
) OH ( *CH

4 O 5
2RCHO + H
2
O
TetraEthyl lead :
4NaPb(alloy 10%Na.) + 4C
2
H
5
Cl(vap.) 3Pb + Pb(Et)
4
+ 4NaCl
It is antiknocking agent.
Lead storage cell :
Pb + PbO
2
+ 2H
2
SO
4
2PbSO
4
+ 2H
2
O
NITROGEN FAMILY
Nitrogen(N
2
)
Occurence: Nitrogen is widely distributed in nature both in free as well as in the combined state. Air is
the most abundant source of free nitrogen. It forms 75% by mass and 78% by volume of the air. In combined
state, it is found as nitrates such as Chile saltpetre (NaNO
3
), Indian saltpetre (KNO
3
) and ammonium
comopunds.
Preparation: Nitrogen can be obtained from the following two sources:
(i) Nitrogen Compounds (ii) Air
(i) Nitrogen from nitrogen compounds: (a) Nitrogen in the laboratory can be obtained by heating
ammonium nitrite or ammonium dichromate.
NH
4
Cl + NaNO
2
NH
4
NO
2
+ NaCl
Ammonium nitrite
NH
4
NO
2
N
2
+ 2H
2
O
(NH
4
)
2
Cr
2
O
7
N
2
+ Cr
2
O
3
+ 4H
2
O
Nitrogen is collected by downward dispalcement of water.
(b) Pure nitrogen can be obtained by passing the ammonia vapours over heated CuO.
2NH
3
+ 3CuO N
2
+ 3Cu + 3H
2
O
NH
3
can also be oxidised to nitrogen by Cl
2
, Br
2
, a hypochlorite, a hypobromite or bleaching powder.
(c) It can be obtained by the action of nitrous acid (or NaNO
2
and dil. H
2
SO
4
) on urea.
NH
2
CONH
2
+ 2HNO
2
2N
2
+ CO
2
+ 3H
2
O
Urea
(d) Pure nitrogen is obtained in small amounts by heating sodium or barium azides in vacuum.
Ba(N
3
)
2
3N
2
+ Ba
Barium azide
(ii) From air: (a) Commercially nitrogen is obtained by liquefaction of air. The resultant liquid isfractionally
distilled in Claudes apparatus.
(b) By removing oxygen of the air with the use of chemical substances.
Purified air Hot Cu Nitrogen
2Cu + O
2
2CuO
Purified air Hot Cake CO
2
, CO, N
2
CO
2
and CO are removed by usual methods.
Purified air Phosphorus P
2
O
5
+ N
2

Properties:
(i) It is a colourless, tasteless and odourless gas. It is slightly lighter than air as its vapour density is 14.0. It
is sparingly soluble in water.
(ii) It can be liquefied to a colourless liquid (b. pt. 195.8
0
C).
(iii) It does not help in combustion. Nitrogen itself is non-combustible.
(iv) It is chemically inert under ordinary conditions. However, it shows chemical activity under high
temperatures.
(a) Nitrogen combines with oxygen under the influence of very high temperature like electric spark.
N
2
+ O
2
2NO (Nitric oxide)
(b) Nitrogen combines with hydrogen in the presence of a catalyst (finely divided iron) at 200 atmospheres
and 400-500
0
C temperature.
N
2
+ 3H
2
2NH
3
(Ammonia)
(c) Nitrogen combines with metals at red heat to form nitrides.
6Li + N
2

450
0
C

2Li
3
N (Lithium nitride)
3Mg + N
2

450
0
C

Mg
3
N
2
(Magnesium nitride)
2Al + N
2

800
0
C

2AIN (Aluminium nitride)
Non-metals like boron, silicon at bright red heat also combine with nitrogen.
2B + N
2
2BN (Boron nitride)
3Si + 2N
2
Si
3
N
4
(Silicon nitride)
(d) Nitrogen combines with calcium carbide to form calcium cyanamide at 1000
0
C.
CaC
2
+ N
2
CaCN
2
+ C
The mixture of calcium cyanamide and carbon is technically known as nitrolinm.
Uses: It is used in the manufacture of NH
3
, HNO
3
, CaCN
2
and other nitrogen compounds.
Active nitrogen: When an electric discharge is allowed to pass through nitrogen under very low pressure
(about 2 mm), a brialliant luminiscence is observed which persists for sometime after the stoppage of the
discharge. It is observed that nitrogen after the discharge is more active. This nitrogen is termed active
nitrogen.
The exact nature of active nitrogen is not yet known.
Important compounds of Nitrogen
1. Ammonia
Nitrogen forms three well known hydrides with hydrogen:
(i) Ammonia, NH
3
, (ii) Hydrazine, NH
2
NH
2
(N
2
H
4
); (iii) Hydrazoic acid, N
3
H. Ammonia is the most
important of these hydrides.
Occurence: NH
3
is found in traces in atmopshere. Ammonium salts such as ammonium chloride and
ammonium sulphate are found in small amounts in the soil.
Discovery: It was first isolated by Priestly by the action of ammonium chloride and lime. It was named
alkaline air.
Preparation: (i) Ammonium is obtained on a small scale from ammonium salts which evolve it when
heated with caustic soda or lime.
NH
4
Cl + NaOH NH
3
+ NaCl + H
2
O
(Laboratory Preparation) 2NH
4
Cl + Ca(OH)
2
2NH
3
+ CaCl
2
+ 2H
2
O
(slaked lime)
(ii) Ammonia is formed when ammonium chloride is heated with litharge.
2NH
4
Cl + PbO 2NH
3
+ PbCl
2
+ H
2
O
(iii) By reacting nitrides with water, ammonia is obtained.
AIN + 3H
2
O Al(OH)
3
+ NH
3
Mg
3
N
2
+ 6H
2
O 3Mg(OH)
2
+ 2NH
3
(iv) Ammonium can also be formed by doing reduction of nitrates and nitrites with zinc and caustic soda.
Zinc and caustic soda produce nascent hydrogen which reacts with nitrates and nitrites to form ammonia.
NaNO
3
+ 8H
Zn/ NaOH

NaOH + NH
3
+ 2H
2
O
NaNO
2
+ 6H
Zn/ NaOH

NaOH + NH
3
+ H
2
O
(v) Calcium cyanamide is also obtained by heating ammonium compounds.
(NH
4
)
2
SO
4

Heat

NH
3
+ NH
4
HSO
4
Ammonium Ammnoium hydrogen
sulphate sulphate
NH
4
H
2
PO
4

Heat

NH
3
+ HPO
3
+ H
2
O
Ammonium Metaphosphoric
dihydrogen phosphate acid
(vi) Urea on treatment with caustic soda forms ammonia.
NH
2
CONH
2
+ 2NaOH Na
2
CO
3
+ 2NH
3
urea
Drying of Ammonia gas:
The common dehydrating agents like sulphuric acid or CaCl
2
or P
2
O
5
cannot be used as these react with
ammonia.
2NH
3
+ H
2
SO
4
(NH
4
)
2
SO
4
Ammonium sulphate
CaCl
2
+ 8NH
3
CaCl
2
8NH
3
Addition product
P
2
O
5
+ 6NH
3
+ 3H
2
O 2(NH
4
)
3
PO
4
Ammonium phosphate
Fro drying, quick lime is used as it does not react with ammonia but reacts readily with moisture.
CaO + H
2
O Ca(OH)
2
quick lime
Manufacture of Ammonia:
(i) Habers process: The method involves the direct combination of nitrogen and hydrogen according to
the following reaction:
N
2
+ 3H
2
2NH
3
+ 24.0 kcal
Raw materials: Nitrogen and hydrogen are the chief raw materials. Nitrogen is obtained from air by
liquefaction followed by fractional evaporation of liquid air. Hydrogen is obtained by electrolysis of water.
(ii) Bosch Process: From Powder gas & water gas
(iii) Cyanamide process: CaCN
2
+ 3H
2
O
180
0
C

CaCO
3
+ 2NH
3
(steam) 3-4 atm
(iv) From ammoniacal liquor obtained during coal distillation: Large quantities of ammonia are obtained
as a by-product in the manufacture of coal gas.
Physical properties: (i) Ammonia is a colourless gas with a characterstic pungent odour. it brings tears
into the eyes.
(ii) It is highly soluble in water. This high solubility is due to the hydrogen bonding. The solubility of
ammonia increases with increase of pressure and decreases with increase of temperature.
(iii) It can be easily liquefied at room temperature by the application of pressure.
(iv) Ammonia molecules link together to form associated molecules through hydrogen bonding.
Higher melting point and boiling point in comparison to other hydrides of V group are due to hydrogen
bonding.
Chemical Properties:(i) Stability : It is highly stable. It decomposes into nitrogen and hydrogen at red
heat or when electric sparks are passed through it.
2NH
3
N
2
+ 3H
2
(ii) Combustion: Ordinary, ammonia is neither combustible nor a supporter of combustion. However, it
burns in the presence of oxygen to form nitrogen and water.
4NH
3
+ 3O
2
2N
2
+ 6H
2
O
(iii) Basic nature: Ammonia is a Lewis base, accepting proton to form ammonium ion as it has tendency
to donate an electron pair.
It forms salts with acids.
NH
3
+ HCl NH
4
Cl (Ammonium chloride)
Thick white fumes
2NH
3
+ H
2
SO
4
(NH
4
)
2
SO
4
(Ammonium sulphate)
Its solution is a weak base. the solution is described as aqueous ammonia. Its ionisation in water is
represented as:
NH
3
+ H
2
O NH
4
OH NH
4
+
+ OH

The solution turns red litmus to blue and phenolphthalein pink.

(iv) Oxidation: It is oxidised to nitrogen when passed over heated CuO or PbO
3CuO + 2NH
3
3Cu + N
2
+ 3H
2
O
3PbO + 2NH
3
3Pb + N
2
+ 3H
2
O
Both chlorine and bromine oxidise ammonia.
2NH
3
+ 3Cl
2
N
2
+ 6HCl
6NH
3
+ 6HCl 6NH
4
Cl

8NH
3
+ 3Cl
2
N
2
+ 6NH
4
Cl
(excess)
When chlorine is in excess an explosive substance nitrogen trichloride is formed.
NH
3
+ 3Cl
2
NCl
3
+ 3HCl
Iodine flakes when rubbed with liquor ammonia form a dark brown precipitate of ammoniated nitrogen
iodide which explodes readily on drying.
2NH
3
+ 3I
2
NH
3
NI
3
+ 3HI
Hypochlorites and hypobromites oxidise ammonia to nitrogen.
2NH
3
+ 3NaClO N
2
+ 3NaCl + 3
2
O
The oxidation of ammonia with bleaching powder occurs on warming.
3CaOCl
2
+ 2NH
3
3CaCl
2
+ N
2
+ 3H
2
O
Thus, ammonia acts as a reducing agent.
The restricted oxidation of NH
3
can be done with air, when the mixture is passed over heated platinum
gauze at 700-800
0
C.
4NH
3
+ 5O
2
4NO + 6H
2
O
This is the Ostwalds process and used for the manufacture of HNO
3
.
(v) Formation of amides: When dry ammonia is passed over heated sodium or potassium, amides are
formed with evolution of hydrogen.
2Na + 2NH
3
2NaNH
2
+ H
2
Sodamide
(vi) Reactions of aqueous ammonia: Many metal hydroxides are formed which may be precipitated or
remain dissolved in the form of complex compound in excess of NH
4
OH.
FeCl
3
+ 3NH
4
OH Fe(OH)
3
+ 3NH
4
Cl
ppt.
AlCl
3
+ 3NH
4
OH Al(OH)
3
+ 3NH
4
Cl
ppt.
CrCl
3
+ 3NH
4
OH Cr(OH)
3
+ 3NH
4
Cl
ppt.
CuSO
4
+ 2NH
4
OH Cu(OH)
2
+ (NH
4
)
2
SO
4
Blue ppt.
Cu(OH)
2
+ (NH
4
)
2
CO
4
+ 2NH
4
OH [Cu(NH
3
)
4
]SO
4
+ 4H
2
O
Tetramine copper
sulphate
(colourless solution)
CdSO
4
+ 4NH
4
OH [Cd(NH
3
)
4
]SO
4
+ 4H
2
O
Cadmium tetramine
sulphate
(Colourless solution)
AgNO
3
+ NH
4
OH AgOH + NH
4
NO
3
White ppt.
AgOH + 2NH
4
OH [Ag(NH
3
)
2
](OH) + 2H
2
O
soluble
AgCl also dissolve in NH
4
OH solution
AgCl + 2NH
4
OH [Ag(NH
3
)
2
]Cl + 2H
2
O
Diamine silver chloride
ZnSO
4
+ 2NH
4
OH Zn(OH)
2
+ (NH
4
)
2
SO
4
ppt.
Zn(OH)
2
+ (NH
4
)
2
SO
4
+ 2NH
4
OH [Zn(NH
3
)
4
]SO
4
+ 4H
2
O
Tetramine zinc sulphate
(soluble) colourless
Nickel salt first gives a green precipitate which dissolves in excess of NH
4
OH.
NiCl
2
+ 2NH
4
OH Ni(OH)
2
+ 2NH
4
Cl
Ni(OH)
2
+ 2NH
4
Cl + 4NH
4
OH [Ni(NH
3
)
6
]Cl
2
+ 6H
2
O
It forms a white precipitate with mercuric chloride.
HgCl
2
+ 2NH
4
OH HgNH
2
Cl + NH
4
Cl + H
2
O
Amido mercuric
chloride
It forms a grey precipitate with mercurous chloride.
Hg
2
Cl
2
+ 2NH
4
OH
Hg HgNH Cl
Grey
+
2

+ NH
4
Cl + H
2
O
(vii) Reaction with Nesslers reagent: A reddish brown ppt. is formed.
2KI + HgCl
2
HgI
2
+ 2KCl
2KI + HgI
2
K
2
HgI
4
Alkaline solution of K
2
HgI
44
is called Nesslers reagent.
This gives brown ppt. with NH
3
called iodide of Millions base.
2K
2
HgI
4
+ NH
3
+ 3KOH H
2
NHgOHgI + 7KI + 2H
2
O
Brown ppt.
Uses: (i) Liquid hydrogen is not safe to transport in cylinders. Ammonia can be easily liquefied and
transported safely in cylinders. Ammonia can be decomposed into hydrogen and nitrogen by passing over
heated metallic catalyst. Thus, ammonia is the source for the production of hydrogen at any destination.
(ii) Ammonia is also used in the manufacture of urea which is an excellent fertilizer of nitrogen.
Hydrazine or Diamide NH
2
NH
2
or N
2
H
4
This is another hydride of nitrogen. It is prepared by following methods:
(i) Raschigs method: A strogn aqueous solution of ammonia is boiled with sodium hypochlorite in presence
of a little glue.
NH
3
+ NaOCl NH
2
Cl + NaOH
NH
2
Cl + NH
3
NH
2
NH
2
+ HCl
Chloramine Hydrazine

2NH
3
+ NaOCl NH
2
NH
2
+ NaCl + H
2
O
It burns in air liberating huge amount of energy. The alkyl derivatives of hydrazine are used these days as
potential rocket fuels. It reacts with nitrous acid to give hydrazoic acid, N
3
H.
N
2
H
4
+ HNO
2
N
3
H + 2H
2
O
Hydrazine and its salts act as powerful reducing agents.
PtCl
4
+ N
2
H
4
Pt + N
2
+ 4HCl
4AgNO
3
+ N
2
H
4
4Ag + N
2
+ 4HNO
3
4AuCl
3
+ 3N
2
H
4
4Au + 3N
2
+ 12 HCl
It reduces Fehlings solution to red cuprous oxide, iodates to iodides and decolourises acidified KMnO
4
solution. It is used as a fuel for rockets, reducing agent and a reagent in organic chemistry.
Structure
Hydrazoic Acid, N
3
H
It is the third hydride of nitrogen. It is an acid while other hydrides, NH
3
and N
2
H
4
are bases. It is prepared
by the action of nitrous acid on hydrazine.
NH
2
NH
2
+ HNO
2
N
3
H + 2H
2
O
It is also formed in the form of sodium salt by passing nitrous oxide on sodamide.

Dry NH
3


N O
2


It reduces acidified KMnO
4
, nitrous acid, etc.
2N
3
H + O 3N
2
+ H
2
O
N
3
H + HNO
2
N
2
+ N
2
O + H
2
O
It oxidises HCl into Cl
2
N
3
H + 2HCl N
2
+ NH
3
+ Cl
2
Oxides of Nitrogen
N
2
O
3
and N
2
O
5
monomeric other are dimeric
Nitrogen forms a number of oxides. The well known oxides of nitrogen are:
(i) Nitrogen oxide, N
2
O
(ii) Nitric oxide, NO
(iii) Nitrogen trioxide, N
2
O
3
(iv) Nitrogen dioxide or Di-nitrogen tetroxide, NO
2
or N
2
O
(v) Nitrogen pentoxide, N
2
O
5
(I) Nitrogen Oxide, N
2
O or Laughing Gas (Neutral)
Preparation:
It can be prepared by heating ammonium nitrate or a mixture of sodium nitrate and ammonium sulphate.
NH
4
NO
3
N
2
O + 2H
2
O
2NaNO
3
+ (NH
4
)
2
SO
4

2NH
4
NO
3
+ Na
2
SO
4

2N
2
O + 4H
2
O
FeSO
4
+ NO FeSO
4
.NO
Addition product
H
2
SO
4
+ 2NH
3

(NH
4
)
2
SO
4
Ammonium Sulphate
The following reactions can also be used to prepare nitrous oxide.
NaNH
2
+ N
2
O

NaN
3
+ NaOH + NH
3
(a) By the action of cold and dilute nitric acid on zinc metal.
Fe/4Zn + 10HNO
3

4Zn (NO
3
)
2
+ N
2
O + 5H
2
O
(b) By reducing nitric acid with stannous chloride and hydrochloric acid.
4SnCl
2
+ 8HCl + 2HNO
3

4SnCl
4
+ N
2
O + 5H
2
O
(c) By reducing nitric oxide with sulphur dioxide.
2NO + SO
2
+ H
2
O

H
2
SO
4
+ N
2
O
(d) By heating the mixture of hydroxylamine hydrochloride and sodium nitrite (1 : 1)
NH
2
OH.HCl + NaNO
2

N
2
O + NaCl + 2H
2
O
Properties:
(a) It is a colourless gas with pleasant odour and sweet taste.
(b) When inhaled in moderate quantity, it produces hysterical laughter, hence named as laughing gas. However,
when inhaled for long, it produces insensibility and may prove fatal too.
(c) It is heavier than air.
(d) It is fairly soluble in cold water but not in hot water.
(e) It is neutral to litmus.
(f) It does not burn but support combustion. The burning material decompose nitrous oxide into nitrogen
and oxygen. The oxygen then helps in the buring.
2N
2
O

C 900 520
o
2N
2
+ O
2
It supports combustion of sulphur, phosphorus, magnesium, sodium, candle and a splineter.
S + 2N
2
O SO
2
+ 2N
2
4P + 10N
2
O

2P
2
O
5
+ 10N
2
Mg + N
2
O

MgO + N
2
(g) It is decomposed by red hot copper.
Cu + N
2
O

CuO + N
2
(h) A mixture of hydrogen and nitrous oxide (equal volumes) explodes with violence.
N
2
O + H
2

N
2
+ H
2
O
(i) N
2
O + NaNH
2

NaH
3
+ NH
3
+ NaOH
Uses:
(i) It is used as the propellant gas for whipped ice-cream.
(ii)A mixture of nitrous oxide and oxygen is used as an ananesthetic in dental and other minor surgical
operations.
Structure:
N
2
O is linear and unsymmetrical molecule. It is considered as a resonance hybrid of the following two
structures:
N :

+
N

: O

N :

2
+
N

It has a very small value of dipole moment (0.116D)
Tests:
(i) It has sweet smell.
(ii) It supports the combustion of glowing splinter.
(iii) It does not form brown fumes with nitric oxide.
(iv) N
2
O does not form H
2
N
2
O
2
with H
2
O nor hyponitrites with alkali.
(II) Nitric oxide, NO Neutral
Preparation:
(a) By the action of dilute nitric acid on copper (Lab. Method). the nitric oxide liberated is collected over
water.
Ag/Hg/Pb/3Cu + 8HNO
3
3Cu(NO
3
)
2
+ 2NO + 4H
2
O
The liberated gas may contain NO
2
and N
2
O. These are separated by passing the mixture through ferrous
sulphate solution. NO forms a dark nitroso-ferrous sulphate. When this solution is heated, pure nitric oxide
is liberated.
FeSO
4
+ NO

FeSO
4
.NO

heate
FeSO
4
+ NO
(impure gas) (Dark Brown) (Pure gas)
(b) A pure sample of nitric oxide is obtained when a mixture of KNO
3
, FeSO
4
and dilute H
2
SO
4
is heated.
This is also a laboratory method.
2KNO
3
+ H
2
SO
4
K
2
SO
4
+ 2HNO
3
2HNO
3
H
2
O + 2NO + 3O
[2FeSO
4
+ H
2
SO
4
+ O Fe
2
(SO
4
)
3
+ H
2
O] x 3

2KNO
3
+ 6FeSO
4
+ 4H
2
SO
4
K
2
SO
4
+ 3Fe
2
(SO
4
)
3
+ 2NO + 4H
2
O

(c) Nitric oxide is the first product obtained from the following two processes during the manufacture of
nitric acid.
(i) Electric arc process:
By passing air through an electric arc, nitrogen and oxygen of the air combine together to form nitric oxide.
N
2
+ O
2
2NO
(ii) Ostwalds process:
By restricted oxidation of ammonia with air in presence of platinum gauze catalyst at 750
0
C, nitric oxide is
formed.
4NH
3
+ 5O
2

Pt gauze
C atm

!

"50 #
0
4NO + 6H
2
O
Properties:
(a) It is a colourless gas, slightly heavier than air.
(b) It is sparingly soluble in water.
(c) It is paramagnetic indicating the presence of unpaired electron in the molecule.
(d) It is neutral to litmus.
(e) It at once reacts with oxygen to give brown fumes of nitrogen dioxide.
2NO + O
2
2NO
2
(f) It is stable oxide. It decomposes into nitrogen and oxygen when heated at 800
0
C.
2NO
800
0
C

N
2
+ O
2
(g) It is combustible and supports combustion of boiling sulphur and burning phosphorus.
S + 2NO SO
2
+ N
2
(h) It dissolves in cold ferrous sulphate solution by forming a hydrated nitrosyl complex.
[Fe(H
2
O)
6
]SO
4
+ NO [Fe(H
2
O)
5
NO]SO
4
+ H
2
O
Ferrous sulphate Hydrated nitrosyl
complex (Brown colour)
Heat
FeSO
4
+ NO + 5H
2
O
(i) It is oxidised to nitric acid by oxidising agents like acidified KMnO
4
or hypochlorous acid. Thus, it acts
as a reducing agent.
6KMnO
4
+ 9H
2
SO
4
+ 10NO 3K
2
SO
4
+ 6MnSO
4
+ 10HNO
3
+ 4H
2
O
[HClO HCl + O] x 3
[NO + O NO
2
] x 3
3HClO + 2NO + H
2
O 2NO
3
+ 3HCl
HNO
3
oxidises nitric oxide into NO
2
.
2HNO
3
+ NO H
2
O + 3NO
2
(j) It acts as an oxidising agent. It oxidises SO
2
to H
2
SO
4
ande H
2
S to S.
SO
2
+ 2NO + H
2
O H
2
SO
4
+ N
2
O
H
2
S + 2NO H
2
O + S + N
2
O
When exploded with hydrogen it liberates nitrogen.
2H
2
+ 2NO 2H
2
O + N
2
However, when a mixture of hydrogen and nitric oxide is passed over platinum black, ammonia is formed.
2NO + 5H
2
2NH
3
+ 2H
2
O
Stannous chloride reduces nitric oxide to hydroxylamine.
[SnCl
2
+ 2HCl SnCl
4
+ 2H] x 3
2NO + 6H 2NH
2
OH

3SnCl
2
+ 6HCl + 2NO 3SnCl
4
2NH
2
OH
(k) Nitric oxide directly combines with halogen (fluorine, chlorine, bromine) to form corresponding nitrosyl
halides.
2NO + X
2
2NOX
(F
2
, Cl
2
or Br
2
) Nitrosyl halide
Uses:
(i) In the manufacture of nitric acid.
(ii) As a catalyst in lead chamber process for the manufacture of sulphuric acid.
(iii) In the detection of oxygen to ditinguish it from nitrous oxide.
Structure:
The molecule NO has eleven valnecy electrons and it is impossible for all of them to be paired.Hence, the
molecule contains an odd electron which makes the gaseous nitric oxide as paramagnetic.
The structure is represented as a resonance hybrid.
In the liquid and solid states NO is known to form a loose dimer, N
2
O
2
(III) Dinitrogen Trioxide, N
2
O
3
This oxide is also called nitrogen sesquioxide or nitrous anhydride.
Preparation: It is obtained by the reduction of nitric acid with arsenious oxide.
2HNO
3
H
2
O + N
2
O
3
+ 2O
As
2
O
3
+ 2O As
2
O
5
As
2
O
5
+ 3H
2
O 2H
3
AsO
4

As
2
O
3
+ 2HNO
3
+ 2H
2
O 2H
3
AsO
4
+ N
2
O
3
It is known in pure state in solid form at very very low temperature. In the vapour state, it is present as an
equimolar mixture of NO and NO
2
. The mixture of NO and NO
2
may be obntained by the action of 6N
nitric acid on copper.
2Cu + 6HNO
3
2Cu(NO
3
)
2
+
NH NO
N O
+
2
2 3

+ 3H
2
O
(a) It condenses to a bluw coloured liquid at 30
0
C. The liquid when warmed at room temperature,
decomposes to a mixture of NO and NO
2
(Brown coloured)
N O
$lue %oloure&
l'(u'&
2 3

)oom *em+erature

NO O
$ro,n %oloure& ga-
+
2

(b) It is an acidic oxide. If forms nitrous acid and water and hence the name nitrous anhydride.
N
2
O
3
+ H
2
O 2HNO
2
The oxide combines with caustic alkali forming corresponding nitrite.
2NaOH + N
2
O
3
2NaNO
2
+ H
2
O
Structure:
Since the oxide is unstable in liquid and gaseous states and decomposes into NO and NO
2
, it may be
assumed that it has the following electronic structure:
or O=NON=O
The structure is supported by its diamagnetic behaviour strucutre of N
2
O
3
is of two forms:

(IV) Nitrogen Dioxide, NO
2
or DInitrogen Tetroxide, N
2
O
4
This oxide exists as NO
2
in gaseous state while at low temperature, it exists as a dimer N
2
O
4
(Solid state)
2NO
2
N
2
O
4
Brown gas Colourless solid
Preparation: It is prespared in the laboratory either by heating nitrates of heavy metal or by the action of
concentrated nitric acid on metals like copper, silver, lead etc.
2Pb(NO
3
)
2
2PbO + 4NO
2
+ O
2
The mixture of nitrogen dioxide and oxygen is passed through a U-tube cooled by freezing mixture. Nitrogen
dioxide condenses to a pale yellow liquid while oxygen escapes.
Zn(NO
3
)
2
ZnO + NO
2
+ O
2
AgNO
3
Ag + NO
2
+ O
2
Cu + 4HNO
3
Cu(NO
3
)
2
+ 2NO
2
+ 2H
2
O
It is also obtained by air oxidation of nitric oxide.
2NO + O
2
2NO
2
Properties:
(a) It is brown colored gas wit pungent odour. Above 140
0
C, it is 100%NO
2
. The liquid as well as solid is
entirely N
2
O
4
(dimer) at low temperature. The liquid boils at 22
0
C and solid melts at 11
0
C.
(b) It decomposes completely into nitric oxide and oxygen at 620
0
C.
NO
2
+ HCl NOCl + Cl
2
+ H
2
O
2NO
2

2
2
NO O
Ga-eou- m'.ture
%olourle--
+

(c) When reacted with cold water, it forms a mixture of nitrous acid and nitric acid.
2NO
2
+ H
2
O HNO
2
+ HNO
3
On account of this, it is known as mixed anhydride of these two acids. However, with an excess of warm
water it forms nitric acid and nitric oxide.
3NO
2
+ H
2
O 2HNO
3
+ NO
(d) When absorbed by alkalies, nitrites and nitrates are formed.
2NO
2
+ 2NaOH NaNO
2
+ NaNO
3
+ H
2
O
(e) It acts as an oxidising agent. It oxidises metals like sodium, potassium, mercury, tin copper, etc.
NO
2
+ 2Na Na
2
O + NO
NO
2
+ 2Cu Cu
2
O + NO
None metals like carbon, sulphur, phosphorus when burnt in its stmosphere, are converted into corresponding
oxides.
5NO
2
+ 2P P
2
O
5
+ 5NO
2NO
2
+ S SO
2
+ 2NO
2NO
2
+ C CO
2
+ 2NO
It liberates iodine from KI and turns starch-iodide paper blue.
2KI + 2NO
2
2KNO
2
+ I
2
In aqueous solution, it oxidises SO
2
to sulphuric acid
SO
2
+ H
2
O + NO
2
H
2
SO
4
+ NO
This reaction is used for the manufacture of H
2
SO
4
by lead chamber process.
H
2
S is oxidised to S and CO to CO
2
.
H
2
S + NO
2
H
2
O + S + NO
CO + NO
2
CO
2
+ NO
(f) It behaves also as a reducing agent. It redduces ozone to oxygen.
2NO
2
+ O
3
N
2
O
5
+ O
2
It decolourises acidified KMnO
4
solution.
2KMnO
4
+ 3H
2
SO
4
K
2
SO
4
+ 2MnSO
4
+ 3O
2
+ 5O
10NO
2
+ 5H
2
O + 5O 10HNO
3
-----------------------------------------------------------------------
2KMnO
4
+ 3H
2
SO
4
+ 10NO
2
+ 2H
2
O K
2
SO
4
+ 2MnSO
4
+ 10 HNO
3
Uses
(i) It is used for the manufacture of nitric acid.
(ii) It is employed as a catalyst in the lead chamber process for the manufacture of sulphuric acid.
Structure
NO
2
molecule has V-shaped structure with O-N-O bond angle 132
o
and N-O bond length of about
1.19 which is intermediate between a single and a double bond. Hence, NO
2
is regarded as a resonance
hybrid of the following two streuctures.

The molecule is an odd electron molecule. The paramagnetic behaviour of NO

2
confirms this view. Due to
prossession of odd eledtron, it is colored and has a tendency to polymerize to form a colour less dimer,
N
2
O
4
. the dimer is planar in structure with N-N bond length 1.75.
(v) Nitrogen Pentoxide, N
2
O
5
This oxide is also known as nitric anhydride.
Preparation
It is prepared by distilling concentrated nitric acid with phosphorus pentoxide in a glass apparatus.
2NHO
3
H
2
O + N
2
O
5
P
2
O
5
+ H
2
O 2HPO
3
----------------------------------------
P
2
O
5
+ 2HNO
3
2HPO
3
+ N
2
O
5
----------------------------------------
It is also prepared by the action of dry chlorine on solid silver nitrate at 95
o
C.
4AgNO
3
+ 2Cl
2
4AgCl + 2N
2
O
5
+ O
2
Properties
(a) It is a white crystalline solid. The crystals melt at 30
o
C giving a yellow liquid which decomposes at 40
o
C
to give brown NO
2
. The decompostion occurs with explosion.
2N
2
O
5
4NO
2
+ O
2
(b) It is an acidic oxide. It reacts with water with hissing sound forming nitric acid.
N
2
O
5
+ H
2
O 2HNO
3
On account of this, it is known as nitric anhydride. With alkalies if forms nitrates.
2NaOH + N
2
O
5
2NaNO
3
+ H
2
O
(c) It acts as a strong oxidising agent. It affect organic substances such as cork, rubber, etc. It oxidises
iodine readily into iodine pentoxide.
I
2
+ 5N
2
O
5
I
2
O
5
+ 10NO
2
(d) With aqueous NaCl, the ionic reaction takes place.
N
2
O
5
+ NaCl naNO
3
+ NO
2
Cl
The reaction proves that N
2
O
5
exists as ionic nitronium nitrate (NO
2
, NO
3
)
(e) N
2
O
5
is decomposed by alkali metals.
N
2
O
5
+ Na naNO
3
+ NO
2
Structure
In the gaseous state, it exists as a symmetrical molecule having the structure O
2
N - O - NO
2
, N - O - N
bond is almost linear. It may be represented as:
X- ray studies suggest that solid N
2
O
5
is ionic in nature, i.e. nitronium nitrate, NO
2
, NO
3
-
.
5. Oxyacids of Nitrogen
Nitrogen forms a number of oxyacids. The most common and important oxyacids are:
(i) Hyponitrous acid, H
2
N
2
O
2
Preparation
Properties
It is colourless, hygroscopic. It is very weak dibasic acid but a strong reducing agent.
H
2
N
2
O
2
H
2
O + N
2
O
It has zero dipole moment which is based on its trans structure.
(ii) Nitrous Acid, HNO
2
The free acid is unknown. It is known only in solution.
Preparation
A solution of nitrous acid can be prepared by acidifying solutions of nitrites with mineral acids.
2NaNO
2
+ H
2
SO
4
Na
2
SO
4
+ 2HNO
2
KNO
2
+ HCl KCl + HNO
2
Nitrates on heating with lead decompose to give nitrite.
NaNO
3
+ Pb

NaNO
2
+ 2HNO
2
An aqueous solution of the acid, free from any salt, can be prepared by treating barium nitrite with calculated
amount of dilute sulphuric acid. Singce the acid is very unstable, the reaction is carried out at low temperature
(freezing mixture temperature). The insoluble barium sulphate is filtered off.
Ba(NO
2
)
2
+ H
2
SO
4
$a/O
'n-o le
4
lu0
+ 2HNO
2
A solution of nitrous acid may also the prepared by dissolving N
2
O
3
in water.
HNO
2
+ NaOH NaNO
2
+ H
2
O
NH
3
+ H
2
O
2
HNO
2
+ H
2
O
Properties
(a) Aqueous solution of nitrous acid is pale blue. This is due to the presence of nitrogen trioxide, N
2
O
3
the
colour fades on standing for sometime.
(b) It is weak acid and reacts with alkalies to form salts known as nitrites.
HNO
2
+ NaOH NaNO
2
+ H
2
O
(c) Auto-oxidation
The acid is unstable and even in cold solution, it undergoes auto-oxidation.
2HNO
2
2NO + H
2
O + O
HNO
2
+ O HNO
3
----------------------------------
2HNO
2
2NO + HNO
3
+ H
2
O
-----------------------------------
On heating, it decomposes into nitric oxide and nitrogen dioxide.
2HNO
2
H
2
O +
(d) Oxidising nature
It acts as an oxidising agent due to ease with which it decomposes to give nascent oxygen. the potential
equation when it acts as an oxidising agent is:
2HNO
2
H
2
O + 2NO + O
(i) Iodine is liberated from potassium iodide.
2KI + H
2
SO
4
+ 2HNO
2
K
2
SO
4
+ 2NO + I
2
+ 2H
2
O
(ii) Stannous chloride is oxidised to stannic chloride.
SnCL
2
+ 2HCL + 2HNO
2
SnCl
4
+ 2NO + 2H
2
O
(iii) Sulphur chloride is oxidised to sulphuric acid.
SO
2
+ 2HNO
2
H
2
SO
4
+ 2NO
(iv) Sulphur is formed by oxidation of hydrogen sulphide.
H
2
S + 2HNO
2
S + 2H
2
O + 2NO
(v) Acidified ferrous sulphate is oxidised to ferric sulphate.
2FeSO
4
+ H
2
SO
4
+ 2HNO
2
Fe
2
(SO
4
)
3
+ 2NO + 2H
2
O
(vi) Sodium arsentie is oxidised to sodium arsenate.
Na
3
AsO
3
+ 2HNO
2
Na
3
AsO
4
+ 2NO + H
2
O
(e) Reducing nature
Nitrous acid acts as a reducing agent as it can be oxidised into nitric acid.
HNO
2
+ O HNO
3
(i) It reduces bromine to hydrobromic acid.
Br
2
+ H
2
O + HNO
2
2HBr + HNO
3
(ii) Acidified potassium permanganate is decolourised.
2KMnO
4
+ 3H
2
SO
4
+ 5HNO
2
K
2
SO
4
+ 2MnSO
4
+ 5HNO
3
+ 3H
2
O
(iii) Acidified potassium dichromate is reduced to chromic sulphate (green)
K
2
Cr
2
O
7
+ 4H
2
SO
4
+ 3HNO
2
K
2
SO
4
+ Cr
2
(SO
4
)
3
+ 3HNO
3
+ 4H
2
O
(iv) Hydrogen peroxide is reduced to water
H
2
O
2
+ HNO
2
HNO
3
+ H
2
O
(f) Reaction with ammonia
It reacts with ammonia to form nitrogen and water.
NH
3
+ HNO
2
1 2 NH NO
3nterme&'ate
4 2
N
2
+ 2H
2
O
(g) Reaction with urea
It decomposes urea and aliphatic primary amines to nitrogen
NH CONH
4rea
2 2
+ 2HNO
2
2N
2
+ CO
2
+ 3H
2
O
C H NH
5thyla e
2 5 2
m'n
+ HO . NO C H OH
5thyl al%ohol
2 5
+ N
2
+ H
2
O
Structure
Since nitrous acid forms two types of organic derivatives, the nitrites (R-ONO) and nitro compounds (R-
NO
2
), it is considered to be a automeric mixture ot two forms.
HON=O and
or and
(iii) Nitric acid, HNO
3
It was named aqua fortis (means strong water) by alchemists.
Preparation
(i) Laboratory Method
KNO
3
+ conc. H
2
SO
4
KHSO
4
+ HNO
3
(vap)
vapours of nitric acid evolved are condensed in a glass receiver.
(ii) Industrial Preparation
(A) Birkeland Eyde Process or arc process
step 1 N
2
+ O
2

3000
0
C
5le%tr'% 6r%

2NO - heat
step 2 NO + O
2
NO
2
step 3 NO
2
+ H
2
O HNO
2
+ HNO
3
step 4 HNO
2
HNO
3
+ NO + H
2
O
(B) Ostwalds Process
step 1 NH
3
+ O
2

Pt gauze
C

"00 800
0
NO + H
2
O + heat
step 2 NO + O
2
NO
2
step 3 NO
2
+ H
2
O HNO
2
+ HNO
3
step 4 HNO
2
HNO
3
+ NO + H
2
O
Properties
Physical
Nitric acid usually acquires yellow colour due to its decomposition by sunlight into NO
2
.
4HNO
3

/unl'ght

4NO
2
+ 2H
2
O + O
2
The yellow colour of the acid can be removed by warming it to 60-80
o
C and bubbling dry air through it.
It has extremely corrosive action on the skin and causes painful sores.
Chemical
(a) It is very strong acid. It exhibits usual properties of acids. It reacts with basic oxides, carbonates,
bicarbonates and hydroxides forming corresponding salts.
CaO + 2HNO
3
Ca(NO
3
)
2
+ H
2
O
Na
2
CO
3
+ 2HNO
3
2NaNO
3
+ H
2
O + CO
2
NaOH + HNO
3
NaNO
3
+ H
2
O
(b)Oxidising nature : Nitric acid acts as a strong oxidising agent as it decomposes to give nascent oxygen
easily.
2HNO
3
H
2
O + 2NO
2
+ O
or 2HNO
3
H
2
O + 2NO + 3O
(i) Oxidation of non-metals: The nascent oxygen oxidises various non-metals to their corresponding
highest oxyacids.
(1) Sulphur is oxides to sulphuric acid
/ HNO
%on% an& hot
+ #
3

H
2
SO
4
+ 6NO
2
+ 2H
2
O
(2) Carbon is oxidised to carbonic acid
C + 4HNO
3
H
2
CO
3
+ 4NO
2
+ 2H
2
O
(3) Phosphorus is oxidised to orthophosphoric acid.
2P + 10HNO
3

2H
3
PO
4
+ 10NO
2
+ 2H
2
O
conc. and hot
(4) Iodine is oxidised to iodic acid
I
2
+ 10HNO
3

2HIO
3
+ 10NO
2
+ 4H
2
O
conc. and hot
(ii) Oxidation of metalloids
Metalloids like non-metals also form highest oxyacids
(1) Arsenic is oxidised to arsenic acid
2As + 10HNO
3

2H
3
AsO
4
+ 10NO
2
+ 2H
2
O
or As + 5HNO
3

H
3
AsO
4
+ 5NO
2
+ H
2
O
conc. and hot
(2) Antimony is oxidised to antimonic acid
Sb + 5HNO
3

H
3
SbO
4
+ 5NO
2
+ H
2
O
conc. and hot
(3) Tin is oxidised to meta-stannic acid.
Sn + 2HNO
3

H
2
SnO
3
+ 4NO
2
+ H
2
O
(iii) Oxidation of Compounds:
(1) Sulphur dioxide is oxidised to sulphuric acid
SO
2
+ 2HNO
3

H
2
SO
4
+ 2NO
2
(2) Hydrogen sulphiode is oxidised to sulphur
H
2
S + 2HNO
3

2NO
2
+ 2H
2
O + S
(3) Ferrous sulphate is oxidised to ferric sulphate in presence of H
2
SO
4
6FeSO
4
+ 3H
2
SO
4
+ 2HNO
3

3Fe
2
(SO
4
)
3
+ 2NO + 4H
2
O
(4) Iodine is liberated from KI.
6KI + 8HNO
3

6KNO
3
+ 2NO + 3I
2
+ 4H
2
O
(5) HBr, HI are oxidised to Br
2
and I
2
, respectively.
2HBr + 2HNO
3

Br
2
+ 2NO
2
+ 2H
2
O
Similarly, 2HI + 2HNO
3

I
2
+ 2NO
2
+ 2H
2
O
(6) Ferrous sulphide is oxidised to ferrous sulphate
FeS + HNO
3

FeSO
4
+ 8NO
2
+ 4H
2
O
(7) Stannous chloride is oxidised to stannic chloride is presence of HCl.
2HNO
3
+ 14H

NH
2
OH + NH
3
+ 5H
2
O
Hydroxylamine
NH
3
+ HNO
3

NH
4
NO
3
------------------------------------------------------------------------------
7SnCl
2
+ 14HCl + 3HNO
3

7SnCl
4
+ Nh
2
OH + NH
4
NO
3
+ 5H
2
O
(8) Cane sugar is oxidised to oxalic acid.
C
12
H
22
O
11
+ 36HNO
3

6(COOH)
2
+ 36NO
2
+ 23H
2
O
(c) Action on Metals: Most of the metals will the exveption of noble metals like gold and platinum are
attacked by Nitric acid plays a double role in the action of metals, i,e, it acts as an acid as well as an
oxidising agent. ARmstrong postulated that primary action of nitric acid is to produce hydrogen in the
nascent form. Before this hydrogen is allowed to escape, it reduces the nitric acid into number of products
like NO
2
, NO, N
2
O, N
2
or NH
3
according to the following reactions:
Metal + HNO
3
Nitrate + H
2HNO
3
+ 2H 2NO + 2H
2
O
2HNO
3
+ 6H 2NO + 4H
2
O
2HNO
3
+ 10H N
2
+ 6H
2
O
2HNO
3
+ 16 H 2NH
3
+ 6H
2
O
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.
--------------------------------------------------------------------------------------------------------
Concentration of Metal Main Products
nitric acid
--------------------------------------------------------------------------------------------------------
Mg, Mn H
2
+ Metal nitrate
Very dilute HNO
3
(6%) ----------------------------------------------------------
Fe, Zn, Sn NH
4
NO
3
+ metal nitrate + H
2
O
--------------------------------------------------------------------------------------------------------
Pb, Cu, Ag, Hg NO + metal nitrate + H
2
O
----------------------------------------------------------
Dilute HNO
3
(20%) Fe, Zn N
2
O + metal nitrate + H
2
O
----------------------------------------------------------
Sn NH
4
NO
3
+ Sn(NO
3
)
2
--------------------------------------------------------------------------------------------------------
Zn, Fe, Pb, Cu, Ag NO
2
+ metal nitrate + H
2
O
Conc. HNO
3
(70%) ----------------------------------------------------------
Sn NO
2
+ H
2
SnO
3
Metastannic acid
--------------------------------------------------------------------------------------------------------
Action on Proteins
(i) 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.
(ii) Oxidation A number of organic compounds are oxidised.
Sawdust catches fire when nitric acid is poured on it. Turpentine oil bursts into flames when treated with
fuming nitric acid. Cane sugar is oxidised to oxalic acid. Toluene is oxidised to benzoic acid with dil.
HNO
3
.
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, NO
2
Cl. It may be structurally represented as below:
or
Gaseous nitric aicd is a planar molecule. The bond lengths and bond angles as present in the molecule are
represented in the figure:
It is supposed to exist in two resonting forms.
PHOSPHORUS
It glows in the dark and was, therefore, called phosphorus (Greek work, phos=light, and phero=1 carry)
Occurrence
Since phosphorus is an active element, it is not found free in nature. It is widely distributed in nature in the
combined state. It occurs as phosphates in the rocks and in the soil and as phosphoproteins in all living beings. It
is an essential constituents of bones, teeth, blood and nervous tissure. It is necessary for the growth of plants.
Bone ash contains about 80% calcium phosphate. it is present in milk, eggs and guano (excreta of seabirds). The
principal minerals of phosphorous are
(i) Phosphorite Ca
3
(FO
4
)
2
(ii) Fluorapatite 3Ca
3
(PO
4
)
2
.CaF
2
(iii) Chlorapatite 3Ca
3
(PO
4
)
2
.CaCl
2
Extraction
Phosphorus is extracted either from phosphorite or bone ash by the application of following two processes.
(i) Retort process or old process.
(ii) Electrothermal process or modern process.
(i) Retort process or old process
The phosphorite mineral or bone ash is digested with concentrated sulphuric acid (about 60%). Insoluble calcium
sulphate and orthophosphoric acid are formed.
Ca(PO
4
)
2
+ 3H
2
SO
4
3CaSO
4
+ 3H
3
PO
4
The syrupy liquid is separated from insoluble residue by filtration. The liquid is evaporated when it changes into
metaphosphoric acid with evolution of water.
H
3
PO
4

a%'&
or'% 7eta+ho-+h
3
HPO
+ H
2
O
The metaphosphoric acid is mixed with powdered coke and distilled in fireclay retorts at a bright red het. The
acid is reduced to phosphorus by carbon which comes in vaporized form. The vapours are condensed below
water.
4HPO
3
+ 10C P
4
+ 10CO + 2H
2
O
(ii) Electrothermal process or modern process.
The mixture of phosphorite, carbon and silica is dried and then introduced into the electric furnace. The furnace
is an iron tank lined inside with refractory bricks. Carbon electrodes are fitted on either side of the furnace. The
furnace has two exits, one for removal of vapours in the upper part of the furnace and the other for removal of
slag in the lower part of furnace. The charge is introduced through the closed hopper arrangement.
The mixture is heated at 1400-1500
o
C by the discharge of an alternating current between carbon electrodes.
Silica combines with calcium phosphate and forms phosphorus pentaxide which is reduced by carbon into
phosphorus.
[Ca
3
(PO
4
)
2
+ 2SiO
2

3CaSiO
3
+ P
2
O
5
] x 2
2P
2
O
5
+ 10C

P
4
+ 10CO
----------------------------------------------------------------
2Ca
3
(PO
4
)
2
+ 6SiO
2
+ 10C

6CaSiO
3
+ P
4
+ 10COs
Vapours of phosphorus and carbon monoxide leave the furnace through the upper exit and are condensed under
water. The liquid slag is tapped out periodically through an exit in the base.s
Purification
Phosphorus obtained is further purified by melting under acidified potassium dichromate solution when the impurities
are oxidised. It is redistilled.
Allotropic modifications of phosphorus
Phosphorus exists in a number of allotropic forms. These forms are:
(i) Yellow or white phosphorus
(ii) Red phosphorus
(iii) Scarlet phosphorus
(iv)

-black phosphorus
(v)

-black phosphorus
(vi) violet phosphorus
The main allotropic forms, however, are white and red.
White or yellow phosphorus
This is the common variety and is obtained by the methods described above. This form is chemically very active.
Properties
(a) The pure form is white but attains yellow colour on long standing due to the formation of a thin film of the red
variety on the surface.
(b) It is a transparent waxy solid (sp. gr. 1.8) and can be easily cut with knife.
(c) It has characteristic garlic smell and is poisonous in nature. 0.15 g is the fatal dose. Vapours are also injurious.
Persons working with phosphorus develop a disease in which the jaw bones decay. This disease is known as
phossy jaw.
(d) It is insoluble in water but readily soluble in carbon disulphide.
(e) It melts at 44
o
C into a yellow liquid. It boils at 280
o
C.
(f) In contact with air, it undergoes slow combustion and glows dark. ths property is called phosphorescence.
(g)Its ignition temperature is low (about 30
o
C). It readily catches fire giving dense fumes of phosphorus pentoxide.
it si, therefore, kept in water.
P
4
+ 5O
2

P
4
O
10
or 2O
2
O
5
(h) It dissolves in caustic alkalies on boiling in an inert atmosphere and forms phosphite.
P
4
+
-o&a
Cau-t'%
NaOH 3
+ 3H
2
O
'te hy+o+ho-+h
-o&'um
2 2
PO NaH 3
+ PH
3

(i) It directly combines with halogens forming first trihalides and then pentahalides.
P
4
+ 6Cl
2
4PCl
3
; P
4
+ 10Cl
2

4PCl
5
(j) It combines with a number of metals forming phosphides.
6Mg + P
4

2Mg
3
P
2
(Magnesium phosphide)
6Ca + P
4

2Ca
3
P
2
(Calcium phosphide)
(k) It combines with sulphur with explosive violence forming a number of sulphides such as P
2
S
3
, P
2
S
5
, P
4
S
3
and
P
4
S
7
.
(l) It acts as a strong reducing agent. It reduces nitric acid and sulphuric acid.
P
4
+ 20HNO
3

4H
3
PO
4
+ 20NO
2
+ 4H
2
O
P
4
+ 10H
2
SO
4

4H
3
PO
4
+ 10SO
2
+ 4H
2
O
It reduces solutions of copper, silver and gold salts to corresponding metals,
P
4
+ 10CuSO
4
+ 16H
2
O

10Cu + 4H
3
PO
4
+ 10H
2
SO
4
When the solution is heated, cuprous phosphide is formed.
3P
4
+ 12 CuSO
4
+ 24 H
2
O

heat
4Cu
3
P + 8H
3
PO
3
+ 12H
2
SO
4
P
4
+ 20AgNO
3
+ 16H
2
O 20Ag + 4H
3
PO
4
+ 20HNO
3
(m) when heated in inert atmosphere at 240
o
C, it changes into red variety.
Yellow P
atm 3nert
C 250 240
o


Red P
(n) Structure
The vapour density of white phosphorus between 500-700
o
C, is 62 which corresponds to the molecular formula
P
4
. The four phosphorus atoms lie at the corners of a regular tetrahedron. Each phosphorus atom is linked to
each of the other three atoms by covalent bonds. The P-P bond length is equal to 2.21. The bond angle is equal
to 60
o
which suggests that he molecule is under strain and hence active in nature.
Red Phosphorus
Preparation
Red phosphorus is formed by heating yellow phosphorus, between 240-250
o
C, in presence of an inert gas. The
heating is done in an egg shaped iron vessel provided with a upright tube closed by safety value. the thermometers
placed in iron tubes help to regulate the temperature.
Structure of red phosphorus
The exact structure of red phosphorus is not yet known. It is regarded as a polymer consisting of chains of P
4
tetrahedral linked together possible in the manner as shown in the figure.
Proposed molecular structure of red phophorus
Comparison between White and Red Phosphorus

S.No. Property White Phosphorus Red Phosphorus

1. Physical State Soft waxy solid Brittle powder

2. Colour White when pure. Attains yellow Red
colour on standing

3. Odour Garlic Odourless
4. Specific gravity 1.8 2.1
5. Melting point 44
0
C Sublimes in absence of air at 290
0
C
6. Ignition temperature Low, 30
0
C High, 260
0
C
7. Solubility in water Insoluble Insoluble
8. Solubility in CS
2
Soluble Insoluble
9. Physiological action Poisonous Non-poisonous
10. Chemical activity Very active Less active
11. Stability Unstable Stable
12. Phosphorescence Glows in dark Does not glow in dark
13. Burning in air Forms P
4
O
10
Forms P
4
O
10
14. Reaction with NaOH Evolves phosphine No action

15. Action of Cl
2
Combines spontaneously to form Reacts on heating to form PCl
3
& PCl
5
PCl
3
& PCl
5
16. Reaction with hot Forms H
3
PO
4
Forms H
3
PO
4
HNO
3
17. Molecular formula P
4
Complex Polymer
Uses of phosphorus
(i) It is largely used in the match industry. Red phosphorus or scarlet phosphorus is preferred to yellow variety.
(ii) Yellow phosphorus is used as a rat poison.
(iii) Red phosphorus is used for the preparation of HBr and HI.
(iv) Radioactive phosphorus (P
32
) is used in th treatement of leukemia and other blood disorders.
(v) It is used for making incendiary bombs and smoke screens.
(vi) It is used in the manufacture of phosphor bronze, an alloy of phosphorus, copper and tin.
(vii)It is used in the manufacture of compounds like hypophosphites (medicine), phosphorus chlorides in industry,
calcium phosphide used in making Holmes signals and orthophosphoric acid.
Compouns of Phosphorus
1. Phosphine, PH
3
It is analogous to ammonia.
Laboratory preparation
It is prepared by blining yellow phosphorus with a concentrated solution of solution of sodium hydroxide in an
inert atmosphere.
P
4
+ 3NaOH + 3H
2
O
'te hy+o+ho-+h
-o&'um
2 2
PO NaH 3
+ PH
3
Besides PH
3
, small amounts of hydrogen and phosphorus dihydride (P
2
H
4
) are also formed.
P
4
+ 4NaOH + 4H
2
O 3NaH
2
PO
2
+ 2H
2
3P
4
+ 8NaOH + 8H
2
O

8NaH
2
PO
2
+ 2P
2
H
4
As soon as the bubbles of the gas come in contact with air, they catch fire spontaneously forming rings of smoke
known as vortex rings. This combustion is due to the presence of highly inflammable phosphorus dihydride
(P
2
H
4
).
2P
2
H
4
+ 7O
2

a%'&
or'% 7eta+ho-+h
3
HPO 4
+ 2H
2
O
P
2
H
4
can be removed from phosphine by the following methods:
(i) By passing the evolved gas through a freezing mixture which condenses P
2
H
4
.
(ii) By passing the gas through HI. PH
3
is absorbed forming phosphonium iodide. This on treatment with casutic
potash gives pure phosphine.
PH
4
I + KOH KI + H
2
O + PH
3
Physical properties
It is a colourless gas having unpleasant garlic like odour or rotten fish odour.
(a) Decomposition
When heated out of contact of air to 440
O
C or when electric sparks are passed through, phosphine decomposes
into red phosphorus and hydrogen.
PH
3

P
4
+ 6H
2
(b) Combustibility
A pure sample of phosphine is not spontaneously inflammable. It burns in air or oxygen when heated at 150
o
C.
2PH
3
+ 4O
2

P
2
O
5
+ 3H
2
O
The spontaneous in flammability of phosphine at the time of preparation is due to the presence of highly inflammable
phosphorus dihydride, P
2
H
4
. This property is used in making Holmes signal. A mixture of calcium carbide and
calcium phosphide is placed in metallic containers. Two holes are made and the container is thrown into the sea.
Water enters and produces acetylene and phosphine respectively. The gaeous mixture catches fire spontaneously
due to the presence of P
2
H
4
. The acetylene produces a bright luminous flame which serves as a signal to the
approaching ship.
(c) Action of chlorine
Phosphine burns in the atmosphere of chlorine and forms phosphorus pentachloride.
PH
3
+ 4Cl
2

PCl
5
+ 3HCl
(d) Basic nature
Phosphine is neutral to litmus. However, it si a weak base, even weaker than ammonia. It reacts with HCl, HBr
or HI to form phosphonium compounds.
PH
3
+ HCl

PH
4
Cl (Phosphonium chloride)
PH
3
+ HBr

PH
4
Br (Phosphonium bromide)
PH
3
+ HI

PH
4
I (Phosphonium iodide)
(e) Action of nitric acid
In contact with nitric acid phosphine begins to burn.
2PH
3
+ 16 HNO
3

P
2
O
5
+ 16NO
2
+ 11H
2
O
(f) Addition compounds
In forms addition compounds with anhydrous AlCl
3
and SnCl
4
AlCl
3
+ 2PH
3

AlCl
3
.2PH
3
SnCl
4
+ 2PH
3

SnCl
4
.2PH
3
When PH
3
is passed through cuprous chloride solution in HCl, it forms an addition compound.
Cu
2
Cl
2
+ 2PH
3

2CuCl. PH
3
(g) Formation of phosphides
(i) When phosphine is passed through copper sulphate solution, a black precipitate of cupric phosphide is
formed.
3CuSO
4
+ 2PH
3

Cu
3
P
2
+ 3H
2
SO
4
(ii) A black precipitate of silver phosphide is formed when phosphine is circulated through silver nitrate solution.
3AgNO
3
+ PH
3

Ag
3
P + 3HNO
3
(h) The mixture of PH
3
and N
2
O or PH
3
and NO explodes in presence of electric spark.
PH
3
+ 4N
2
O

H
3
PO
4
+ 4N
2
2. Oxides of Phosporus
Phosphorus forms three important oxides. These exist in dimeric forms.
(i) Phosphorus trioxide, P
2
O
3
or P
4
O
6
(ii) Phosphorus tetroxide, P
2
O
4
or P
4
O
8
(iii) Phosphorus pentoxide, P
2
O
5
or P
4
O
10
(i) Phosphorus trioxide P
2
O
3
or P
4
O
6
It is formed by burning phosphorus in limited supply of air.
P
4
+ 3O
2

P
4
O
6
The pentoxide, formed in small amount, is removed by passing through glass wool. The vapours of trioxide pass
through the glass wool and are condensed in a reveiver cooled by a freezing mixture.
Structure of Phosphine
Phosphine is a covalent molecule. It has pyramidal structure like ammonia.
The bond angle H-P-H is 93
o
.
Uses:
(i) For making Holmes signals.
(ii) For making smoke screens.
(iii) For making metallic phosphides.
Vapours of phosphorus at low pressure react with N
2
O at 600
o
C to form P
2
O
3
.
P
4
+ 6N
2
O

C #00
o
2P
2
O
3
+ 6N
2
Properties
(a) It is a waxy solid having garlic odour.
(b) It is poisonous in nature.
(c) It is soluble in benzene or chloroform.
(d) When heated above 210
o
C, it forms red phosphorus and another oxide, P
4
O
8
.
4P
4
O
6

tetro.'&e
Pho-+horu-
8 4
O P 3
+
& )e
P 4
When heated at about 440
o
C, it dissociates to phosphorus dioxide.
2P
2
O
3
3PO
2
+ P
(e) In contact with air, it is oxidised to phosphorus pentoxide.
P
4
O
6
+2O
2

P
4
O
10
(f) It burns in chlorine forming oxy-chlorides.
P
4
O
6
+ 4Cl
2

%hlor'&e O.y
Pho-+horu-
3
POCl 2

+
%hlor'&e O.y
oru- 7eta+ho-+h
2
Cl PO 2

(g) In cold water it dissolves slowly forming phosphorus acid.

P
4
O
6
+ 6H
2
O (cold) 4H
3
PO
3
With hot water, a violent reaction occurs forming orthophosphoric acid and phosphine.
P
4
O
6
+ 6H
2
O (hot)

3H
3
PO
4
+ PH
3
The above reaction is actually the conversion of phosphorus acid into orthophosphoric acid and phosphine.
4H
3
PO
3

3H
3
PO
4
+ PH
3
This oxide is known as acid anhydride of phosphorus acid.
Structure of phosphorus trioxide
(ii) Phosphorus pentoxide, P
4
O
10
It is prepared by heating phosphorus in a free supply of air or oxygen.
P
4
+ 5O
2
P
4
O
10
It is further purified by sublimation.
Phosphorus burns in CO
2
at 100
o
C to form P
2
P
5
.
2P + 5CO
2

P
2
O
5
+ 5CO
Properties
(a) It is a white crystalline compounds
(b) It is odourless when pure. The usual garlic odour is due to presence of small amount of P
4
O
6
as impurity.
(c) It sublimes on heating.
(d) It has great affinity for water. The final product is orthophosphoric acid. It is therefore, termed phosphoric
anhydride.
i.e.P
4
O
10
+ 6H
2
O 4H
3
PO
4
It is, thus used as a powerful dehydrating or drying agent. It removes water from inorganic and organic compounds
like H
2
SO
4
, HNO
3
, RCOOH, RCONH
2
, etc.
2H
2
PO
4
+ P
4
O
10
2SO
3
+ 4HPO
3
4HNO
3
P
4
O
10

2N
2
O
5
+ 4HPO
3
4CH
3
-
COOH + P
4
O
10

2(CH
3
CO)
2
O + 4HPO
3
2CH
3
CONH
2
+ P
4
O
10

2CH
3
Cn + 4HPO
3
It also chars wood, paper, sugar etc.
(e) when heated strongly with carbon, it forms red phosphorus.
P
4
O
10
+ 10C

10CO + 4P(red phosphorus)

(f) when fused with basic oxides, it forms phosphates.
6CaO + P
4
O
10

2Ca
3
(PO
4
)
2
(g) 30% H
2
O
2
react on P
2
O
5
in acetonitrile solution at low temperature to form peroxy monophosphoric acid.
P
2
O
5
+ 2H
2
O
2
+ H
2
O

2H
3
PO
5
(h) Mixture of P
2
O
5
and O
2
in vapour state combine in presence of electric discharge to form P
2
O
6
called
phosphorus peroxide.
P
2
O
5
+ 1/2O
2

P
2
O
6
Uses
It is most effective drying or dehydrating agent below 100
o
C
Structure of phosphorus pentoxide
3. Oxyacids of phosphorus
Phosphorus forms a number of oxyacids. Common oxyacids are given below.
Name of Oxyacid Formula Basicity Oxidation state of P
Hydrophosphorus acid H
3
PO
2
1 +1
Phosphorus acid H
3
PO
3
2 +3
Orthophosphoric acid H
3
PO
4
3 +5
Metaphosphoric acid HPO
3
1 +5
Hypophosphoric acid H
2
P
2
O
6
4 +4
Pyrophosphoric acid H
4
P
2
O
7
4 +5
(i) Phosphorus acid, H
3
PO
3
, Prepartion
(i) It is obtained by dissolving phosphorus trioxide in water.
P
4
O
6
+ 6H
2
O H
3
PO
3
(ii) It is also obtained by hydrolysis of phosphorus trichloride.
PCl
3
+ 3H
2
O

H
3
PO
3
+ 3HCl
Chlorine is passed over molten white phosphorus under water when phosphorus trichloride formed undergoes
hydrolysis.
2P + 3Cl
2

2PCl
3
The solution is heated until the temperature becomes 180
o
C. On cooling crystals of phosphorus acid are obtained.
Properties
(a) It is colourless crystalline compound. It melts at 73
o
C. It is highly soluble in water.
(b) When heated, it forms orthophosphoric acid and phosphine.
4H
3
PO
3


C 200
o
3H
3
PO
4
+ PH
3
(c) It si strong acid. It is diabasic in nature.
H
3
PO
3
H

+ H
2
PO
3

2H

+ HPO
3

K
1
= 10
1
; K
2
= 2 x 10
7
It thus forms two series of salts such as NaH
2
PO
3
adn Na
2
HPO
3
known as primary phosphites and secondary
phosphites respectively.
(d) It acts as a strong reducing agent. The potential equation is:
H
3
PO
3
+ H
2
O H
3
PO
4
+ 2H
It reduces CuSO
4
to Cu, AgNO
3
to Ag, HgCl
2
to Hg
2
Cl
2
, I
2
to HI and acidfied KMnO
4
solution.
CuSO
4
+ 2H

Cu + H
2
SO
4
AgNO
3
+ H

Ag + HNO
3
2HgCl
2
+ 2H

Hg
2
Cl
2
+ 2HCl
I
2
+ 2H

2HI
2KMnO
4
+ 3H
2
SO
4

K
2
SO
4
+ 2MnSO
4
+ 3H
2
O + 5O
[H
3
PO
3
+ O

K
3
PO
4
] x 5
----------------------------------------------------------------------------
2KMnO
4
+ 3H
2
SO
4
+ 5H
3
PO
3

K
2
SO
4
+ 2MnSO
4
+ 5H
3
PO
4
+ 3H
2
O
Structure of Phosphorus acid
It is diabasic acid, i.e. two hydrogen atoms are insoluble or two hydroxyl groups are present. Thus, the structure
is:
The phosphorus lies in sp
3
hybrid state.
(ii) Orthophosphoric aicd, H
3
PO
4
This acid is commonly called as phosphoric acid.
Preparation
(i) It is formed when phosphorus pentoxide is boiled with hot water.
(ii) ORthophosphoric acid is also formed when PCl
5
(Phosphorus pentachloride) is boiled with water.
PCl
5
+ 4H
2
O H
3
PO
4
+ 5HCl
(iii) Laboratory preparation
The best method for its preparation in the laboratory is to heat red phosphorus with concentrated nitric acid in a
flask with a reflux condenser.
P + 5HNO
3

H
3
PO
4
+ H
2
O + 5NO
2
The reaction is usually carried out is presence of a crystal of iodine. The iodine acts as a catalyst.
P + 3I

PI
3
PI
3
+ 3H
2
O

H
3
PO
3
+ 3HI
3HI + 3HNO
3

3H
2
O + 3NO
2
+ 3I
H
3
PO
3
+ 2HNO
3

H
3
PO
4
+ H
2
O + 2NO
2
------------------------------------------------------------
P + 5HNO
3

H
3
PO
4
+ 5NO
2
+ H
2
O
The solution is concentrated till it becomes syrupy about 170
o
C. It is cooled over conc. H
2
SO
4
in vacuum
dessicator when crystals of orthophosphoric acid are formed.
Manufacture
It is prepared on large scale from bone ash or phosphoric mineral.
(a) By decomposing calcium phosphate present is bone ash or phosphoric meneral with conc. H
2
SO
4
.
Ca
3
(PO
4
)
2
+ 3H
2
SO
4

3CaSO
4
+ 2H
3
PO
4
On standing calcium sulphate settles down and the clear supernatant liquid separates out. The liquid is concentrated
when about 85% concentrated orthophosphoric acid is obtained.
(b) The bone ash is dissolved in minimum amount of nitric acid and lead acetate is added as to precipitate lead
phosphate. The lead salt is then decomposed by passing H
2
S.
Pb
3
(PO
4
)
2
+ 3H
2
S

le lu0 'n-o
P0/ 3
+
-olut'on
4 3
PO H 2
(c) Bone ash or calcium phosphate is converted into phosphorous pentoxide when heated with silica in electric
furnace.
2Ca
3
(PO
4
)
2
+ 6SiO
2
6CaSiO
3
+ P
4
O
10
P
4
O
10
is then dissolved in hot water.
P
4
O
10
+ 6H
2
O

4H
3
PO
4
properties
(a) It is transparent deliquescent solid. It melts at 42.3
o
C. It absorbs water and forms colourless syrupy mass. It
is highly soluble in water.
(b) Heating effect
When heated at 250
o
C, it is converted into pyrophosphoric acid.
2H
3
PO
4


C 250
o
H
4
P
2
O
7
+ H
2
O
On further heating, it is converted into metaphosphoric acid.
H
3
PO
4

C #00
heat
o

HPO
3
+ H
2
O
H
4
P
2
O
7


heat
2HPO
3
+ H
2
O
When strongly heated at red heat, it forms P
4
O
10
.
(c) Acidic mature
It is tribasic acid, i.e. all the three hydrogen atoms are ionizable. It forms three series of salts.
H
3
PO
4
H
+
+ H
2
PO
4
-

2H
+
+ HPO
4
2-

3H
+
+ PO
4
3-
8 -alt +r'mary 9
4 2
PO NaH

8 -alt on&ary 9-e%
4 2
HPO Na
8 -alt normal 9
4 3
PO Na
Primary salt on heating forms a slat of metaphosphoric acid.
+ho-+hate
&'hy&rogen /o&'um
4 2
PO NaH


heat
ate meta+ho-+h
/o&'um
3
NaPO
+ H
2
O
Secondary salt on heating forms a slat of pyrophosphoric acid.
+ho-+hate
Hy&rogen D'-o&
3 2
HPO Na 2
heat

ate +yro+ho-+h
/o&'um
" 2 4
O P Na
+ H
2
O
Normal salt is not affected by heating.
In case, ammonium ion is present in the slat it behaves as hydrogen.
2MgNH
4
PO
4


heat
Mg
2
P
2
O
7
+ 2NH
3
+ H
2
O
NaNH
4
HPO
4


heat
naPO
3
+ NH
3
+ H
2
O
(d) Reaction with AgNO
3
A yellow precipitate of silver phosphate is formed.
3AgNO
4
+ H
3
PO
4

++t yello,
4 3
PO 6g
+ 3HNO
3
(e) Reaction with BaCl
2
A white ppt. of barium phosphate is formed in neutral or alkaline solution.
3BaCl
2
+ 2H
3
PO
4

++t ,h'te
2 4 3
8 PO 9 $a
+ 6HCl
(f) Reaction with bromides and iodides
Hydrobromic and hydroiodic acids are liberated from bromides and iodides respectively. This is te laboratory
preparation of HBr and HI.
3NaBr + H
3
PO
4
Na
3
PO
4
+ 3HBr
3NaI + H
3
PO
4

Na
3
PO
4
+ 3HI
(g) Reaction with magnesium salt
Magnesium slats combine with orthophosphoric acid in presence o ammonium chloride nd ammonium hydroxide
to form a white precipitate of magnesium ammonium phosphate.
MgSO
4
+ NH
4
Cl + H
3
O
4

Mg(NH
4
)PO
4
+ H
2
SO
4
+ HCl
This reaction is used to test Mg
2+
ion.
(h) On heating orthophosphoric acid is presence of nitric acid with ammonium molybdate a canary yellow ppt. of
ammonium phosphomolybdate is formed.
H
3
PO
4
+ 21 HNO
3
+ 12 (NH
4
)
2
MoO
4

oly0&ate hom +ho-+ 6mmon'um
3 4 3 4
7oO 12 PO 8 NH 9
+ 21 NH
4
NO
3
+ 12 H
2
O
This reaction is used to test PO
4
3
ion.
Structure of orthophosphoric acid
Orthophosphoric acid is a tribasic. i.e. 3 hydroxyl groups are present. The structure of the acid is thus represented
as:
Phosphorus atom lies in sp
3
hybrid state.
* * * * *
CHALCOGENS
Oxygen
Preparation: Oxygen can be obtained in the laboratory by Iollowing methods:
(i) From Oxides: (a) By thermal decomposition oI the oxides oI metals which are in lower part oI
electrochemical series.
2HgO
450
0
C

2Hg O
2
; 2AgO
2
350
0
C

4Ag O
2
(b) By the thermal decomposition oI higher oxides.
3MnO
2
Heat

Mn
3
O
4
O
2
; 2Pb
3
O
4
Heat

6PbO O
2
2BaO
2
Heat

2BaO O
2
(c) By action oI conc. H
2
SO
4
on MnO
2
2MnO
2
2H
2
SO
4
2MnSO
4
2H
2
O O
2
(d) By action oI water on sodium peroxide (oxone),
2Na
2
O
2
2H
2
O 4NaOH O
2
(ii) From salts: (a) Alkali nitrates on heating evolve oxygen.
2NaNO
3
2NaNO
2
O
2
; 2KNO
3
2KNO
2
O
2
(b) K
2
Cr
2
O
7
, KMnO
4
and KClO
3
decompose at high temperatures evolving oxygen.
4K
2
Cr
2
O
7
400
0
C

4K
2
CrO
4
2Cr
2
O
3
3O
2
2KMnO
4
250
0
C

K
2
MnO
4
MnO
2
O
2
2KClO
3
400
0
C

2KCl 3O
2
(c) By heating KMnO
4
or K
2
Cr
2
O
7
with concentrated H
2
SO
4
.
4KMnO
4
6H
2
SO
4
2K
2
SO
4
4MnSO
4
6H
2
O 5O
2
2K
2
Cr
2
O
7
8H
2
S
4
2K
2
SO
4
2Cr
2
(SO
4
)
3
8H
2
O 3O
2
(d) By adding H
2
O
2
to acidiIied KMnO
4
solution.
2KMnO
4
3H
2
SO
4
(dil.) K
2
SO
4
4MnSO
4
3H
2
O 5|O|
|H
2
O
2
O H
2
O O
2
| x 5

2KMnO
4
3H
2
SO
4
5H
2
O
2
K
2
SO
4
2MnSO
4
8H
2
O 5O
2
4KClO
3
3KClO
4
KCl
Potassium Potassium
chlorate perchlorate
KClO
4
650
0
C

KCl 2O
2
Manufacture: Oxygen is obtained on commercial scale by Iollowing methods:
(a) By Brin`s process
(b) By electrolysis oI water
Properties : Oxygen is a colourless, odourless and tasteless gas. It is little heavier than air and is slightly
soluble in water. this small amount oI dissolved oxygen in water supports the respiration oI Iish and other
aquatic animals. It is soluble in alkaline pyrogallol. It exhibits allotropy. Its allotropic madoIications is ozone
(O
3
). There are three isotopes oI oxygen with mass numbers 16, 17 and 18 (O
16
, O
17
and O
18
). O
16
is the
main one with an abundance oI nearly 99.8.
Oxygen is not a combustible gas, but it is a strong supporter oI combustion. It is very active element.
Structure: According to the M.O.T. structure oI O
2
molecule is as Iollows:
KKo(2s)
2
o*(2s)
2
o(2p
x
)
2
t(2p
y
)
2
t(2p
z
)
2
t*(2p
y
)
1
t*(2p
z
)
1
Bond order in this case is (8 4) 2
Properties:
Oxygen combines nearly with all other elements excepts inert gases, noble metals and halogens. The
binary compounds of oxygen with other elements are called oxides. However, the compounds oI
oxygen and Iluorine (OF
2
, O
2
F
2
) are not called as oxides but oxygen Iluorides as Iluorine is more
electronegative than oxygen.
Oxides may be prepared by burning oI elements such as C, P, S, Na, K, Mg, etc. in air or oxygen
atmosphere.
C O
2
CO
2
(Carbon burns with Ilush light)
S O
2
SO
2
(Sulphur burns with blue light)
4Na O
2
2Na
2
O (Sodium burns with yellow light)
4K O
2
2K
2
O (Potassium burns with violet light)
2Mg O
2
2MgO (Magnesium burns with white light)
Peroxide: The oxides when treated with dilute acids Iorm hydrogen peroxide. These oxides are considered
as derivatives oI H
2
O
2
and contain peroxo linkage in their molecule.
Examples: NaO
2
, K
2
O
2
, BaO
2
etc.
Na
2
O
2
H
2
SO
4
(dil.) Na
2
SO
4
H
2
O
2
BaO
2
H
2
SO
4
(dil.) BaSO
4
H
2
O
2
Na
2
O
2
can be written as NaOONa. The linkage OO is called peroxo linkage.
Super oxides contain O
2

ion. The superoxides known are KO

2
, RbO
2
and CsO
2
. These react with water
to give hydrogen peroxide and oxygen.
2KO
2
2H
2
O 2KOH H
2
O
2
O
2
OZONE
Laboratory preparation: Ozone is obtained by passing silent electric discharge through dry oxygen. It is
believed that some oI the oxygen molecules dissociate and then atomic oxygen combines with oxygen
molecules to Iorm ozone.
O
2
Energy

O O
O
2
O O
3
3O
2
2O
3
energy
The mixture obtained consists oI 510 ozone by volume and the mixture is called ozonised oxygen. The
apparatus used Ior this purpose is known as ozoniser. The commnoly used ozonisers are:
(i) Siemen`s ozoniser; and (ii) Brodie`s ozoniser
Manufacture: For the manuIacture oI ozonised air Seimen and Halske`s ozoniser is employed.
Recovery of Pure Ozone from Ozonised Oxygen
The ozonised oxygen is passed through a spiral cooled by liquid air. Ozone condenses as its condensation
temperature is 112.4
0
C. The liquid ozone thus obtained may contain some dissolved oxygen. This liquid
is Iractionally distilled to get pure ozone.
Some Reactions Forming Ozone
(i) Fluorine reacts with water at a very low temperature when mixture oI ozonised oxygen is Iormed.
2 2 4
3 3 6
2 2 2
2 2 3
F H O HF O
F H O HF O
ozonised oxygen
+ +
+ +

(ii) By action oI ultraviolet rays, oxygen can be converted into ozone.

O
2
UV

O O
O
2
O O
3
(iii) The electrolysis oI acidiIied water with high current density and platinum anode yields ozone on the
anode. Nascent oxygen discharged at anode combines with molecular oxygen to Iorm ozone.
Physical properties: (a) It is a pale blue gas with a charactersticstrong smell.
(b) It is slightly soluble in water but more soluble in turpentine oil, glacial acetic acid, or carbon tetrachloride.
Chemical properties:
(a) Decomposition: It is unstable and decomposes completely into oxygen at 300
0
C.
2O
3
Heat

3O
2
68kcal
MnO
2
, platinum black, silver, lead dioxide etc., decompose ozone at ordinary temperature, i.e., they catalyse
its decomposition.
(b) Oxidising nature: Due to the ease with which it can liberate nascent oxygen, it acts as a powerIul
oxidising agent. The potential equation is:
O
3
O
2
O
The oxidation potential in acid medium is 2.07 V.
O
3
2H

2e

O
2
H
2
O E
0
2.07 V
2HCl O
3
H
2
O Cl
2
O
2
(ii) AcidiIied Ierrous sulphate into Ierric sulphate.
2FeSO
4
H
2
SO
4
O
3
Fe
2
(SO
4
)
3
H
2
O O
2
(iii) It liberates iodine Irom neutral KI solution.
2KI H
2
O O
3
2KOH I
2
O
2
(iv) Lead sulphide (black) is oxidised to lead sulphate (colourless).
PbS 4O
3
PbSO
4
4O
2
Similarly, CuS, ZnS and CdS are oxidised to CuSO
4
, ZnSO
4
and CdSO
4
, respectively.
(v) It oxidises nitrites into nitrates, sulphites into sulphates, arsenites to arsenates, manganate to permanganate
and Ierroxyanide to Ierricyanide.
NaNO
2
O
3
NaNO
3
O
2
Na
2
SO
3
O
3
Na
2
SO
4
O
2
Na
3
AsO
3
O
3
Na
3
AsO
4
O
2
sodium arsenite sodium arsenate
2K
2
MnO
4
H
2
O O
3
2K
3
Fe(CN)
6
2KOH O
2
Potassium Potassium
manganate permanganate
2K
4
Fe(CN)
6
H
2
O O
3
2K
3
Fe(CN)
6
2KOH O
2
Potassium Potassium
Ierrocyanide Ierricyanide
(vi) Moist iodine is oxidised to iodic acid.
I
2
H
2
O 5O
3
2HIO
3
5O
2
Iodic acid
Similarly moist sulphur, phosphorus and arsenic are oxidised to their corresponding oxyacids.
S H
2
O 3O
3
H
2
SO
4
3O
2
2P 3H
2
O 5O
3
2H
3
PO
4
5O
2
2As 3H
2
O 5O
3
2H
3
AsO
4
5O
2
(vii) H
2
S is oxidised to sulphur
H
2
S O
3
H
2
O S O
2
(viii) Alkaline KI is oxidised to potassium iodate and periodate.
KI 3O
3
KIO
3
3O
2
Potassium iodate
KI 4O
3
KIO
4
4O
2
Pot. periodate
(ix) Dry iodine is oxidised to yellow powder, I
4
O
9
|O
3
O
2
O| x 9
2I
2
9O I
4
O
9 .

2I
2
9O
3
I
4
O
9
9O
2
(x) Silver metal is blackened due to alternate oxidation oI the metal and reduction oI oxide.
2Ag O
3
Ag
2
O O
2
Ag
2
O O
3
2Ag 2O
2
(xi) Mercury in presence oI ozone is oxidised to suboxide which dissolves in mercury. It starts sticking to
glass and loses mobility. Hence, mercury loses its meniscus in contact with ozone. This is termed as the
tailing oI mercury.
2Hg O
3
Hg
2
O O
2
(xii) Ozone reacts with KOH and Iorms potassium ozonide, KO
3
, which is an orange coloured solid and
contains paramagnetic O
3
ion.
2KOH 5O
3
3KO
3
5O
2
H
2
O
In all above reactions, oxygen is evolved.
There are Iew reactions in which whole oI the oxygen is used up in the process oI oxidation.
1. Oxidises SO
2
to SO
3
3SO
2
O
3
3SO
3
2. AcidiIied stannous chloride is oxidised to stannic chloride.
3SnCl
2
6HCl O
3
3SnCl
4
4H
2
O
(c) Bleaching property: It is a good bleaching agent. The bleaching action is due to its oxidising action
on the organic matter.
coloured substance O Colourless
It bleaches oil, ivory, Ilour, starch, waxes, wood pulp, etc.
(d) Formation of ozonides: Ozone reacts with unstaurated organic compounds containing double bonds.
The products Iormed are known as ozonides. The ozonides break up when treated with water to Iorm
carbonyl compounds. The process is called ozonolysis. H
2
O
2
is evolved in most oI the cases.
(e) Reaction withe peroxide: Reaction oI ozone with peroxide results in their mutual reduction with the
liberation oI oxygen.
BaO
2
O
3

BaO 2O
2
H
2
O
2
O
3

H
2
O 2O
2
Uses: (i) As a germicide and disinIectant Ior sterilizing water and improving the atmosphere oI crowded
places like tube railways mines and cinema halls.
(ii) As a bleaching agent Ior oils, Ilour, ivory, wax and delicate Iabrics.
Structure oI Ozone:
The bond length is intermediate between that Ior a single bond (1.48A as in H
2
O
2
) and Ior a double bond
(1.21A as in O
2
). Ozone is, thereIore, considered to be a resonance hybrid oI the Iollowing two Iorms.
Distinction between Ozone and Hydrogen Peroxide
Ozone Hydrogen peroxide
SULPHUR
Occurrence: It occurs in abundance in the combined state as:
(i) Sulphide ores, e.g., Zine blende (ZnS), galena (PbS), cinnabar (HgS), copper pyrites (CuFeS
2
) and
iron pyrites (FeS
2
).
(ii) Sulphate ores, e.g., Gypsum (CaSO
4
.2H
2
O), barytes (BaSO
4
), Epsom salt (MgSO
4
7H
2
O) and celesite
(SrSO
4
).
(iii) H
2
S and SO
2
in volcanic gases. H
2
S in spring waters, coal gas, sewage gas, etc.
(iv) Organic compounds oI plant and animal origin, e.g., onion, garlic, mustard, eggs, proteins, hair, wool,
etc. contain organic sulphur compounds.
Extraction: (i) To extract underground sulphur, Frasch process is used. Three concentric pipes are sunk
deep into the ground. Super heated water at 170
o
C is Iorced down the outer pipe into sulphur which is
melted. Compressed air blown through inner pipe Iorces the sulphur as a liquid to the surIace where it is
allowed to solidiIy. 99.5 pure sulphur is obtained by this process.
(ii) Sulphur as a byproduct:(a) From alkali waste of Leblanc`s process: The alkali waste (mainly
CaS) is suspended in water and carbon dioxide is circulated. Hydrogen sulphide is liberated which is burnt
in an insuIIicient supply oI air.
CaS H
2
O CO
2

CaCO
3
H
2
S
2H
2
S O
2

2H
2
O 2S
(Air)
1. Pale blue gas with a strong rotten smell.
2. It does not decolourise acidiIied potassium
permanganate.
3. Mercury loses its meniseus in contact with
ozone. It starts sticking to glass.
4. It turns an alcoholic solution oI benzidine
brown.
5. It turns an alcoholic solutionoI tetramethyl
base violet.
6. It does not turn starch-iodide paper blue in
presnece oI Ierrous sulphate.
7. No action with titanium sulphate solution.
8. No action with acidiIied potassium
dichromate in presence oI ether.
Colourless and odourless syrupy liquid.
It decolourises acidiIied potassium permanganate.
No action on mercury.
No action.
No action.
It turns starch-iodide paper blue in presence oI Ierous
sulphate.
Orange colour with titanium sulphate solution is
developed.
Blue colour in ether layer when H
2
O
2
is added to
mixture containing potassium dichromate and
concentrated H
2
SO
4
in presence oI ether.
(b) From the spent oxides of the gas works: It contains Ierric sulphide (Fe
2
S
3
). It is exposed to air Ior
a Iew days when sulphur is deposited.
2Fe
2
S
3
3O
2

2Fe
2
O
3
6S
(c) From iron pyrites: Iron pyrites is a good source oI sulphur. It is recovered when pyrite is distilled.
3FeS
3
Distillation

Fe
3
S
4
2S
Pure sulphur is obtained by boiling impure sulphur at 444
o
C. The vapours oI sulphur evolved are condensed
on the cold walls as a light yellow powder.
Allotropic forms: Sulphur exists in several allotropic Iorms, the important ones are described below:
1. Rhombic or octahedral or osulphur: This is the common Iorm oI sulphur. It is pale yellow in colour. .
It melts at 114.5
o
C. Its speciIic gravity is 2.06. It is insoluble in water but readily soluble in carbon disulphide.
It is a crystalline variety and consists oI S
8
structural units packed together into octahedral shape. This is
the stable variety at orginary temperature and all other Iorms gradually change into this Iorm.
2. Monoclinic or prismatic or |sulphur: This Iorm is Iormed by melting sulphur in a dish and cooling
till crust is Iormed. Two holes are made in the crust and liquid is poured out. On removing the crust, needle
shaped crystals oI monoclinic sulphur are obtained.
This Iorm oI sulphur is stable above 95.6
o
C. The crystals are amber yellow in colour and have speciIic
gravity oI 1.96. Crystals melt at 119
o
C. It is also soluble in carbon disulphide. Below 95.6
o
C, it changes
into rhombic Iorm. Thus, 95.6
o
C is the transition temperature.
Rhombic Sulphur Monoclinic Sulphur
3. Plastic sulphur: This is obtained when boiling sulphur is poured into cold water. It is soIt rubber like
mass which hardens on standing and gradually changes into rhombic sulphur. It is amberbrown in colour
and has speciIic gravity oI 1.95. It is insoluble in CS
2
and has no sharp melting point. It consists oI a
completely random arrangement oI chains oI sulphur atoms.
Action of heat on sulphur: Orginary sulphur melts at 114
o
C to a pale yellow mobile liquid. On heating
Iurther instead oI becoming more mobile, it grows thicker. The colour changes to reddish brown and then
to almost black. At about 180
O
C. the viscosity increases so much that it cannot be poured out by inverting
the container. At about 200
o
C the viscosity begins to decrease and at its boiling point oI 444
o
C, the liquid
is again mobile. No diIinite explanation oI these observations is known uptil now.
Uses: Sulphur is used:
(i) In the manuIacture oI SO
2
, H
2
SO
4
, CS
2
, matches, gun powder, Iire works. etc.
(ii) Ior vulcanising rubber and in the manuIacture oI sulphur dyes.
COMPOUNDS OF SULPHUR
Hydrogen Sulphide or Sulphuretted Hydrogen (H
2
S)
Laboratory preparation: Hydrogen sulphide is obtained in the laboratory by the action oI dilute sulphuric
acid on Ierrous sulphide.
FeS H
2
SO
4

FeSO
4
H
2
S
As the gas is required intermittently in the laboratory, it is prepared in the well known Kipp`s apparatus.
The gas obtained is always impure as it is contaminated with hydrogen. Pure hydrogen sulphide can be
prepared by the action oI pure HCl on antimony sulphide.
Sb
2
S
3
6HCl

2SbCl
3
3H
2
S
Physical properties: (a) It is a colourless gas with unpleasant odour oI rotten eggs.
(b) It is slightly heavier than air and moderatory soluble in cold water. The solubility decreases in hot water.
(c) It is poisonous in nature. It produces headache when inhaled in small quantities but may cause death
when inhaled Ior a long time.
(d) It can be easily liqueIied by pressure. The boiling point is about 60
0
C. It Ireezes to a transparent solid
at 85.6
0
C.
Chemical properties: (a) Combustibility: The gas burns with a blue Ilame in oxygen on air Iorming
sulphur dioxide and water.
2H
2
S 3O
2
2H
2
O 2SO
2
In restricted supply oI oxygen, sulphur is Iormed due to incomplete combustion.
2H
2
S O
2
2H
2
O 2S
(b) Thermal decomposition: The gas is not so stable as water. It decomposes on heating. The decomposition
starts at 310
0
C and completes at 1700
0
C.
H
2
S H
2
S
(c) Reducing nature: Hydrogen sulphide acts as a strong reducing agent as it decomposes evolving
hydrogen. The Iollowing are the important examples oI its reducing action:
(i) It reduces halogens into corresponding hydracids.
H
2
S X
2
2HX S (X
2
F
2
, Cl
2
, Br
2
or I
2
)
(ii) It reduces Ierric chloride to Ierrous chloride.
2FeCl
3
H
2
S 2FeCl
2
2HCl S
(iii) Sulphur dioxide is reduced to sulphur in presence oI moisture.
SO
2
2H
2
S 3S 2H
2
O
The occurrence oI sulphur in volcanic regions is attributed due to the above reaction as both gases are
present in volcanic gases.
(iv) H
2
O
2
is reduced to water.
H
2
O
2
H
2
S 2H
2
O S
(v) O
3
is reduced to O
2
.
H
2
S O
3
H
2
O S O
2
(vi) HNO
3
is reduced to NO
2
.
2HNO
3
H
2
S 2NO
2
S 2H
2
O
(vii) H
2
SO
4
is reduced into SO
2
H
2
SO
4
H
2
S 2H
2
O SO
2
S
(viii) AcidiIied KMnO
4
is decolourised
2KMnO
4
3H
2
SO
4
5H
2
S K
2
SO
4
2MnSO
4
8H
2
O 5S
(ix) AcidiIied K
2
Cr
2
O
7
is reduced Iorming green chromic sulphate.
K
2
Cr
2
O
7
4H
2
SO
4
3H
2
S K
2
SO
4
Cr
2
(SO
4
)
3
7H
2
O 3S
(d) Acidic nature: The aqueous solution oI H
2
S acts as a weak dibasic acid. It ionises as Iollows:
H
2
S H

HS

2H

It Iorms two series oI salts, hydrosulphides and sulphides.

NaOH H
2
S NaHS H
2
O
Sodium hydro
sulphide
2NaOH H
2
S Na
2
S 2H
2
O
Sodium sulphide
(e) Reaction with metals and metal oxides: H
2
S reacts with metals and metal oxides to Iorm
corresponding sulphides.
2Na H
2
S Na
2
S H
2
Cu H
2
S CuS H
2
2Ag H
2
S Ag
2
S H
2
Pb H
2
S PbS H
2
CaO H
2
S
Heat

CaS H
2
O
ZnO H
2
S
Heat

ZnS H
2
O
(f) Action on salts: Hydrogen sulphides reacts with salts oI various metals Iorming corresponding sulphides.
The metal sulphides can be divided into three groups.
1. Sulphides precipitated in acidic medium: These are sulphides oI Hg, Ag, Pb, Cu, Bi, Cd, As, Sb and
Sn.
CuSO
4
H
2
S CuS H
2
SO
4
Pb(CH
3
COO)
2
H
2
S PbS 2CH
3
COOH
CdSO
4
H
2
S CdS H
2
SO
4
HgS CuS PbS Black
Bi S Brown
CdS Yellow
Inso le in yellow
ammonium sulphide
, ,
lub

2 3
SnS As S Yellow
Sb S Orange
SnS Chocolate
So le in yellow
ammonium sulphide
2 2 3
2 3
,
lub

2. Sulphides precipitated in alkaline medium: These are the sulphides oI Zn, Co, Ni, Mn and Fe.
MnCl
2
H
2
S MnS 2HCl
Ni(NO
3
)
2
H
2
S NiS 2HNO
3
ZnSO
4
H
2
S ZnS H
2
SO
4
CoS, NiS; Black, ZnS; White, MnS; Flesh coloured
3. Sulphides which are precipitated neither in acidic nor in alkaline medium: These are the sulphides
oI Cr, Al, Mg, Ba, Sr, Ca, K and Na.
(g) Formation of polysulphides: Polysulphides oI metals are obtained by passing H
2
S through their
hydroxides.
Ca(OH)
2
H
2
S CaS 2H
2
O
CaS 4H
2
S CaS
3
4H
2
On passing excess oI H
2
S through ammonium sulphide, yellow ammonium sulphide is Iormed.
2NH
4
OH H
2
S (NH
4
)
2
S 2H
2
O
(NH
4
)
2
S xH
2
S (NH
4
)
2
S
x1
xH
2
Ammonium
polysulphide
Structure of H
2
S: The shape oI the H
2
S molecule is similar to that oI the water molecule, i.e., Vshaped
structure with bond length (HS) 1.35A and bond angle (HSH) 92.5
0
.
Oxides of Sulphur
Sulphur Iorms a number oI oxides. These are:
(i) Sulphur suboxide, S
2
O (colourless gas)
(ii) Sulphur monoxide, SO (colourless gas)
(iii) Sulphur sesquioxide, S
2
O
3
(green crystalline solid)
(iv) Sulphur dioxide, SO
2
(colourless gas)
(v) Sulphur trioxide, SO
3
(volatile liquid)
(vi) Sulphur heptoxide, S
2
O
7
(liquid)
(vii) Sulphur tetroxide, SO
4
(white solid)
Out oI these, sulphur dioxide and sulphur trioxide are common and important and described here.
1. Sulphur dioxide, SO
2
The Iollowing reactions can be used Ior the preparation oI sulphur dioxide.
(a) By burning sulphur in air or oxygen.
S O
2
SO
2
(b) By heating sulphur with concentrated sulphuric acid
S 2H
2
SO
4
Heat

2H
2
O 3SO
2
(c) By heating copper or silver with concentrated sulphuric acid.
Cu 2H
2
SO
4
CuSO
4
2H
2
O SO
2
2Ag 2H
2
SO
4
Ag
2
SO
4
2H
2
O SO
2
(d) By reacting sodium sulphite or sodium hydrosulphite with dil. HCl
Na
2
SO
3
2HCl 2NaCl H
2
O SO
2
NaHSO
3
HCl NaCl H
2
O SO
2
(e) By roasting oI sulphides
2ZnS 3O
2
2ZnO 2SO
2
4FeS
2
HO
2
2Fe
2
O
3
8SO
2
The reactions b, c and d can be used Ior the preparation oI SO
2
in the laboratory while the reactions (a)
and (e) are used in industry to obtain SO
2
.
In places where gypsum or anhydride are Iound in abundance, sulphur dioxide can be obtained on a large
scale by heating gypsum or anhydride with carbon at about 1000
0
C.
2CaSO
4
C 2CaO 2SO
2
CO
2
Physical properties : (a) It is a colourless gas with a pungent, suIIocating odour.
(b) It is highly soluble in water.
Chemical properties: (a) It neither burns nor it helps in burning. However, burning magnesium and potassium
continue to brun in its atmosphere.
3Mg SO
2
2MgO MgS
4K 3SO
2
K
2
SO
3
K
2
S
2
O
3
(b) Thermal decomposition: It decomposes at 1200
0
C producing sulphur trioxide and sulphur.
3SO
2
2SO
3
S
(c) Acidic nature: It is an acidic oxide. It dissolves in water Iorming sulphurous acid.
SO
2
H
2
O H
2
SO
3
(Sulphurous acid)
The gas is, thereIore, known as sulphurous anhydride. It combines with basic oxides and Iorms sulphites.
BaO SO
2
BaSO
3
(d) Addition reactions: (i) It combines directly with halogens to Iorm sulphuryl halides.
SO
2
Cl
2
SO
2
Cl
2
(sulphuryl chloride)
(ii) It combines directly with oxygen in presence oI a catalyst (platinised asbestos)
2SO
2
O
2
2SO
3
(iii) It directly combines with lead dioxide to Iorm lead sulphate
PbO
2
SO
2
PbSO
4
(e) Reducing nature: The aqueous solution oI SO
2
acts as a reducing agent as sulphurous acid changes
into aulphuric acid giving nascent hydrogen.
H
2
O SO
2
H
2
SO
3
H
2
SO
3
H
2
O H
2
SO
4
2H
Examples: (i) It reduces halogens to their respective hydracids.
SO
2
2H
2
O Cl
2
H
2
SO
4
2HCl
(ii) AcidiIied KMnO
4
is reduced, i.e., it is decolourised
2KMnO
4
5SO
2
2H
2
O K
2
SO
4
2MnSO
4
2H
2
SO
4
(iii) AcidiIied K
2
Cr
2
O
7
is turned green due to Iormation oI chromic sulphate
K
2
Cr
2
O
7
3SO
2
2H
2
SO
4
K
2
SO
4
Cr
2
(SO
4
)
3
H
2
O
(green)
(iv) Ferric sulphate is reduced to Ierrous sulphate
Fe
2
(SO
4
)
3
SO
2
2H
2
O 2FeSO
4
2H
2
SO
4
(v) It reduces acidiIied iodates to iodine
2KIO
3
5S
2
4H
2
O K
2
SO
4
4H
2
SO
4
I
2
(f) Oxidising nature: It also acts as an oxidising agent particularly when treated with stronger reducing
agents.
(i) It oxidises H
2
S into S
2H
2
S SO
2
2H
2
O 3S
(ii) Metals are oxidised by SO
2
3Mg SO
2
2MgO MgS
4K 3SO
2
K
2
SO
3
K
2
S
2
O
3
3Fe SO
2
2FeO FeS
(iii) CO is oxidised to CO
2
by SO
2
2CO SO
2
2CO
2
S
(iv) At 1000
0
C, it oxidises hydrogen into water.
SO
2
2H
2
2H
2
O S
(v) Stannous and mercurous salts are oxidised in presence oI excess oI HCl.
2SnCl
2
SO
2
4HCl 2SnCl
4
2H
2
O S
2Hg
2
Cl
2
SO
2
4HCl 4HgCl
2
2H
2
O S
(g) Bleaching action: SO
2
in presence oI moisture acts as a bleaching agent. This is due tothe reducing
nature oI SO
2
.
SO
2
2H
2
O H
2
SO
4
2H
Coloured matter H Coloureless matter
The bleaching is temporary. The bleached matter when exposed to air regains its colour due to oxidation.
Uses: (i) As a reIrigent in the Iorm oI liquid SO
2
.
(ii) It is used as an antichlor Ior removing chlorine Irom a Iabric aIter bleaching.
2. Sulphur Trioxide, SO
3
Preparation: Sulphur trioxide is obtained:
(i) by dehydrating sulphuric acid with excess oI phosphorus pentoxide.
6H
2
SO
4
P
4
O
10
4H
3
PO
4
6SO
3
(ii) by heating Ierric sulphate strongly
Fe
2
(SO
4
)
3
Fe
2
O
3
3SO
3
(iii) by oxidation oI SO
2
with oxygen in presence oI a catalyst (commercial method)
2SO
2
O
2
2SO
3
Both SO
2
and O
2
should be completely dry. The mixture is passed over platinised asbestos at 400
0
C, when
SO
3
is Iormed.
Properties: (i) SO
3
exists in three allotropic Iorms:
(a) SO
3
. It is chemically active Iorm. It Iorms long transparent ice like crystals. The melting point oI this
Iorm is 17
0
C.
(b) SO
3
. It is dimeric (S
2
O
6
). It Iorms needle like silky white crystals. t melts at 32.5
0
C. Above 50
0
C,
it changes to oIorm.
(c) SO
3
. It is like |Iorm and obtained by completely drying |SO
3
. It melts at 62.2
0
C under 2
atmospheric pressure.
(ii) SO
3
is an acidic oxide. It dissolves in water Iorming sulphuric acid with evolution oI heat.
SO
3
H
2
O H
2
SO
4
heat
It reacts with basic oxides Iorming sulphates
CaO SO
3
CaSO
4
Na
2
O SO
3
Na
2
SO
4
(iii) It dissolves in concentrated sulphuric acid Iorming oleum (Iuming sulphuric acid)
H
2
SO
4
SO
3
H
2
S
2
O
7
(iv) It dissociates on heating at 1000
0
C into SO
2
and O
2
2SO
3
1000
0
C

2SO
2
O
2
(v) It combines with concentrated hydrochloric acid and Iorms chlorosulphonic acid, a derivative oI
sulphuric acid.
SO
3
HCl SO
2
(OH)Cl
Chlorosulphonic acid
(vi) SO
3
acts as an oxidisng agent.
Examples: 2SO
3
S
100
0
C

3SO
2
5SO
3
2P 5SO
2
P
2
O
5
SO
3
PCl
5
POCl
3
SO
2
Cl
2
Phosphoryl
chloride
SO
3
2HBr H
2
O Br
2
SO
2
Uses: (i) In the manuIacture oI sulphuric acid and oleum.
(ii) It is used as a drying agent Ior gases.
Oxyacids of Sulphur: Oxyacids with SS links are called thioacids. Acids having sulphur in lower oxidation
state belong to ous series while those having sulphur in higher oxidation state belong to ic series. For
example:
Sulphurous acid (H
2
SO
3
) O.N. sulphur, 4
Sulphuric acid (H
2
SO
4
) O.N. sulphur, 6
The Iollowing are main oxyacids oI sulphur:
1. Sulphurous acid series :
(i) Sulphurous acid, H
2
SO
3
(ii) Thiosulphurous acid, H
2
S
2
O
2
(iii) Hyposulphurous acid, H
2
S
2
O
4
(iv) Pyrosulphurous acid, H
2
S
2
O
5
2. Sulphuric acid series :
(i) Sulphuric acid, H
2
SO
4
(ii) Thiosulphuric acid, H
2
S
2
O
3
(iii) Pyrosulphuric acid, H
2
S
2
O
7
3. Thionic acid series :
(i) Dithionic acid, H
2
S
2
O
6
(ii) Polythionic acid, H
2
S
n
O
6
(n 3, 4, 5, 6)
4. Peroxy acid series :
(i) Peroxy monosulphuric acid, H
2
SO
5
(Caro`s acid)
(ii) Peroxy disulphuric acid, H
2
S
2
O
8
(Marshall`s acid)
Only two oxyacids (sulphurous acid and sulphuric acid are described below)
3. Sulphurous acid, H
2
SO
4
This acid is known only in solution. The solution is obtained by dissolving sulphur dioxide in water.
SO
2
H
2
O H
2
SO
3
The solution gives a smell oI sulphur dioxide which is evolved completely on heating. It is, thus, believed
that the acid is present in equilibrium with the Iree gas.
H
2
SO
3
H
2
O SO
2
Properties: It is a strong dibasic acid. It ionises in two stages.
H
2
SO
3
H

HSO
3

2H

SO
3

It thus Iorms two series oI salts. The salts are known as bisulphites (e.g. NaHSO
3
) and sulphites (e.g.
Na
2
SO
3
). The salts are Iairly stable.
Like SO
2
, it acts as a reducing agent and shows bleaching properties. These properties have been described
under sulphur dioxide.
The acid also acts as an oxidising agent particularly when treated with strong reducing agents.
(i) The preparation oI sulphurous acid by the action oI H
2
O on thionyl chloride.
(ii) The molecule oI sulphurous acid readily takes up oxygen or sulphur atom. This can be explained iI
symmetrical Iormula is accepted.
4. Sulphuric Acid (oil of vitriol) H
2
SO
4
In ancientdays, it was called oil oI vitriol as it was prepared by distilling Ierrous sulphate (Green Vitriol).
2FeSO
4
7H
2
O
Heat

Fe
2
O
3
H
2
SO
4
SO
2
13H
2
O
(Green vitriol) (oil oI vitriol)
Native sulphur is the starting material Ior the preparation oI sulphuric acid. Sulphur is burnt and easily
converted into sulphur dioxide. The conversion oI sulphur dioxide into sulphur trioxide is a matter oI diIIiculty.
It requires either a catalyst or a strong oxidising agent. The trioxide dissolves in water to Iorm sulphuric
acid. The whole process may be summarised as:
S SO
2
SO
3
H
2
SO
4
For the oxidation oI sulphur dioxide into sulphur trioxide, the Iollowing reactions may be used:
(i) By atmospheric oxygen in presence oI a catalyst, V
2
O
5
, at 400
0
C.
2SO
2
O
2
V O
C
2 5
0
400

2SO
3
SO
3
H
2
O H
2
SO
4
(ii) By Cl
2
or Br
2
in presence oI moisture.
SO
2
2H
2
O Cl
2
H
2
SO
4
2HCl
SO
2
2H
2
O Br
2
H
2
SO
4
2HBr
(iii) By H
2
O
2
SO
2
O
3
H
2
SO
4
(iv) By ozone (O
3
) 3SO
2
O
3
3SO
3
SO
2
H
2
O H
2
SO
4
(v) By conc. HNO
3
SO
2
2HNO
3
H
2
SO
4
2NO
2
Manufacture: Sulphuric acid is manuIactured these days by the Iollowing two processes:
(a) Lead chamber process (b) Contact process
Lead chamber process
Principle: The mixture containing sulphur dioxide, air and nitric oxide when treated with steam, sulphuric
acid is Iormed.
2SO
2
O
2
2H
2
O |NO| 2H
2
SO
4
|NO|
(Air) catalyst catalyst
Nitric oxide acts as a catalyst in this reaction.
Contact process
Principle: This process involves the oxidation oI sulphur dioxide by air in the presence oI a catalyst.
2SO
2
O
2
2SO
3
Sulphur trioxideis dissolved in 98 sulphuric acid when oleum is Iormed.
H
2
SO
4
SO
3
H
2
S
2
O
7
(Oleum)
Sulphuric acid oI any desired concentration can be obtained Irom oleum by dilution with water.
H
2
S
2
O
7
H
2
O 2H
2
SO
4
The oxidation oI sulphur dioxide is reversible and exothermic.
2SO
2
O
2
2SO
3
46.98 kcal
Comparison between the Lead Chamber and Contact Process
Lead chamber process Contact process
1. Catalyst used is a gasnitric oxide 1. Catalyst used is a solid vanadium pentoxide or
platinum asbestos.
2. Acid obtained is impure 2. Acid obtained is pure.
3. Acid obtained is 80 3. Oleum is obtained. Sulphuric acid oI any
concentration can be obtained Irom oleum.
4. Methods oI concentration oI the acid are 4. Furhter concentration is not necessary.
troublesome.
5. It is not necessary to puriIy the gases 5. It is absolutely necessary to puriIy the gases as
impurities acts as poison to catalyst.
6. It is a cheaper method. 6. It is a costlier method. The cost had been reduced
by the use oI V
2
O
5
in place oI platinum.
Physical properties: (a) It is a colourless syrupy liquid. It contains 98.3 sulphuric acid. Its speciIic
gravity is 1.84 at 15
0
C.
(b) It Iumes strongly in moist air and is highly corrosive in nature.
(c) It is highly soluble in water. Various hydrates such as H
2
SO
4
H
2
O, H
2
SO
4
2H
2
O, H
2
SO
4
4H
2
O, are
known. Heat is evolved when dissolved in water, usually bumping occurs. Water should not be added to
concentrated sulphuric acid for dilution but concentrated sulphuric acid should be added slowly to
cold water with constant stirring. Due to its great aIIinity Ior water, it is used as a dehydrating substance.
(e) It is a conductor oI heat and electricity.
Chemical properties: (a) Dissociation: At 444
0
C, the vapours oI sulphuric acid dissociate into steam
and sulphur trioxide,
H
2
SO
4
H
2
O SO
3
(b) Acidic nature: Dilute sulphuric acid is a strong dibasic acid. It ionises as:
H
2
SO
4
H

HSO
4

2H

SO
4
2
(i) It Iorms two series oI salts with bases.
NaOH H
2
SO
4
NaHSO
4
H
2
O;
sodium
bisulphate
2NaOH H
2
SO
4
Na
2
SO
4
H
2
O
sodium
sulphate
(ii) It decomposes carbonates and bicarbonates into carbon dioxide.
Na
2
CO
3
H
2
SO
4
Na
2
SO
4
H
2
O CO
2
NaHCO
3
H
2
SO
4
NaHSO
4
H
2
O CO
2
(iii) It reacts with electropositive metals evolving hydrogen.
Zn H
2
SO
4
ZnSO
4
H
2
Fe H
2
SO
4
FeSO
4
H
2
(iv) It displaces more volatile acids Irom their metal salts.
2NaCl H
2
SO
4
Na
2
SO
4
2HCl
Ca
3
(PO
4
)
2
3H
2
SO
4
3CaSO
4
2H
3
PO
4
CaC
2
O
4
H
2
SO
4
CaSO
4
H
2
C
2
O
2
Calcium oxalate oxalic acid
FeS H
2
SO
4
FeSO
4
H
2
S
2CH
3
COONa H
2
SO
4
Na
2
SO
4
2CH
3
C OH
2NaNO
3
H
2
SO
4
Na
2
SO
4
2HNO
CaF
2
H
2
SO
4
CaSO
4
2HF
2NaNO
2
H
2
SO
4
Na
2
SO
4
2HNO
2
+
NO NO
2
H
2
O
(c) Oxidising nature: It acts as a strong oxidising agent. The potential equation is:
H
2
SO
4
H
2
O SO
2
O
(Hot conc.)
or 2H
2
SO
4
2e

SO
4
2
2H
2
O SO
2
(i) Nonmetals such as carbon and sulphur are oxidised to their oxides.
C 2H
2
SO
4
CO
2
2SO
2
2H
2
O
S 2H
2
SO
4
3SO
2
2H
2
O
Phosphorus is oxidised to orthophosphoric acid
(ii) Metals like copper, silver, mercury, etc., are Iirst oxidised by conc. H
2
SO
4
and then the oxides combine
with acid to Iorm corresponding sulphates.
H
2
SO
4
H
2
O SO
2
O
Cu O CuO
CuO H
2
SO
4
CuSO
4
2H
2
O

Cu 2H
2
SO
4
CuSO
4
SO
2
2H
2
O

2Ag 2H
2
SO
4
Ag
2
SO
4
SO
2
2H
2
O
Hg 2H
2
SO
4
HgSO
4
SO
2
2H
2
O
(iii) Iodine is liberated Irom KI (HI is oxidised to I
2
)
2KI 2H
2
SO
4
K
2
SO
4
SO
2
I
2
2H
2
O
Similarly, bromine is liberated Irom KBr (HBr is oxidised to Br
2
).
2KBr 2H
2
SO
4
K
2
SO
4
SO
2
Br
2
2H
2
O
(iv) In presence oI Hg as a catalyst, naphthalene is oxidised to phthalic acid.
C
10
H
8
9H
2
SO
4
C
8
H
6
O
4
10H
2
O 9SO
2
2CO
2
Phthalic acid
(d) Dehydrating nature: As sulphuric acid has great aIIinity Ior water, it acts as a powerIul dehydrating
agent. Its corrosive action on skin is also due to dehydration oI skin. It absorbs water Irom organic
compounds.
C
12
H
22
O
11
H SO
H O
2 4
2
11

( )
12 C
Cane sugar
C
6
H
12
O
6
H SO
H O
2 4
2
6

( )
6 C
Glucose
(COOH)
2
H SO
H O
2 4
2

( )
CO CO
2
Oxalic Acid
HCOOH
H SO
H O
2 4
2

( )
CO
Formic acid
2C
2
H
5
OH
H SO
H O
2 4
2

( )
C
2
H
5
OC
2
H
5
Ethyl alcohol Ether
Cloth, wood, starch, paper, etc., are all charred in concentrated sulphuric acid.
(e) Miscellaneous reactions: (i) Sulphonation: Aromatic compounds react with sulphuric acid Iorming
sulphonic acid.
C
6
H
6
H
2
SO
4
C
6
H
5
SO
3
H H
2
O
Benzene Benzene
Sulphonic acid
(ii) Action oI PCl
5
: The molecule oI sulphuric acid contains two hydroxyl groups. One or both the hydroxyl
groups can be replaced by chlorine when treated with PCl
5
.
(iii) On heating potassium Ierrocyanide with concentrated sulphuric acid, carbon monoxide is evolved.
K
4
Fe(CN)
6
6H
2
SO
4
6H
2
O 2K
2
SO
4
FeSO
4
3(NH
4
)
2
SO
4
6CO
(iv) On heating potassium chlorate with concentrated sulphuric acid, carbon dioxide is evolved with explosion
3KClO
3
3H
2
SO
4
3KHSO
4
HClO
4
2ClO
2
H
2
O
(v) Sulphuric acid reacts with barium and lead salts to Iorm insoluble sulphates. These sulphates are even
insoluble in conc. HCl and conc. HNO
3
.
BaCl
2
H
2
SO
4
BaSO
4
2HCl
Pb(NO
3
)
2
H
2
SO
4
PbSO
4
2HNO
3
(vi) H
2
SO
4
absorbs sulphur trioxide Iorming oleum or Iuming sulphuric acid.
H
2
SO
4
SO
3
H
2
S
2
O
7
Oleum
(vii) H
2
SO
4
when treated with phosphorus pentoxide loses water and Iorms sulphur trioxide.
H
2
SO
4
P
2
O
5
2HPO
3
SO
3
XENON FLUORIDES
XePtF
6
was first real compound of any of the noble gases. In a short time three Iluorides oI xenon, XeF
2
,
XeF
4
and XeF
6
had been obtained as white crystalline solids.
Xenon difluoride,
Preapation of XeF
2
:
Xenone Iluoride is Iormed by heating a mixture oI xenon and Iluorine in molecular ratio 1 : 2 at 400
o
C in a nickel
tube.
Xe F
2
XeF
2
Dioxygen Iluride reacts with Xe at about 118
o
C to give XeF
2
Xe O
2
F
2

C 118
o
XeF
2
O
2
`
In presence oI mercury arc light, Xe and Iluorine combine
Xe F
2
XeF
2
Properties:
It is a colourless, crystalline solid (m. pt. 140
o
C)
It is decomposed by hydrogen and water.
XeF
2
H
2
Xe H
2
F
2
2XeF
2
2H
2
O 2Xe 2H
2
F
2
O
2
It is acts as a strong oxidising agent.
XeF
2
I
2

3
BF
2IF Xe
XeF
2
2HCl Xe H
2
F
2
Cl
2
XeF
2
dissolved in HF but do not react with HF.XeF
2
Iorms addition compound with Lewis acids by itselI acting
as Lewis base, e.g.,
Lewis base Lewis acid Adduct
XeF
2
2SbF
5
XeF
2
.2SbF
5
or
|XeF|

|Sb
2
F
11
|

XeF
2
IF
5
|XeF|

|IF
6
|

XeF
2
undergoes hydrolysis in aqueous alkaline solution, e.g.,
2XeF
2
4OH

2Xe 4F

2H
2
O O
2
Lastly, XeF
2
acts as Iluorinating agent also.
XeF
2
HF Xe
2NO XeF
2
2NOF Xe
2NO
2
XeF
2
Xe 2NO
2
F
Note: Vessels oI monel metal (alloy oI nickel) are used to store XeF
2
.
Xenon tetrafluoride, XeF
4
Perparation: It is Iormed by heating a mixture oI xenon and Iluorine in the molecular ratio 1 : 10 at 400
o
C in a
nickel tube.
Xe 2F
2
Ni
C 400
o

XeF
4
It is never synthesized in pure because its Iormation is accompanied with the Iormation oI XeF
2
and XeF
6
.
properties: It is a colourless, crystalline solid (m. Pt. 107
o
C). It undergoes sublimation. It is reduced by hydrogen,
mercury and boron trichloride.
XeF
4
2H
2
Xe 2H
2
F
2
XeF
4
2Hg Xe 2Hg F
2
3XeF
4
4BCl
3
4BF
3
3Xe 6Cl
2
It Iorms a highly explosive solid, xenon trioxide (XeO
3
) when treated with water.
2XeF
4
3H
2
O Xe XeO
3
3H
2
F
2
F
2
It is soluble in Iluoro acetic acid (CF
3
COOH). When it is heated with excess oI Xe it changes to XeF
2
.
XeF
4
Xe (excess)

warm
2XeF
2
It undergoes addition reaction like XeF
2
, Iorming adducts
XeF
4
SbF
5
|XeF
3
|

|SbF
6
|

Lewis base Lewis acid Adduct

Other Lewis acids like PF
5
, AsF
5
, SbF
5
, NbF
5
, RuF
5
, OsF
5
also undergo similar addtion reactions.
Like XeF
2
, tetraIluoride also acts as Iluorinating agent, e.g.,
XeF
4
Pt Xe PtF
4
4NO XeF
4
Xe 4NOF
4NO
2
XeF
4
Xe 4NO
2
F
Xenon hexafluoride, XeF
6
Preparations: It is Iormed by heating xenon and Iluorine in molecular ratio 1 : 20 under pressure in a nickel
tube.
Xe 3F
2
. atm 50
C 300
o

XeF
6
Properties: It is a colourless crystalline solid (m. Pt. 49.5
o
C).
It is reduced by H
2
, HCl and NH
3
.
XeF
6
3H
2
Xe 3H
2
F
2
3Cl
2
XeF
6
8NH
3
Xe 6NH
4
F N
2
The hydrolysis oI XeF
6
with water yields new compounds.
XeF
6
H
2
O XeOF
4
H
2
F
2
XeOF
4
H
2
O XeO
2
F
2
H
2
F
2
XeO
2
F
2
H
2
O XeO
3
H
2
F
2
Like other xenon Iluorides, XeF
6
is also stored in nickel alloy (monel metal vessel). It cannot be stored in glass
vessel because silica in glass reacts with XeF
6
.
2XeF
6
3SiO
2
2SiF
4
2XeO
3
XeF
6
dissolved in HF according to the Iollowing reaction
XeF
6
HF |XeF
5
|

|HF
2
|

XeF
6
undergoes thermal decomposition
XeF
6
XeF
2
XeF
4
3F
2
Like XeF
2
and XeF
4
, XeF
6
also acts as Iluorinating agent. XeF
6
has strongest Iluorinating tendancey. XeF
6
udnergoes addition reactions with Lewis acids, e.g,
XeF
6
AsF
5
|XeF
5
|

|AsF
6
|

XeF
6
BF
3
|XeF
5
|

|BF
4
|

XeF
6
NaF NaXeF
7
2NOF XeF
6
|NO|
2
2
|XeF
8
|
2
HexaIluoride undergoes hydrolysis in strongly alkaline medium.
2XeF
6
16OH

8H
2
O 12F

XeO
6
4
Xe O
2
* * * * *
HALOGEN ACIDS OR HYDRACIDS
Preparation (HCl, HBr and HI)
(i) By direct combinations of elements: Hydrogen chloride (HCl) is formed by burning chlorine in
excess of hydrogen.
H
2
+ Cl
2
2HCl
HBr can be prepared by passing a mixture of H
2
and Br
2
over a platinum spiral heated to redness by an
electric current.
H
2
+ Br
2


Pt
2HBr
HI can also be prepared in small quantities by passing hydrogen and iodine vapours over red hot fine
platinum.
H
2
+ I
2
2HI
(ii) By heating a halide with acid: Hydrogen chloride is prepared by heating sodium chloride with
concentrated sulphuric acid.
2NaCl + H
2
SO
4
Na
2
SO
4
+ 2HCl
HBr and HI cannot be prepared by heating bromides and iodides with concentrated H
2
SO
4
because
HBr and HI are strong reducing agents and reduce H
2
SO
4
to SO
2
and get themselves oxidised to
bromine and iodine, respectively.
KBr + H
2
SO
4

KHSO
4
+ HBr
KI + H
2
SO
4

KHSO
4
+ HI
H
2
SO
4
+ 2HBr

SO
2
+ Br
2
+ 2H
2
O
H
2
SO
4
+ 2HI

SO
2
+ I
2
+ 2H
2
O
Thus, HBr and HI are prepared by heating bromides and iodides respectively with conc. orthophosphoric
acid.
3KBr + H
3
PO
4

K
3
PO
4
+ 3HBr
KI + H
3
PO
4

K
3
PO
4
+ 3HI
(iii) HBr and HI can be prepared by hydorlysis of coresponding phosphorus trihalides.
2P + 3Br
2

2PBr
3
2P + 3I
2

2PI
3
PBr
3
+ 3H
2
O

H
3
PO
3
+ 3HBr
PI
3
+ 3H
2
O

H
3
PO
3
+ 3HI
Hydrogen fluoride : It is an associated molecule and is represented by formula, H
2
F
2
.
Pure anhydrous hydrogen fluoride is obtained by heating potassium hydrogen fluoride (dry) in a platinum
retort.
2KHF
2

K
2
F
2
+ H
2
F
2
The Vapours are condensed in a platinum condenser and collected in a platinum receiver.
The aqueous solution of H
2
F
2
can be obtained by heating calcium fluoride with 90% conc. sulphuric acid in
a lead retort. The vapours are condensed in a strongly colled lead receiver. Aqueous acid of about 40%
strength can be obtained by passing the vapours through water in a lead receiver.
CaF
2
+ H
2
SO
4

CaSO
4
+ H
2
F
2
The aqueous solution of H
2
F
2
is kept in qutta-percha bottles when dilute and in wax bottles when
concentrated. The anhydrous acid is stored in well cooled platinum, gold or silver vessels or steel cylinders.
Properties
(i) Physical state: Except H
2
F
2
, other hydrogen halides are gases. They fume in air and have pungent
odour. These are colourless liquids.
Their melting and boiling points increase with increase in atomic mass of the halogen. The low values are
due to covalent nature.
Order of M.P. & B.P. HCl > HBr > HI
H
2
F
2
is a liquid with boiling point 19.5
o
C. This behaviour is due to association of HF molecules through
hydrogen bonding.
H-F---H-F---H-F---H-F---
(ii) Stability: The bond strength H-X decreases from HF to HI. Thus, HF is most stable while HI is least
stable. The decrease in stability is due to decrease in electronegativity from F to I. This is also observed in
the values of dissociation energy of H-X bond.
Order of Dissociation energy H-F >H-Cl > H-Br >H-I
HBr and HCl are stable upt 1200
o
C, HBr dissociates slightly and HI dissociated considerably (20%) at
440
o
C.
(iii) Acid strength: HF is only slightly ionised but HCl, HBr and HI are almost completely ionised, i.e., the
relative strength increases from HF to HI. HF is the weakest acid and HI is the strongest acid. On the
basis of electronegativity, this appears to rather surprising. [The electronegativity difference suggests that
HF should be strongest and HI should be weakest acid.]
The lower strength of HF is largely due to its high bond dissociation energy as the bond length is very small
(1.01
A
).
(iv) Reducing nature: The reducing nature increases from HF to HI as the stability decreases form HF to
HI. HF does not show reducing nature. It cannot be oxidised even by strong oxidising agents. HI is the
strongest reducing agent. Its aqueous solution gets oxidised even by atmospheric oxygen.
4HI + O
2

2H
2
O + 2I
2
The reducing action can also be explained on the basis of increasing size of the halide ions from F
-
to I
-
.
The bigger ion can lose electron easily.
HCl can be oxidised by strong oxidising agents like MnO
2
, KMnO
4
, K
2
Cr
2
O
7
, PbO
2
, Pb
3
O
4
, etc.
HBr acts stronger reducing agent than HCl. It can be oxidised by H
2
SO
4
and atmospheric oxygen.
H
2
SO
4
+ 2HBr

SO
2
+ Br
2
+ 2H
2
O
4HBr + O
2

2H
2
O + Br
2
HI is the strongest reducing agent.
It reduces H
2
SO
4
to SO
2
, S and H
2
S, nitric acid to NO
2
, nitrous acid to NO, FeCl
3
to FeCl
2
, cupric salt to
cuprous salt, etc.
H
2
SO
4
+ 2HI

SO
2
+ I
2
+ 2H
2
O
H
2
SO
4
+ 6HI

S + 3I
2
+ 4H
2
O
H
2
SO
4
+ 8HI

H
2
S + 4I
2
+ 4H
2
O
2HNO
3
+ 2HI

2NO
2
+ 2H
2
O + I
2
2HNO
2
+ 2HI

2NO + 2H
2
O + I
2
2FeCl
3
+ 2HI

2FeCl
2
+ I
2
+ 2HCl
2CuSO
4
+ 4HI

Cu
2
I
2
+ 2H
2
SO
4
+ I
2
Potassium peroxy- K
2
S
2
O
8
+ 2HI K
2
SO
4
+ H
2
SO
4
+ I
2
disulphate
(vi) Precipitation reactions: HCl forms insoluble chlorides with the solube salts of Ag, Pb and Hg(ous).
AgNO
3
+ HCl

AgCl + HNO
3
(white)
Pb(NO
3
)
2
+ 2HCl

PbCl
2
+ 2HNO
3
(white)
Hg
2
(NO
3
)
2
+ 2HCl

Hg
2
Cl
2
+ 2HNO
3
(white)
AgCl is insoluble in HNO
3
but soluble in NH
4
OH.PbCl
2
is soluble in hot water while Hg
2
Cl
2
is soluble in
aqua-regia.
HBr reacts with soluble salts of Ag and Pb.
AgNO
3
+ HBr

AgBr + HNO
3
(Pale yellow)]
Pb(NO
3
)
2
+ 2HBr

PbBr
2
+ 2HNO
3
(white)
AgBr is insoluble in HNO
3
but sparingly soluble in NH
4
OH. PbBr
2
is soluble in hot water.
HI forms insoluble iodides with the salts of Ag, Pb and Hg (ic),
AgNO
3
+ HI

AgI + HNO
3
(Yellow)
Pb(CH
3
COO)
2
+ 2HI

PbI
2
+ 2CH
3
COOH
(Yellow)
HgCl
2
+ 2HI

HgI
2
+ 2HCl
(Scarlet)
AgI is insoluble in HNO
3
and NH
4
OH. PbI
2
is soluble in hot water.
(vii) Action of halogens: F
2
can displace Cl
2
, Br
2
and I
2
from HCl, HBr and HI.
2HCl + F
2

2HF + Cl
2
2HBr + F
2

2HF + Br
2
2HI + F
2

2HF + I
2
Cl
2
can displace Br
2
and I
2
from HBr and HI and Br
2
can displace only I
2
from HI. Iodine can displace
none.
(viii) Reaction with ammonia: HCl, HBr and HI combine with ammonia giving white fumes of ammonium
halides.
NH
3
+ HCl

NH
4
Cl (Ammonium chloride)
NH
3
+ HBr

NH
4
Br (Ammonium bromide)
NH
3
+ HI

NH
4
I (Ammonium iodide)
(ix) Acidic properties: All the three (HCl, HBr and HI) react with certain metals, their oxides, carbonates,
hydroxides, etc., and form salts.
Mg + 2HX

MgX
2
+ H
2
MgO + 2HX

MgX
2
+ H
2
CaCO
3
+ 2HX

CaX
2
+ H
2
O + CO
2
NaHCO
3
+ HX

NaX + H
2
O + CO
2
NaOH + HX

NaX + H
2
O
[HX = HCl, HBr or HI]
(x) Action of salts: HCl, HBr or HI decompose the salts of weaker acids.
Na
2
S + 2HX

2NaX + H
2
S
Ca
3
P
2
+ 6HX

3CaX
2
+ 2PH
3
Na
2
SO
3
+ 2HX

2NaX + H
2
O + SO
2
2NaNO
2
+ 2HX

2NaX + NO + NO
2
+ H
2
O
OXIDES OF CHLORINE
Chlorine forms a number of oxides such as Cl
2
O, ClO
2
, Cl
2
O
6
and Cl
2
O
7
. All of them are unstable and
highly reactive.
(i) Dichloro oxide, Cl
2
O: It is prepared by passing dry chlorine over freshly precipitated yellow mercuric
oxide.
HgO + 2Cl
2
(dry)

HgCl
2
+ Cl
2
O
It is a brownish-yellow gas which condenses to an orange coloured liquid in a freezing mixture (b. pt. =
2
o
C). It has characteristic penetrating odour. Liquid Cl
2
O explodes readily on heating or sparking Cl
2
and
O
2
. It also undergoes photochemical decomposition.
2Cl
2
O

2Cl
2
+ O
2
It dissolves inn water giving golden yellow solution of hypochlorous acid. HClO. It is thus anhydride of
hypochlorous acid.
Cl
2
O + H
2
O 2HClO
Its gaseous mixture with ammonia explodes violently.
3Cl
2
O + 10NH
3
2N
2
+ 6NH
4
Cl + 3H
2
O
it is a strong oxidising agent. It oxidises HCl to Cl
2
.
Cl
2
O + 2HCl

2Cl
2
+ H
2
O
Cl
2
O has V-shaped structure. The oxygen atom undergoes sp
3
hybridization. The Cl - O - Cl bond angle
is 110.9
o
C.
(ii) Chlorine dioxide, ClO
2
: Pure ClO
2
is obtained by passing dry Cl
2
over AgClO
3
heated to 90
o
C.
2AgClO
3
+ Cl
2
(dry)

2AgCl + 2ClO
2
+ O
2
It can also be obtained by the action of Cl
2
on sodium chlorite.
2NaClO
2
+ Cl
2

2NaCl + 2ClO
2
It can be condensed by cooling to a coloured liquid (b.pt. 11
o
C). The gas explodes and is decomposed to
Cl
2
and O
2
by an electric spark. It dissolves in water giving a mixture of chlorous acid and chloric acid.
2ClO
2
+ H
2
O

HClO
2
+ HClO
3
With alkalies, it gives a mixture of chlorite and chlorate.
2ClO
2
+ 2KOH

KClO
2
+ KClO
3
+ H
2
O
(iii) Dichlorine hexoxide, Cl
2
O
6
: It is obtained by mixing chlorine dioxide with ozonised air at 0
o
C.
2ClO
2
+ 2O
3

Cl
2
O
6
+ 2O
2
It is a dark red liquid. It is unstable and decomposed into ClO
2
and O
2
. It is a strong oxidising agent. It
reacts with water forming chloric and perchloric acids.
Cl
2
O
6
+ H
2
O

HClO
3
+ HClO
4
It reacts with alkalies to give chlorates and perchlorates.
Cl
2
O
6
+ 2KOH

KClO
3
+ KClO
4
+ H
2
O
With HF, it gives HClO
4
and chloryl fluride.
Cl
2
O
6
+ HF

HClO
4
+ ClO
2
F
In the vapour state it exists as ClO
3
molecule which has odd number of electrons and hence paramagnetic
while in liquid state it is in dimeric form having even number of electrons and hence diamagnetic in nature.
2ClO
3
Cl
2
O
6
The exact structure is unknown. However, the following structure containing Cl-Cl linkage is proposed in
which each chlorine is sp
3
hybridized.
(iv) Chlorine heptoxide, Cl
2
O
7
: It is formed by dehydration of perchloric acid with P
2
O
5
at -10
o
C.
2HClO
4


5 2
O P
Cl
2
O
7
+ H
2
O
It is a colourless oily liquid which is explosive in nature. It slowly reacts with water forming perchloric acid.
It is, thus, anhydride of perchloric acid.
Cl
2
O
7
+ H
2
O 2HClO
4
It is less reactive in comparison to lower oxides of chlorine. Cl
2
O
7
has the structure O
3
Cl - O - ClO
3
in
which two tetrahedral are sharing one O-atom.
OXY- -- --ACIDS OF CHLORINE
(i) Hypo- -- --chlorous acid, HClO: The acid is known only in solution. It is obtained by shaking precipitated
HgO with chlorine water.
2HgO + 2Cl
2
+ H
2
O Hg
2
OCl
2
+ 2HClO
(Oxychloride of mercury)
Commerciall, it is obtained by passing CO
2
through suspension of bleaching powder and then distilling.
2CaOCl
2
+ H
2
O + CO
2

CaCl
2
+ CaCO
3
+ 2HClO
It is a weak acid. Its concentrated solution is yellow in colour while dilute solution is colourless. It is
unstable and decomposes.
2HClO

2HCl + O
2
It dissolves magnesium with evilution of hydrogen.
Mg + 2HClO

Mg(ClO)
2
+ H
2
With alkalies, it forms salts called hypochlorites.
It acts as a powerful oxidising and bleaching agent. This is due to release of nascent oxygen easily.
HClO

HCl + O
Bleaching Powder, CaOCl
2
.H
2
O
Bleaching powder is also called calcium chlorohypochlorite because it is considered as a mixed salt of
hydrochloric acid and hypochlorous acid. It is represented as:
(Odling formula)
It is manufactured by the action of chlorine on dry slaked lime, Ca(OH)
2
, at 40
o
C.
Ca(OH)
2
+ Cl
2
Ca(OCl)Cl + H
2
O
This is the Odling view about its formation. There is another view proposed by Clifford according to which
bleaching powder is a mixture of calcium hypochlorite and basic calcium chloride.
2Ca(OH)
2
+ 2Cl
2

Ca(OCl)
2
+ CaCl
2
+ 2H
2
O
O H O H ) OH ( Ca CaCl ) OCl ( Ca ) OH ( Ca 3 Cl 2
O H ) OH ( Ca . CaCl O H ) OH ( Ca CaCl
2
powder Bleaching
2 2 2 2 2 2
2 2 2 2 2 2
+ + +
+ +

The manufacture of bleaching powder is carried ot in any one of the following plants:
(i) Hasenclevers plant (Old process),
(ii) Backmanns plant (Modern process).
Properties: (a) It is a pale yellow powder. It has a strong smell of chlorine. It is soluble in water but a
clear solution is never formed due to the presence of impurities.
(b) On long standing, it undergoes auto-oxidation into calcium chlorate and calcium chloride.
6CaOCl
2
Ca(ClO
3
)
2
+ 5CaCl
2
(c) In presence of cobalt chloride, CoCl
2
, it loses its oxygen.
2CaOCl
2


2
CoCl
2CaCl
2
+ O
2
(d) In presence of a slight amount of a dilute acid, it loses oxygen.
2CaOCl
2
+ H
2
CO
4
CaCl
2
+ CaSO
4
+ 2HClO
HClO

HCl + O
On account of the formation of nascent oxygen, it shows oxidising and bleaching properties.
(i) Oxidising properties:
CaOCl
2
+ H
2
S

CaCl
2
+ H
2
O + S
CaOCl
2
+ 2FeSO
4
+ H
2
SO
4

Fe
2
(SO
4
)
3
+ CaCl
2
+ H
2
O
CaOCl
2
+ KNO
2

CaCl
2
+ KNO
3
3CaOCl
2
+ 2NH
3

3CaCl
2
+ 3H
2
O + N
2
CaOCl
2
+ 2KI + 2HCl

CaCl
2
+ 2KCl + H
2
O + I
2
Na
3
AsO
3
+ CaOCl
2

CaCl
2
+ Na
3
AsO
4
(ii) Bleaching action:
Coloured matter + [O]

Colourless product
(e) It loses its chlorine by the action of dilute acids (in excess) or carbon dioxide.
CaOCl
2
+ 2HCl

CaCl
2
+ H
2
O + Cl
2
CaOCl
2
+ H
2
SO
4

CaSO
4
+ H
2
O + Cl
2
CaOCl
2
+ CO
2

CaCO
3
+Cl
2
The amount of chlorine obtained from a sample of bleaching powder by treatment with excess of
dilute acids or carbon dioxide is called available chlorine. A good sample of bleaching powder contains
35-38% of available chlorine.
(f) Bleaching powder converts acetone or ethyl alcohol into chloroform.
CaOCl
2
+ H
2
O

Ca(OH)
2
+ Cl
2
Uses of bleaching powder: It is used (i) as a disinfectant and germicide especially in the sterlisation of
drinking water. (ii) for manufacture of chloroform. (iii) for making wool unshrinkable. (iv) as an oxidising
agent in industry. (v) mainly as bleaching agent for cotton, linen and wood pulp. However, delicate articles
like straw, silk, ivory, etc., are not bleached by bleaching powder.
Bleaching process: In textile industry, the cotton cloth is mainly bleached with the help of bleaching
powder. The following procedure is followed.
(i) Cloth is first made to pass through a very dilute hot solution of caustic soda as to remove the greasy
matter.
(ii) It is now passed through a bath containing bleaching powder solution.
(iii) The cloth is next passed through a bath containing a very dilute solution of HCl. Nascent oxygen is
given out which bleaches the cloth. Some chlorine remains sticking to the fibre and its removal is necessary
otherwise the cloth is likely to be damaged.
(iv) For the removal of chlorine, the cloth is passed through a bath containing the solution of hypo (antichlor).
Na
2
S
2
O
3
+ Cl
2
+ H
2
O Na
2
SO
4
+ 2HCl + S
(v) Finally the cloth is washed in running water and thus the club is freed from all the sticking chemical
substances.
Chlorous Acid, HClO
2
: It is obtained in aqueous solution when barium chlorite suspension in water is
treated with H
2
SO
4
. The insoluble barium sulphate is filtered off.
Ba(ClO
2
)
2
+ H
2
SO
4

BaSO
4
+ 2HClO
2
The freshly prepared solution is colourless but it soon decomposes to ClO
2
which makes the solution
yellow.
5HClO
2

4ClO
2
+ HCl + 2H
2
O
The acid liberates iodine from KI
4KI + HClO
2
+ 2H
2
O

4KOH + HCl + 2I
2
Chloric Acid, HClO
3
: This acid is only known in solution. The acid is prepared by the action of dilute
H
2
SO
4
on barium chlorate.
Ba(ClO
3
)
2
+ H
2
SO
4

BaSO
4
+ 2HClO
3
BaSO
4
is filtered off.
Concentrated acid is colourless and pungent smelling liquid. It decomposes in light. However, it is stable in
dark. It acts as a strong oxidising and bleaching agent in light. Organic substances like paper, cotton, wool,
etc. catch fire in contact with the acid.
Per- -- --chloric acid, HClO
4
: It is the most stable oxy acid of chlorine. Anhydrous HClO
4
is obtained by
doing distillation of KClO
4
, potassium perchlorate, with 96-97.5% H
2
SO
4
under low pressure at 90-
160
o
C.
KClO
4
+ H
2
SO
4

KHSO
4
+ HClO
4
An aqueous solution of the acid is obtained by reaction Ba(ClO
4
)
2
, barium perchlorate with calculated
quantity of dilute H
2
SO
4
. The insoluble barium sulphate is removed by filtration.
Ba(ClO
4
)
2
+ H
2
SO
4

BaSO
4
+ 2HClO
4
Anhydrous HClO
4
is a colourless oily liquid which turns dark on keeping. It fumes in moist air. It is one of
the strongest acid and ionises as follows:
HClO
4
H
+
+ ClO
4
-
It dissolves most of the metals.
Zn + 2HClO
4
Zn(ClO
4
)
2
+ H
2
It is an oxidising agent and explodes in contact with organic matter.When dehydrated with P
2
O
5
, it yields,
Cl
2
O
7
.
2HClO
4
+ P
2
O
5

2HPO
3
+ Cl
2
O
7
FLUORINE
Occurence: Fluorine is extremely reactive and hence does not occur in free state. It is widely found in the
combined state as fluorides. The important minerals are:
(i) Feldspar (Fluorite) , CaF
2
(ii) Cryolite , Na
3
AlF
6
(iii) Fluorapatite , CaF
2
3Ca
3
(PO
4
)
2
Isolation
In modern methods, fluorine is prepared by electrolysis of a fused fluoride (usually potassium hydrogen
fluoride, KHF
2
). The electrolytic cells are made of copper, nickel or monel metal. The anode is generally of
graphite and the fluorine set free contains some carbon tetrafluoride.
Reactions in the electrolytic cell
KHF
2
KF + HF

K
+
+ e K F

F + e
K + HF KF + H 2F F
2
2H H
2
Dennis Method
Whytlaw Gray Method
Properties: (a) The gas is pale greenish yellow in colour. It can be condensed to yellow liquid at 188
0
C
and pale yellow solid at 223
0
C. (b) It has pungent odour resembling that of a mixture of ozone and
chlorine. (c) It is a poisonous gas but less poisonous than HF gas. (d) It is the most reactive element.
(i) It can displace all the halogens from their halides
F
2
+ 2NaX 2NaF + X
2
(X = Cl

, Br

or I

) (X
2
= Cl
2
, Br
2
or I
2
)
(ii) It combines with most of the metals and non-metals to form fluorides.
2Ag + F
2
2AgF
2Al + 3F
2
2AlF
3
Mg + F
2
MgF
2
Hydrogen explodes violently in fluorine even in the dark.
H
2
+ F
2
H
2
F
2
A mixture of oxygen and fluorine explodes in presence of silent electric discharge.
O
2
+ F
2
O
2
F
2
(Dioxygen difluorides)
It reacts with wood, charcoal, phosphorus, arsenic, antimony, boron, silicon producing a flame.
C + 2F
2
CF
4
; Si + 2F
2
SiF
4
2P + 3F
2
2PF
3
; 2As + F
2
2AsF
3
2B + 3F
2
2BF
3
However, fluorine does not react with oxygen, nitrogen and inert gases directly under ordinary
conditions.
(iii) Fluorine reacts vigorously with water giving O
2
and O
3
.
2H
2
O + 2F
2
4HF + O
2
3H
2
O + 3F
2
6HF + O
3
(iv) Fluorine reacts with dilute alkalies to form oxygen difluorides (OF
2
) and with conc. alkalies O
2
is
formed.
2F
2
+ NaOH OF
2
+ 2NaF + H
2
O
2F
2
+ 4NaOH 4NaF + 2H
2
O + O
2
(v) It acts as a strong oxidising agent. It oxidises chlorates to perchlorates, iodates to periodates and
bisulphates to peroxysulphates.
KClO
3
+ F
2
+ H
2
O KClO
4
+ H
2
F
2
KIO
3
+ F
2
+ H
2
O KIO
4
+ H
2
F
2
2NaHSO
4
+ F
2
a
2
S
2
O
8
+ 2HF
(vi) It attacks glass at about 100
0
C forming SiF
4
. However, the attack of dry fluorine is slow. At low
temperatures, dry fluorine can be stored in dry galss vessel.
(vii) It reacts with hydrocarbons explosively and forms fluorinated hydrocarbons.
CH
4
F
2

CH
3
F
F
2

CH
2
F
2
F
2

CHF
3

F
2

CF
4
Fluorine reacts with NH
3
to form nitrogen and H
2
S forming SF
6
(H
2
S burns)
2NH
3
+ 3F
2
N
2
+ 6HF
H
2
S + 4F
2
SF
6
+ 2HF
(viii) It combines with xenon to form XeF
2
, XeF
4
, XeF
6
(ix) Fluorination of methanol
CH
3
OH + 2F
2

AgF
2

CF
3
OF + 4HF
CF
3
OF is very strong oxidising agent.
CHLORINE
Occurrence: Chlorine is widely distributed in nature in the combined state in the form of chlorides of
various metals. Common salt (NaCl) is the most important chloride which occurs in seawater, lakes and in
rocks. The other important chloride minerals are:
(i) Sylvine (potassium chloride), KCl
(ii) Carnallite, KCl, MgCl
2
.6H
2
O
(iii) Chlorapatite, 3Ca
3
(PO
4
)
2
.CaCl
2
(iv) Horn silver, AgCl
Preparation: (i) By the oxidation of hydrochloric acid. The oxidising agents which can be used are MnO
2
,
PbO
2
, Pb
3
O
4
(red lead), KMnO
4
(Potassium permanganate), K
2
Cr
2
O
7
(Potassium dechromate), NaClO
(Sodium hypochlorite), O
3
, etc.
(a) MnO
2
+ 4HCl MnCl
2
+ 2H
2
O + Cl
2
(b) PbO
2
+ 4HCl

PbCl
2
+ 2H
2
O + Cl
2
(c) Pb
3
O
4
+ 8HCl

3PbCl
2
+ 4H
2
O + Cl
2
(d) 2KMnO
4
+ 16HCl

2KCl + 2MnCl
2
+ 8H
2
O + 5Cl
2
(e) K
2
Cr
2
O
7
+ 14HCl

2KCl + 2CrCl
3
+ 7H
2
O + 3Cl
2
(f) NaClO + 2HCl

NaCl + H
2
O + Cl
2
(g) O
3
+ 2HCl

O
2
+ H
2
O + Cl
2
(ii) By the action of mineral acids or carbon dioxide on bleaching powder.
CaOCl
2
+ H
2
SO
4

CaSO
4
+ H
2
O + Cl
2
CaOCl
2
+ 2HCl

CaCl
2
+ H
2
O + Cl
2
CaOCl
2
+ CO
2

O
2
+ H
2
O + Cl
2
(iii) By heating any chloride with concentrated H
2
SO
4
in presence of MnO
2
.
2NaCl + MnO
2
+ 3H
2
SO
4

2NaHSO
4
+ MnSO
4
+ 2H
2
O + Cl
2
Pure chlorine: It may be obtained by heating dry platinic chloride (PtCl
4
) or gold chloride (AuCl
3
) in a
hard glass tube.
PtCl
4

C 374
o

PtCl
2
+ Cl
2


C 582
o
Pt + 2Cl
2
2AuCl
3


C 175
o
2AuCl + Cl
2


C 185
o
2Au + 3Cl
2
Manufacture: Bulk of chlorine required for commercial purposes is obtained as a by-product in the
manufacture of caustic soda by electrolysis of brine solution or in the manufacture of sodium by electrolysis
of fused sodium chloride.
The other methods used for its manufacture are:
(i) Weldons process
(ii) deacons process
(iii) Nitrosyl chloride process
These chemical methods are bit costlier and only the nitrosyl chloride process is used these days to
manufacture chlorine.
1. Weldons process: This process involves the heating of pyrolusite mineral (MnO
2
) with concentrated
hydrochloric acid in stone-ware stills.
MnCl
2
+ Ca(OH)
2
Mn(OH)
2
+ CaCl
2
2Mn(OH)
2
+ O
2
(Air)

2MnO
2
+ 2H
2
O
MnO
2
+ Ca(OH)
2

anganite Calci!
3
Ca"nO
+ H
2
O
Calcium manganite settles down to the bottom as a dark coloured mud. This is used for oxidation of fresh
quantities of hydrochloric acid.
CaMnO
3
+ 6HCl CaCl
2
+ MnCl
2
+ Cl
2
+ 3H
2
O
(ii) Deacons process: This process is superior to Weldons process. In this process, chlorine is obtained
by the oxidation of HCl with air in presence of cupric chloride heated to 400
o
C.
4HCl + O
2

C 4##
CaCl
o
2

2Cl
2
+ 2H
2
O
The catalytic action of cupric chloride can be explained with the following mechanism.
2CuCl
2


. tep High
Cu
2
Cl
2
+ Cl
2
2Cu
2
Cl
2
+ O
2
(air)
e o$%chlorid Copper
2 2
OCl C! 2
Cu
2
OCl
2
+ 2HCl 2CuCl
2
+ H
2
O
(iii) Nitrosyl chloride process: In this process, common salt (NaCl) is treated with concentrated nitric
acid, when a mixture of chlorine and nitrosyl chloride is evolved.
[NaCl + HNO
3

NaNO
3
+ HCl] x 3
O H 2 Cl &OCl &a&O 3 H&O 4 &aCl 3
O H 2 Cl &OCl HCl 3 H&O
2 2 3 3
2 2 3
+ + + +
+ + +
The gaseous mixture is oxidised with oxygen.
2NOCl + O
2

2NO
2
+ Cl
2
The gases are liquefied and chlorine distilled out. Nitrogen dioxide is absorbed in water in presence of
oxygen to form nitric acid which can be used again.
4NO
2
+ O
2
+ 2H
2
O

4HNO
3
Properties of chlorine
Physical:(a) Chlorine is a yellowish-green gas with a pungent suffocating smell.
Chemical
(a) Combustibility: Chlorine does not burn and also does not help in burning.
(b) Combination with elements: It combines with all the nonmetals except nitrogen, oxygen, carbon and
inert gases.
It combines with hydrogen in light (but not in dark) with explosion to form HCl. However, in presence of
charcoal as a catalyst, the reaction is safe.
H
2
+ Cl
2

2HCl
Arsenic, boron, sulphur, phosphorus (red), etc., combine with chlorine when heated.
2As + 3Cl
2

e trichlorid Ar'enic
3
A'Cl 2
2B + 3Cl
2

e trichlorid Boron
3
BCl 2
2S + 3Cl
2

dichloride (i'!lph!r
2 2
Cl )
) d (*e
P 2
+ 3Cl
2

e trichlorid Pho'phor!'
3
PCl 2
Yellow phosphorus readily catches fire in chlorine.
2Na + Cl
2
2NaCl : 2Fe + 3Cl
2

2FeCl
3
2Al + 3Cl
2

) Cl Al or (
3
+ 2
AlCl 2
: Cu + Cl
2
CuCl
2
Mg + Cl
2

MgCl
2
: Zn + Cl
2

ZnCl
2
(c) Affinity for hydrogen: It has great affinity for hydrogen. It decopses several hydrogen compounds
forming HCl.
(i) Turpentine burns in chlorine forming HCl and carbon.
C
10
H
16
+ 8Cl
2

10C + 16HCl
(ii) It reacts with water in the presence of sunlight and forms O
2
.
2H
2
O + 2Cl
2

4HCl + O
2
Chlorine water loses its yellow colour on exposure to sunlight. This is due to the formation of HCl.
(iii) It reacts with ammonia under two conditions:
1. When ammonia in excess: The products are nitrogen and ammonium chloride.
8NH
3
+ 3Cl
2

N
2
+ 6NH
4
Cl
2. When chlorine in excess: The products are nitrogen trichloride and HCl.
NH
3
+ 3Cl
2

NCl
3
+ 3HCl
(iv) It removes hydrogen from H
2
S
H
2
S + Cl
2

2HCl + S
(d) Oxidising and bleaching nature: In presence of moisture, chlorine acts as an oxidising and a bleaching
agent. Chlorine reacts with water forming HCl and HClO (hypochlorous acid). HClO is not so stable and
decoposes giving nascent oxygen which is responsible for oxidising and bleaching properties of chlorine.
Cl
2
+ H
2
O

HCl + HclO
O HCl 2 O H Cl
O HCl HClO
2 2
+ +
+
Coloured matter + Nascent oxygen

Colourless matter
The bleaching action is permanent. The delicate articles should not be bleached with chlorine.
1. It displaces bromine and iodine from bromides and iodides respectively.
2KBr + Cl
2

2KCl + Br
2
2KI + Cl
2

2KCl + I
2
2. Ferrous chloride/ferrous sulphate containing dilute H
2
SO
4
, is converted to ferric chloride/ferric sulphate.
2FeCl
2
+ Cl
2

2FeCl
3
2FeSO
4
+ H
2
SO
4
+ Cl
2

Fe
2
(SO
4
)
3
+ 2HCl
3. Moist sulphur dioxide is oxidised to H
2
SO
4
.
SO
2
+ 2H
2
O + Cl
2

H
2
SO
4
+ 2HCl
4. Sulphites are oxidised to sulphates.
Na
2
SO
3
+ H
2
O + Cl
2

Na
2
SO
4
+ 2HCl
5. Sulphur is precipitated from sodium thiosulphate.
Na
2
S
2
O
3
+ H
2
O + Cl
2

Na
2
SO
4
+ 2HCl + S
(e) Action of alkalies: When passed into cold dilute solution of alkalies, it forms chlorides and hypochlorites.
2NaOH + Cl
2

NaCl + NaClO + H
2
O
2KOH + Cl
2

KCl + KClO + H
2
O
dil!te and Cold
2
) OH ( Ca 2
+ 2Cl
2
CaCl
2
+ Ca(ClO)
2
+ 2H
2
O
With hot concentrated alkali solutions, chlorates are formed.
6NaOH + 3Cl
2

5NaCl + NaClO
3
+ 3H
2
6KOH + 3Cl
2

5KCl + KClO
3
+ 3H
2
O
. conc and Hot
2
) OH ( Ca +
+ 6Cl
2
CaCl
2
+ Ca(ClO
3
)
2
+ 6H
2
O
However, when chlorine is passed over dry slaked lime, bleaching powder is obtained.
e li )la,ed
2
) OH ( Ca
+ Cl
2

powder Bleaching
2 2
O H . CaOCl
(f) Additionm reactions: Chlorine forms addition compounds with SO
2
, CO and unsaturated hydrocarbons.
SO
2
+ Cl
2

chloride )!lph!r%l
2 2
Cl )O
: CO + Cl
2

) Pho'gene (
chloride Car-on%l
2
COCl
Phosgene is highly poisonous gas.
C
2
H
4
+ Cl
2

chloride .th%lene
2 4 2
Cl H C
BROMINE
Occurrence: It is neve found in free state in nature. The chief sources of bromine are:
(i) Sea water contains bromides such as NaBr, KBr, MgBr
2
, CaBr
2
, etc., in minute amounts.
Preparation: The following reactions can be used for its preparation.
(i) By passing chlorine through the solution of potassium or magnesium bromide.
2KBr + Cl
2
2KCl + Br
2
MgBr
2
+ Cl
2

MgCl
2
+ Br
2
(ii) By adding hydrochloric acid to the mixture containing potassium bromide and potassium bromate.
5KBr + KBrO
3
+ 6HCl

6KCl + 3Br
2
+ 3H
2
O
(iii) By heating mixture of potassium bromide and manganese dioxide with conc. H
2
SO
4
.
MnO
2
+ H
2
SO
4

MnSO
4
+ H
2
O + O
[KBr + H
2
SO
4

KHSO
4
+ HBr] x 2
O H 2 Br "n)O /H)O 2 )O H 3 "nO /Br 2
Br O H O HBr 2
2 2 4 4 4 2 2
2 2
+ + + + +
+ +
This reaction is commonly used in the laboratory for the preparation of bromine.
Manufacture
1. From carnallite mother-liquor
2. From sea water
Properties
Physical: (a) It is a reddish brown, heavy mobile liquid.
Chemical: In chemical behaviour, bromine closely resembles chlorine.
(a) Combination with elements:
(i) Bromine reacts directly with hydrogen, though less readily than chlorine. The reaction,
H
2
+ Br
2
2HBr
is slightly reversible. It combines with hydrogen at 200
o
C or at room temperature in presence of platinum
as catalyst.
(ii) It combines with sulphur, phosphorus, arsenic, etc.
2P + 3Br
2
2PBr
3
2As + 3Br
2

2AsBr
3
2B + 3Br
2


heat d *e
2BBr
3
(iii) It combines directly with many metals.
2Na + Br
2
2NaBr (Slow reaction)
2K + Br
2

2KBr (Fast reaction)

2Al + 3Br
2

2AlBr
3
(Violent reaction)
Zinc reacts in presence of moisture with bromine.
Zn + Br
2

ZnBr
2
(b) Oxidising action: Bromine is a good oxidising agent. It ordinarily does not react with water but in
presence of an oxidisable substance it forms hydrogen bromide and oxygen with water.
Br
2
+ H
2
O

2HBr + O
ce tan '!-' O$idi'a-le
0
+ O XO
(i) It oxidises sO
2
into sulphuric acid
SO
2
+ Br
2
+ 2H
2
O

2HBr + H
2
SO
4
]
(ii) It oxidises sulphites into sulphates
Na
2
SO
3
+ Br
2
+ H
2
O

Na
2
SO
4
+ 2HBr
(iii) It oxidises arsenites into arsenates.
Na
3
AsO
3
+ Br
2
+ H
2
O

Na
3
AsO
4
+ 2HBr
(iv) It oxidises thiosulphate into sulphate
Na
2
S
2
O
3
+ Br
2
+ H
2
O

Na
2
SO
4
+ S + 2HBr
(v) Sulphur is formed by oxidation of hydrogen sulphide.
H
2
S + Br
2

2HBr + S
(vi) Iodine is liberated from iodides.
2KI + Br
2

2KBr + I
2
(c) Action with alkalies: The actiion of bromine on alkalies is similar to that of chlorine, a hypobromite
with a cold dilute solution and a bromate with a hot solution are formed.
) cold and . (il (
/OH 2
+ Br
2
KBr + e h%po-roit . Pot
/BrO
+ H
2
O
) hot and . Conc (
/OH +
+ 3Br
2
5KBr +
-roate . Pot
3
/BrO
+ 3H
2
O
) hot and . Conc (
2
) OH ( Ba +
+ 6Br
2
5BaBr
2
+
-roate Bari!
2 3
) BrO ( Ba
+ 6H
2
O
) hot and . Conc (
3 2
CO &a 3
+ 3Br
2
5NaBr + NaBrO
3
+ 3CO
2
However, with slaked lime (dry) it forms a compound similar to bleaching powder.
) dr% (
e li )la,ed
2
) OH ( Ca
+ Br
2
CaOBr
2
+ H
2
O
(d) Action of ammonia: It is similar to that of chlorine.
8NH
3
+ 3Br
2

6NH
4
Br + N
2
(e) Action of organic compounds: It forms addition compounds with unsturated compounds and substituted
products with the saturated compounds.
C
2
H
4
+ Br
2

C
2
H
4
Br
2
; CH
4
+ Br
2

CH
3
Br + HBr
(f) Bleaching action: The bleaching actionn of bromine is weaker than that of chlorine. The bleaching
action is due to its oxidising property.
(g) Action of mercuric oxide: Bromine water reacts with mercuric oxide to form mercury oxybromide.
2HgO + 2Br
2
+ H
2
O

o$%-roide "erc!r%
2
HgO . HgBr
+ 2HBrO
However, on passing bromine vapours over dry HgO at 60
o
C, bromine monoxide is obtained.
HgO + 2Br
2
Br
2
O + HgBr
2
Uses of bromine: (i) The chief use of bromine is in the manufacture of ethylene bromide (C
2
H
4
Br
2
) which
is extensively employed as a component of anti-knock gasoline.
(ii) It is used in the manufacture of NaBr and KBr (used in medicine as sedative), and certain organic dyes.
(iii) Bromine water is used in organic chemistry to test the unsturation of organic compounds.
(iv) It is used as germicide.
(v) It is employed as an oxidising agent and in organic synthesis.
IODINE
Source: Caliche or crude chile saltpetre which contains about 0.2% of NaIO
3
(sodium iodate).
Preparation: The following reactions can be applied for the preparation of iodine:
(i) By passing chlorine through potassium iodide solution.
2KI + Cl
2

2KCl + I
2
(ii) By adding potassium iodide solution to copper sulphate solution.
CuSO
4
+ 2KI

CuI
2
+ K
2
SO
4
2CuI
2
Cu
2
I
2
+ I
2
Cupric Cuprous
iodide iodide
(iii) By adding conc. sulphuric acid to a mixture of sodium/potassium iodide and sodium/potassium
iodate.
NaIO
3
+ 5NaI + 6H
2
SO
4
6NaHSO
4
+ 3H
2
O + 3I
2
(iv) By adding an oxidising agent such as hydrogen peroxide, ozone, acidified potassium permanganate
or acidified potassium dichromate to potassium iodide.
2KI + H
2
O
2
2KOH + I
2
(v) By reacting sodium iodate with sodium hydrogen sulphite.
2NaIO
3
+ 5NaHSO
3
3NaHSO
4
+ 2Na
2
SO
4
+ I
2
+ H
2
O
(vi) By heating mixture of potassium iodide and manganese dioxide with conc. H
2
SO
4
.
2KI + MnO
2
+ 3H
2
SO
4
2KHSO
4
+ MnSO
4
+ 2H
2
O + I
2
Manufacture:
(i) From Caliche: 2NaIO
3
+ 5NaHSO
3
* 3NaHSO
4
+ 2Na
2
SO
4
+ H
2
O + I
2
*NaHSO
3
if present in excess, HI is produced, NaHSO
3
+ I
2
+ H
2
O NaHSO
4
+ 2HI
Chemical properties: Iodine is chemically less reactive in comparison to chlorine and bromine.
(a) Combination with element: It combines directly with many elements.
H
2
+ I
2

Heat
Pt

2HI
2P + 3I
2

Heat

2PI
3
2KI + I
2
2KI
2Fe + 3I
2

Heat

2FeI
3
(b) Oxidising properties: It is a weak oxidising agent. The following reactions show its oxidising
nature.
(i) H
2
S + I
2
2HI + S
(ii) SO
2
+ I
2
+ 2H
2
O H
2
SO
4
+ 2HI
(iii) Na
2
SO
3
+ I
2
+ H
2
O Na
2
SO
4
+ 2HI
(iv) Na
3
AsO
3
+ I
2
+ H
2
O Na
3
AsO
4
+ 2HI
(v) 2FeSO
4
+ H
2
SO
4
+ I
2
Fe
2
(SO
4
)
3
+ 2HI
(c) Reaction with alkalies: Iodine reacts with cold dilute solution of NaOH forming hypoiodite. The
colour of the solution becomes faint yellow. However, hypoiodite undergoes hydrolysis forming HIO.
2NaOH + I
2
NaIO + NaI + H
2
O
NaIO + H
2
O NaOH + HIO

NaOH + I
2
NaI + HIO
Hypoiodous acid
Iodine when heated with concentrated alkali solution, iodide and iodate are formed. The colour of iodine
disappears.
6NaOH + 3I
2
5
3
&a1 &a1O
colo!rle''
+

+ 3H
2
O
(d) Iodine does not displace chlorine and bromine from clorides and bromides, respectively but it
displaces them from their oxy salts.
2KCIO
3
+ I
2
2KIO
3
+ Cl
2
2KBrO
3
+ I
2
2KIO
3
+ Br
2
(e) Reaction with sodium thiosulphate: Iodine solution is decolourised by sodium thiosulphate (hypo)
as sodium tetrathionate and sodium iodide are formed. Both are colourless and soluble.
2Na
2
S
2
O
3
+ I
2
2NaI + Na
2
S
4
O
6
Sodium thiosulphate Sodium tetrathionate
This reaction is involved in iodometric titrations in presence of starch indicator.
(f) Action of NH
3
: Iodine forms a mild explosive with ammonia.
2NH
3
+ 3I
2
NI
3
NH
3
+ 3HI
Explosive
8NI
3
NH
3
5N
2
+9I
2
+ 6NH
4
I
(g) Reaction with strong oxidising agents: Strong oxidising agents convert iodine to iodic acid (HIO
3
).
(i) with conc. HNO
3
I
2
+ 10HNO
3
2HIO
3
+ 10NO
2
+ 4H
2
O
(ii) with ozone
I
2
+ H
2
O + 5O
3
2HIO
3
+ 5O
2
(iii) with chlorine water
I
2
+ 5Cl
2
+ 6H
2
O 2HIO
3
+ 10HCl
(h) Reaction with freshly precipitated mercuric oxide: Iodine forms hypoiodous acid with mercuric
oxide
2HgO + 2I
2
+ H
2
O HgI
2
HgO + 2HIO
(i) Iodine when warmed with alcohol and alkali forms iodoform.
C
2
H
5
OH + 6KOH + 4I
2
CHI
3
+ HCOOK + 5KI + + 5H
2
O
(j) Reaction with chlorine: When chlorine is passed over iodine, at first iodine monochloride, ICI
(dark liquid) and finally iodine trichloride, ICI
3
(yellow solid) is formed.
(k) Reaction with starch: Iodine turns starch solution blue. This is one of the tests of iodine.
(l) Action on unsaturated organic compounds: Addition products are formed with unsaturated organic
compounds.
C
2
H
4
+ I
2
C
2
H
4
I
2
Uses of Iodine: (a) It is used in medicine, e.g. tincture of iodine [OZ. iodine, 1/4OZ. KI and 1 pint
rectified spirit] and iodex as antiseptic and analgesic. Solutions of iodine in KI are used in the treatment of
goitre.
* * * * *
Compounds of Zinc
Zinc, Oxide, ZnO: Zinc oxide is also called zinc white or Chinese white or philosopher`s wool.
It occurs in nature as the mineral zincite or red zinc ore.
Preparation: It is obtained by the combustion oI zinc or by the calcination oI zinc carbonate,
zinc nitrate or zinc hydroxide.
2Zn O
2
2ZnO
ZnCO
3
ZnO CO
2
2Zn(NO
3
)
2
2ZnO 4NO
2
O
2
Zn(OH)
2
ZnO H
2
O
Very pure zinc oxide is prepared by mixing a solution oI zinc sulphate with sodium carbonate.
The basic zinc carbonate thus, precipitated on heating gives pure zinc oxide.
4ZnSO
4
4Na
2
CO
3
3H
2
O ZnCO
3
.3Zn(OH)
2
ppt. 4Na
2
SO
4
3CO
2
ZnCO
3
.3Zn(OH)
2

Heat
4ZnO 3H
2
O CO
2
Properties:
(i) It is a white powder. It becomes yellow on heating and again turns white on cooling.
(ii) It is very light. It is insoluble in water. It sublimes at 400
o
C.
(iii) It is an amphoteric oxide and dissolves readily in acids Iorming corresponding zinc
salts and alkalies Iorming zincates.
ZnO H
2
SO
4
ZnSO
4
H
2
O
ZnO 2HCl ZnCl
2
H
2
O
ZnO 2NaOH
zincate Sodium
2 2
ZnO Na
H
2
O
(iv) When heated in hydrogen above 400
o
C, it is reduced to metal.
ZnO H
2
Zn H
2
O
It is also reduced by carbon into zinc.
ZnO C Zn CO
(v) When zinc oxide is heated with cobalt nitrate, a green mass is Iormed due to Iormation
oI cobalt zincate which is known as Riemann`s green.
2Co(NO
3
)
2
2CoO 2NO
2
O
2
ZnO CoO CoZnO
2
or CoO.ZnO
Uses:
(i) Zinc oxide is used as a white pigment (paint). No doubt its covering power is less than
but it is superior because it is not blackened in atmosphere oI hydrogen sulphide. It can be
used both as oil and water paint.
(ii) It is used to prepare Rinmann`s green which is empolyed as a green pigment.
(iii) It Iinds use as a catalyst along with Cr
2
O
3
in the manuIacture oI methyl alcohol Irom
water gas.
Zinc chloride, ZnCl
2
.2H
2
O
Preparation: It is obtained by treating zinc oxide or zinc carbonate or zinc hydroxide with dilute
hydrochloric acid. The solution on concentration and cooling gives hydrated zinc choloride
crystals, ZnCl
2
.2H
2
O.
ZnO 2HCl ZnCl
2
H
2
O
ZnCO
3
2HCl ZnCl
2
CO
2
H
2
O
Zn(OH)
2
2HCl ZnCl
2
2H
2
O
Anhydrous zinc chloride cannot be obtained by heating crystals oI hydrated zinc chloride as
hydrolysis occurs and basic chloride (zinc hydroxy chloride) is Iormed which on Iurther
heating gives zinc oxide.
ZnCl
2
.2H
2
O Zn(OH)Cl HCl H
2
O
Zn(OH)Cl ZnO HCl
The anhydrous zinc chloride is obtained by heating zinc in the atmosphere oI dry chlorine or
dry HCl gas.
Zn Cl
2
ZnCl
2
Zn 2HCl ZnCl
2
H
2
This can also be Iormed by distilling zinc powder with mercuric chloride.
Zn HgCl
2
ZnCl
2
Hg
Properties:
(a) Anhydrous zinc chloride is a white solid, deliquescent and soluble in water. It melts at
660
o
C and boils at 730
o
C.
(b) Hydrated zinc chloride on heating Iorms zinc hydroxy chloride or zinc oxychloride.
ZnCl
2
.2H
2
O Zn(OH)Cl HCl H
2
O
2ZnCl
2
.2H
2
O Zn
2
OCl
2
2HCl 3H
2
O
(c) When H
2
S is passed through the solution, a white precipitate oI zinc sulphide, is Iormed.
ZnCL
2
H
2
S ZnS 2HCl
(d) When NaOH is added, a white precipitate oI zinc hydroxide appears which dissolves in
excess oI sodium hydroxide Iorming sodium zincate.
ZnCl
2
2NaOH Zn(OH)
2
2NaCl
Zn(OH)
2
2NAOH Na
2
ZnO
2
2H
2
O
(e) On adding NH
4
OH solution, a white precipitate oI zinc hydroxide appears which dissolves
in excess oI ammonia Iorming a complex salt.
ZnCl
2
2NH
4
OH Zn(OH)
2
2NH
4
Cl
Zn(OH)
2
2NH
4
OH 2NH
4
Cl

chloride zinc Tetrammine
2 4 3
Cl ) Zn(NH
4H
2
O
(I) When the solution oI zinc chloride is treated with a solution oI sodium carbonate, a
white precipitate oI basic zinc carbonate is Iormed.
4ZnCl
2
4Na
2
CO
3
3H
2
O
carbonate zinc Basic
2 3
.3Zn(OH) ZnCO
8NaCl 3CO
2
But when a solution oI sodium bicarbonate is used, a white precipitate oI normal zinc carbonate
is Iormed.
ZnCl
2
2NaHCo
3
ZnCO
3
2NaCl H
2
O CO
(g) Anhydrous zinc chloride absorbs ammonia gas and Iorms an addition compound.
ZnCl
2
4NH
3
ZnCl
2
.4NH
3
(i) Its syrupy solution when mixed with zinc oxide, ZnO, sets to a hard mass Iorming an
oxychloride, ZnCl
2
.3ZnO.
Zinc sulphate (White vitriol), ZnSO
4
.7H
2
O
Preparation: It is prepared by reacting zinc with dilute sulphuric acid. It can also be prepared by
dissolving zinc oxide or carbonate in dilute sulphuric acid. The solution on concentration
and crystallisation below 39
o
C gives colourless crystals oI zinc sulphate, ZnSO
4
.7H
2
O.
Zn H
2
SO
4
ZnSO
4
H
2
ZnO H
2
SO
4
ZnSO
4
H
2
O
ZnCO
3
H
2
SO
4
ZnSO
4
H
2
O CO
2
Properties: (a) It is a colourless, crystalline solid. It is an eIIlorescent substance. It is Ireely
soluble in water.
(b) On heatng, the Iollowing changes occur.
ZnSO
4
.7H
2
O
C
o
70 Below
C
o
39 Above
ZnSO
4
.6H
2
O
C
o
0 7 Above
ZnSO
4
.H
2
O
C
o
280 Above
O
2
SO
2
ZnO
C
o
800
) (anhydrous
4
ZnSO
ZnSO
4

C
o
800
ZnO SO
3

SO
2
O
2
(c) When sodium hydroxide is added to the solution oI zinc sulphate, a white precipitate oI
zinc hydroxide appears which dissolves in excess oI NaOH Iorming sodium zincate.
ZnSO
4
2NaOH Zn(OH)
2
Na
2
SO
4
Zn(OH)
2
2NaOH Na
2
ZnO
2
2H
2
O
(d) When sodium carbonate solution is added to the solution oI zinc su;phate, a white
precipitate oI basic zinc carbonate is Iormed.
4ZnSO
4
4Na
2
CO
3
3H
2
O ZnCO
3
.3Zn(OH)
2
4Na
2
SO
4
3CO
2
However, when the solution oI sodium becarbonate is added, normal zinc carbonate is Iormed.
ZnSO
4
2NaHCO
3
ZnCO
3
Na
2
SO
4
H
2
OCO
2
(e) With alkali metal sulphates and (NH
4
)
2
SO
4
, it Iorms double sulphates such as
K
2
SO
4
.ZnSO
4.
6H
2
O
.
Compounds of Silver
Silver nitrate (Lunar caustic), AgNO
3
Silver nitrate is the most common and important salt oI silver.
Preparation: It is prepared by heating silver with dilute nitric acid. The solution is concentrated
and cooled when the crystals oI silver nitrate separate out.
3Ag
(Dilute)
3
4HNO

Heat
3AgNO
3
NO 2H
2
O
Properties:
(a) It is a colourless crystalline compound, soluble in water and alcohol. It melts at 212
o
C.
(b) In contact with organic substance it blackens due to decomposition into metallic silver.
Thus, it leaves black stains when comes in contact with skin and clothes. It produces burning
sensation like caustic and leaves a white stain (usually a black stain) like the moon luna on
skin and thus, called Lunar caustic. It is decomposed by light also and thereIore stored in
coloured bottles.
(c) On heating above its melting point, it decomposes to silver nitrtie and oxygen.
2AgNO
3
2AgNO
2
O
2
When heated at red heat, it Iurther decomposes to metallic silver.
2AgNO
3
2Ag 2NO
2
O
2
(d) Solutions oI halides, phosphates, sulphides, chromates, thiocyanates, sulphates and
thiosulphates, all give a precipitate oI the corresponding silver salt with silver nitrate solution.
On account oI these reactions, silver nitrate is an excellent laboratory regent Ior the
identiIication oI various acidic radical.
(e) Solid AgNO
3
absorbs ammonia gas with the Iormation oI an addition compound,
AgNO
3
.3NH
3
.
(I) When treated with a solution oI NaOH, it Iorms precipitate oI silver oxide. Originally, it
has brown colour but turns black when dried.
2AgNO
3
2NaOH Ag
2
O 2NaNO
3
H
2
O
(g) When KCN is added to silver nitrate, a white precipitate oI silver cyanide appears which
dissolves in excess oI KCN Iorming a cimplex salt, potassium argento cyanide.
AgNO
3
KCN AgCN KNO
3
AgCN KCN
nide argentocya Potassium
2
KAg(CN)
(h) When sodium thiosulphate is added to silver nitrate, a white precipitate oI silver
thiosulphate appears. This precipitate, however, dissolves in excess oI sodium thioslphate
Iorming a complex salt.
2AgNO
3
Na
2
S
2
O
3
Ag
2
S
2
O
3
2NaNO
3
Ag
2
S
2
O
3
3Na
2
S
2
O
3

osulphate argentothi Sodium
2 3 2 3
| ) O |Ag(S 2Na
(i) AgNO
3
reacts with iodine in two ways:
(a) 6AgNO
3
(excess) 3I
2
3H
2
O AgIO
3
5AgI 6HNO
3
(b) 5AgNO
3
3I
2
(excess) 3H
2
O HIO
3
5AgI 5HNO
3
(j) Silver is readily displaced Irom as aqueous silver nitrate solution by the base metals,
particularly, iI the solution is somewhat acidic,
2AgNO
3
Cu 2Ag Cu(NO
3
)
2
2AgNO
3
Zu 2Ag Zn(NO
3
)
2
(k) Phosphine, arsine and stibine all precipitate silver Irom silver nitrate solution.
PH
3
6AgNO
3
3H
2
O 6Ag 6HNO
3
H
3
PO
3
AsH
3
6AgNO
3
3H
2
O 6Ag 6HNO
3
H
3
AsO
3
(l) All halogen acids, except HF, precipitate silver halides Irom aqueous solution oI AgNO
3
.
AgNO
3
HX AgX HNO
3
(b) It converts glucose to gluconic acid.
Ag
2
O C
6
H
12
O
6
2Ag C
6
H
12
O
7
(c) It oxidies Iormaldehyde to Iormic acid.
Ag
2
O HCHO 2Ag HCOOH
Uses: (i) It is used as a laboratory reagent Ior the identiIication oI various acidic radicals especially
Ior chloride, bromide and iodide. The ammonical silver nitrate solution, i.e., Tollen`s reagent
sugars, etc.
(ii) Silver nitrate is used Ior making silver halides which are used in photography.
(v) It is used extensivley Ior the preparation oI silver mirrors. The process oI depositing a
thin and uniIorm layer oI silver on a clean glass surIace is known as silvering oI mirrors. It
is employed Ior making looking glasses, concave mirrors and reIlecting surIaces. The process
is based on the reduction oI ammonical silver nitrate solution by some reducing agent like
Iormaldehyde, gloucose, etc. The silver Iilm deposited on the glass is Iirst coated with a
varnish and Iinally painted with red lead to prevent its being scraped oII.
Compounds of Copper
Copper forms two series of compounds
1. Cuprous compounds: In which copper is monovalent. Most oI the cuprous compounds are
colourless and diamagnetic as 3d shell is completely Iilled. Cu
2
O and Cu
2
S are red and
black, respectively, which are exceptions. Cuprous compounds are generally insoluble in
water. The soluble compounds are unstable in aqueous solutions, since they disproportionate
to Cu
2
and Cu.
2Cu

Cu
2
Cu
Cuprous compounds can be obtained by passing sulphur dioxide through a solution containing
copper sulphate and sodium salt. Some examples are given below:
(i) 2CuSO
4
2NaCl SO
2
2H
2
O
chloride Cuprous
2CuCl
Na
2
SO
4
2H
2
SO
4
(ii) 2CuSO
4
2NaBr SO
2
2H
2
bromide Cuprous
2CuBr
Na
2
SO
4
2H
2
SO
4
(iii) 2CuSO
4
2NaI SO
2
2H
2
O
iodide Cuprous
2CuI
Na
2
SO
4
2H
2
SO
4
(iv) 2CuSO
4
2NaCN SO
2
2H
2
O
cyandia Cuprous
2CuCN
Na
2
SO
4
2H
2
SO
4
(v) 2CuSO
4
2NaCNS SO
2
2H
2
O
te thiocyana Cuprous
2CuCNS
Na
2
SO
4
2H
2
SO
4
The reactions (iii) and (iv) can take place even in absence oI sulphur dioxide.
2CuSO
4
4NaI 2CuI 2Na
2
SO
4
I
2
2CuSO
4
4NaCN 2CuCN 2Na
2
SO
4
(CN)
2
The true molecular Iormula oI cuprous compounds is still doubtIul. There are expermental
evidences Ior dimeric molecule. The most important compound oI this class is cuprous
chloride.
Cuprous Chloride, Cu
2
Cl
2
Preparation: It is prepared (i) by heating excess oI copper with concentrated hydrochloric acid in
presence oI a little potassium chlorate.
Cu 2HCl O CuCl
2
H
2
O
CuCl
2
Cu Cu
2
Cl
2
(ii) By boiling copper sulphate solution with excess oI copper turnings in presence oI
hydrochloric acid.
CuSO
4
2HCl CuCl
2
H
2
SO
4
CuCl
2
CuCu
2
CL
2
(iii) By heating cupric chloride with zinc or sulphur dioside.
2CuCl
2
Zn Cu
2
Cl
2
ZnCL
2
2CuCl
2
2H
2
O SO
2
Cu
2
Cl
2
2HCl H
2
SO
4
(iv) By passing SO
2
thruough the solution containing copper sulphate and sodium chloride.
2CuSO
4
2NaCl 2H
2
O SO
2
Cu
2
Cl
2
Na
2
SO
4
2H
2
SO
4
Properties:(i) It is a white solid. It is insoluble in water but soluble in excess oI hydrochloric acid.
Cu
2
Cl
2
4HCl 2H
2
CuCl
3
Cu
2
Cl
2
6HCl 2H
3
CuCl
4
(ii) It gradually turns green on exposure in air due to oxidation.
2Cu
2
Cl
2
2H
2
O O
2
2|CuCl
2
.Cu(OH)
2
|
(iii) The solution oI cuprous chloride in HCl is oxidised by air or oxidising agents into
cupric chloride.
Cu
2
Cl
2
2HCl
2
O
2
1
2CuCl
2
H
2
O
(iv) The solution oI cuprous chloride in HCl absorbs carbon monoxide and Iorms an addition
compound.
Cu
2
Cl
2
2CO 2CuCl. CO
The addition compound decomposes on heating evolving carbon monoxide. The reaction is
uitilised Ior the removel oI carbon monoxide.
(v) It dissolves in aqueous ammonia Iorming a colourless soultion due to the Iormation oI
the complex Cu(NH
3
)
2
Cl.
(vi) The ammonical cuprous chloride solution absorbs acetylene to Iorm bright red precipitate
oI cuprous acetylide, Cu
2
C
2
.
2Cu(NH
3
)
2
Cl C
2
H
2
Cu
2
C
2
2NH
3
2NH
4
Cl
Acetylene can be regenerated by treating the acetylide with strong HCl. The reaction is ,
thereIore, used Ior the puriIication and separation oI acetylene.
Cu
2
C
2
2HCl C
2
H
2
Cu
2
Cl
2
(vii) Cuprous chloride with caustic alkalies gives a yellow precipitate oI cuprous oxide
which gradually changes to red.
Cu
2
Cl
2
2NaOH
red to
changing Yellow
2
O Cu
2NaCl H
2
O
(viii) With H
2
S, cuprous chloride Iorms a black precipitate oI cuprous sulphide.
Cu
2
Cl
2
H
2
S Cu
2
S 2HCl
(ix) With sodium chloride or potassium chloride solution cuprous chloride Iorms a soluble
complex.
Cu
2
Cl
2
6NaCl 2Na
3
CuCl
4
Cu
2
Cl
2
6KCl 2K
3
CuCl
4
(x) Dry cuprous chloride Iorms addition compounds with ammonia gas oI the Iormula
CuCl.nNH
3
where n 1,
2
1
1
, 3.
Uses: (i) Ammonical solution oI cuprous chloride is used Ior absorbing acetylene.
(ii) HCl solution oI cuprous chloride is used Ior absorption oI carbon monooxide.
(iii) It is also used Ior absorption oI ammonia gas.
Cupric compounds: In which copper is divalent, cupric compounds are more stable, more
common and generally more stable. Most oI the anhydrous cupric compounds are colourless
while the hydrated compounds are generally blue due to the Iormation oI blue hydrated ion,
|Cu(H
2
O)
4
|
2
or |Cu(H
2
O)
6
|
2
. Compounds oI Cu
2
ions are paramagenetic due to presence
oI one unpaired electron in 3d energy shell, i.e., conIiguration oI Cu
2
is 3d
9
. Some important
cupric compounds are described here.
Cupric Oxide, CuO
It is called black oxide oI copper.
Preparation: It is prepared-
(i) By heating Cu
2
O in air or by heating copper Ior a long time in air (The temperature should
not exceed above 1100
o
C).
Cu
2
O
2
O
2
1

2CuO
2Cu O
2
2CuO
(ii) by heating cupric hydroxide,
Cu(OH)
2
CuO H
2
O
(iii) by heating copper nitrate,
2Cu(NO
3
)
2
2CuO 4NO
2
O
2
(iv) on a commercial scale, it is obtained by heating malachite which is Iound in nature.
CuCO
3
.Cu(OH)
2
2CuO CO
2
H
2
O
Properties:
(a) It is black powder and stable to moderate heating.
(b) The oxide is insoluble in water but dissolves in acids Iorming corresponding salts.
CuO 2HCl CuCl
2
H
2
O
CuO H
2
SO
4
CuSO
4
H
2
O
CuO 2HNO
3
Cu(NO
3
)
2
H
2
O
(c) When heated to 1100 - 1200
o
C, it is converted into cuprous oxide with evolution oI
oxygen.
4CuO 2Cu
2
O O
2
(d) It is reduced to metallic copper by reducing agents like hydrogen, carbon and carbon
monoxide.
CuO H
2
Cu H
2
O
CuO C Cu CO
CuO CO Cu CO
2
Cupric Chloride, CuCl
2
.2H
2
O
Preparation: (i) The metal or cupric oxide or cupric hydroxide or copper carbonate is dissolved
in conc. HCl. The resulting solution on crystallisation gives green crystals oI hydrated cupric
chloride.
2Cu 4HCl O
2
2CuCl
2
2H
2
O
CuO 2HCl CuCl
2
H
2
O
Cu(OH)
2
CuCO
3
4HCl 2CuCl
2
3H
2
O CO
2
(ii) Anhydrous cupric chloride is obtained as a dark brown mass when copper metal is heated
in excess oI chlorine gas or by heating hydrated cupric chloride in HCl gas at 150
o
C.
Cu Cl
2
CuCl
2
CuCl
2
.2H
2
O
gas HCl
C 150


CuCl
2
2H
2
O
Properties: (i) It is deliquescent compound and is reado;u soluble in water. The dilute solution is
blue but concentrated solution is, however, green. It changes to yellow whne conc. HCl is
added. The blue colour is due to complex cation |Cu(H
2
O)
4
|
2
and yellow colour due to
complex anion |CuCl
4
|
2-
and green when both are present.
(ii) The aqueous solution is acidic due to its hydrolyis.
CuCl
2
2H
2
O Cu(OH)
2
2HCl
(iii) The anhydrous salt on heating Iorms Cu
2
Cl
2
and Cl
2
.
2CuCl
2
Cu
2
Cl
2
Cl
2
while the hydrated salt on strong heating gives CuO, Cu
2
Cl
2
, HCl and Cl
2
.
3CuCl
2
.2H
2
O CuO Cu
2
Cl
2
2HCl Cl
2
5H
2
O
(iv) It is readily reduced to Cu
2
Cl
2
by copper turnings, or SO
2
gas, or hydrogen (Nascent -
obtained by the action oI HCl on Zn) or SnCl
2
.
CuCl
2
Cu Cu
2
Cl
2
2CuCl
2
SO
2
2H
2
O CuCl
2
2HCl H
2
SO
4
2CuCl
2
2H CuCl
2
2HCl
2CuCl
2
SnCl
2
Cu
2
Cl
2
SnCl
4
(v) A pale blue precipitate oI basic cupric chloride, CuCl
2
.3Cu(OH)
2
is obtained when NaOH
is added.
CuCl
2
2NaOH Cu(OH)
2
2NaCl
CuCl
2
3Cu(OH)
2
CuCl
2
.3Cu(OH)
2
It dissolves in ammonium hydroxide Iorming a deep blue solution. On evaporating oI this
solution deep blue crystals oI tetrammine cupric chloride are obtained.
CuCl
2
4NH
4
OH Cu(NH
3
)
4
Cl
2
.H
2
O 3H
2
O
Copper Sulphate (Blue Vitriol), CuSO
4
.
.
5H
2
O
Copper sulphate is the most common compound oI copper. It is calles as blue vitriol or Nila Thotha.
Preparation: (i) Copper sulphate is prepared in the laboratory by dissolving cupric oxide or
hydroxide or carbonate in dilute sulphuric acid. The solution is evaporated and crystallised.
CuO H
2
SO
4
CuSO
4
H
2
O
Cu(OH)
2
H
2
SO
4
CuSO
4
2H
2
O
Cu(OH)
2
CuCO
3
2H
2
SO
4
2CuSO
4
3H
2
O CO
2
(ii) On a commercial scale, it is prepared Irom scrap copper is placed in a perIorated lead
bucket which is dipped into hot dilute sulphuric acid. Air is blown thruough the acid. Copper
sulphate is crystallised Irom the solution.
Cu H
2
SO
4

CuSO
4
H
2
O
Properties: (a) It is a blue crystalline compound and is Iairly soluble in water.
(b) Heating eIIect: CuSO
4
.5H
2
O crystals eIIloresce on exposure and converted into a pale
blue powder, CuSO
4
.3H
2
O is Iormed. The monohydrate loses last molecule oI water at 230
o
C
giving the anhydrous salt, CuSO
4
, which is white.
CuSO
4
.5H
2
O
blue Pale
2 4
O .3H CuSO
te Bluish whi
2 4
O .H CuSO
White
4
CuSO
Anhydrous copper sulphate (white) regains its blue colour when moistened with a drop oI
water (test oI water).
II the anhydrous salt is heated at 720
o
C, it decomposes into cupric oxide and sulphur trioxide.
CuSO
4


C 720
CuO
(c) Action of NH
4
OH: With ammonia solution, it Iorms the soluble blue complex. First it Iorms
a precipitate oI Cu(OH)
2
which dissolves in excess oI ammonia solution.
CuSO
4
2NH
4
OH Cu(OH)
2
(NH
4
)
2
SO
4
Cu(OH)
2
2NH
4
OH (NH
4
)
2
SO
4

sulphate cupric Tetrammine
4 4 3
SO ) Cu(NH
4H
2
O
The complex is known as Schwixer`s reagent which is used Ior dissolving cellulose in the
manuIacture oI artiIicial silk.
(d) Action of alkalies: Alkalies Iorm a pale blue precipitate oI copper hydroxide.
CuSO
4
2NaOH Cu(OH)
2
Na
2
SO
4
(e) Action of potassium iodide: First cupric iodide is Iormed which decomposes to give white
cuprous iodide and iodide.
|CuSO
4
2KI CuI
2
K
2
SO
4
| x 2
2CuI
2
Cu
2
I
2
I
2

2CuSO
4
4KI Cu
2
I
2
2K
2
SO
4
I
2
(f) Action of potassium cyanide: First cupric cyanide is Iormed which decomposes to give cuprous
cyanide and cyanogen gas. Cuprous cyanide dissolves in excess oI potassium cyanide to
Iorm a complex, potassium cupro cyanide |K
3
Cu(CN)
4
|.
|CuSO
4
2KCN Cu(CN)
2
K
2
SO
4
| x 2
2Cu(CN)
2
Cu
2
(CN)
2
(CN)
2
Cu
2
(CN)
2
6KCN 2K
3
Cu(CN)
4

2CuSO
4
10KCN 2K
3
Cu(CN)
4
2K
2
SO
4
(CN)
2
(g) Action of potassium ferrocyanide: Reddish brown precipitate oI cupric Ierrocyanide is Iormed.
(test oI Cu
2
ion)
2CuSO
4
K
4
Fe(CN)
6
Cu
2
Fe(CN)
6
2K
2
SO
4
(h) Addition of electropositive metals: Electropositive elements like zinc and iron precipitate
copper Irom a solution oI copper sulphate.
CuSO
4
Fe Cu FeSO
4
CuSO
4
Zn Cu ZnSO
4
(i) Action of H
2
S: When H
2
S is passed through copper sulphate solution, a black precipitate oI
copper sulphide is Iormed.
CuSO
4
H
2
S CuS H
2
SO
4
The black precipitate dissolves in conc. HNO
3
.
3CuS 8HNO
3
3Cu(NO
3
)
2
2NO 3S 4H
2
O
(j) Action of potassium sulphocyanide: Cupric sulphocyanide is Iormed.
CuSO
4
2KCNS Cu(CNS)
2
K
2
SO
4
II SO
2
is passed through the solution, a white precipitate oI cuprous sulphocyanide is Iormed.
2CuSO
4
2KCNS SO
2
2H
2
O Cu
2
(CNS)
2
K
2
SO
4
2H
2
SSO
4
|This is the general method Ior obtaining cuprous compounds|.
(k) Double sulphates: Copper sulphate Iorms double salts with alkali sulphate to Iorm cupric
thiosulphate which is reduced by sodium thiosulphate. The cuprous compound thus Iormed
dissolves in excess oI sodium thiosulphate to Iorm a complex.
CuSO
4
Na
2
S
2
O
3
CuS
2
O
3
Na
2
SO
4
2CuS
2
O
3
Na
2
S
2
O
3
Cu
2
S
2
O
3
Na
2
S
4
O
6
3Cu
2
S
2
O
3
2Na
2
S
2
O
3
Na
4
|Cu
6
(S
2
O
3
)
5
|
Uses: (i) Copper sulphate is used Ior the preparation oI other copper compounds.
(ii) It Iinds use in electroplating, electrotyping, calicoprinting and dyeing.
(iii) It is used in agriculture as aIungicide and germicide.
Bordeaux mixture consisting copper sulphate and lime is used to kill moulda and Iungi on vines,
trees, potatoes, etc.
(iv) It is used as a laboratory reagent especially in the preparation oI Fehling`s soluton.
(v) It Iinds use as an antiseptic in medicine.
(vi) It is extensivley used in electric batteries.
Compounds of Iron
Ferrous sulphate (Green witriol), FeSO
4
.7H
2
O
This is the best known Ierrous salt. It occurs in nature as copper and is Iormed by the oxidation
oI purites under the action oI water and atmospheric air.

2
7O
2
H
2
O 2FeSO
4
2H
2
SO
4
Preparation:
(i) It is obtained by dissolving scrap iron in dilute sulphuric acid.
Fe H
2
SO
4
FeSO
4
H
2
The solution is crystallised by the addition oI alcohol as Ierrous sulphate is sparingly soluble
in it.
Manufacture: Commercially, Ierrous sulphate is obtained by the slow oxidation oI iron pyrites in
the presence oI air and moisture. The pyrites are exposed to air in big heaps.
2FeS
2
2H
2
O 7O
2
2FeSO
4
2H
2
SO
4
Properties:
(i) Hydrated Ierrous sulphate (FeSO
4
.7H
2
O) is green crystalline compound. Due to atmospheric
oxidation, the crystals acquire brownish-yellow colour due to Iormation oI basic Ierric
sulphate.
4FeSO
4
2H
2
O O
2

sulphate Ierric Basic
4
4Fe(OH)SO
(ii) Action oI heat: At 300
o
, it becomes anhydrous. The anhydrous Ierrous sulphate is colourless.
The anhydrous salt when strongly heated, breaks up to Iorm Ierric oxide with the evolution
oI SO
2
and SO
3
.
. O
2
7H
C 300
White
4
Green
2 4
FeSO O .7H FeSO
Temp
High

Fe
2
O
3
SO
2
SO
3
(iii) The aqueous solution oI Ierrous sulphate is slightly acidic due to its hydrolysis.
FeSO
4
2H
2
O
base Weak
2
Fe(OH)

acid Strong
4 2
SO H
(iv) Ferrous sulphate is a strong reducing agent.
(a) It decolourises acidiIied potassium permanganate.
2KMnO
4
3H
2
SO
4
K
2
SO
4
2MnSO
4
3H
2
O 5|O|
|2FeSO
4
H
2
SO
4
O Fe
2
(SO
4
)
3
H
2
O| x 5

10FeSO
4
2KMnO
4
8H
2
SO
4
5Fe
2
(SO
4
)
3
K
2
SO
4
2MnSO
4
8H
2
O
(b) It turns potassium dichromate (acidiIied) green as dichromate is reduced to chromic salt (green).
K
2
Cr
2
O
7
4H
2
SO
4
K
2
SO
4
Cr
2
(SO
4
)
3
4H
2
O 3|O|
|2FeSO
4
, H
2
SO
4
O Fe
2
(SO
4
)
3
H
2
O x 3

6FeSO
4
K
2
Cr
2
O
7
7H
2
SO
4
3Fe
2
(SO
4
)
3
K
2
SO
4
Cr
2
(SO
4
)
3
7H
2
O
(c) It reduces gold chloride to gold.
AuCl
3
3FeSO
4
Au Fe
2
(SO
4
)
3
FeCl
3
(d) It reduces mercuric chloride to mercurous chloride.
|2HgCl
2
Hg
2
Cl
2
2Cl| x 3
|3FeSO
4
3Cl Fe
2
(SO
4
)
3
FeCl
3
| x 2

6HgCl
2
6FeSO
4
3Hg
2
Cl
2
2Fe
2
(SO
4
)
3
2FeCl
3
(v) A cold solution oI Ierrous sulphate absorbs nitirc oxide Iorming dark brown addition compound,
nitroso Ierrous sulphate.
FeSO
4
NO
(Brown)
sulphate Ierrous Nitroso
4
.NO FeSO
The NO gas is evolved when the solution is heated.
(vi) It Iorms double sulphates oI the composition R
2
SO
4
.FeSO
4
.6H
2
O where R an alkali metal
metal or NH
4

radical. (NH
4
)
2
SO
4
.FeSO
4
.6H
2
O (Ierrous ammonium sulphate) is known as
Mohr`s salt.
(vii) It combines with potassium cyanide (excess) Iorming potassium Ierrocyanide, K
4
Fe(CN)
6
.
FeSO
4
2KCN Fe (CN)
2
K
2
SO
4
Fe(CN)
2
4KCN K
4
Fe(CN)
6

FeSO
4
6KCN K
4
Fe(CN)
6
K
2
SO
4
Ferrous Ammonium Sulphate (Mohr`s salt). (NH
4
)
2
SO
4
.FeSO
4
.6H
2
O
Preparation: The double salt is best prepared by making saturated solutions oI pure Ierrous sulphte
and pure ammonium sulphate in air Iree distilled water at 40
o
C. Both the solutions are mixed
and allowed to cool. Generally, Iew drops oI sulphuric acid and a little iron wire are added
beIore crystallisation as to prevent oxidation oI Ierrous sulphate into Ierric sulphate. The
salt is obtained as pale green crystals.
Properties: It is pale green crystalline compound which does not eIIloresce like Ierrous sulphate.
It is less readily oxidised in the solid state.
Ferric chloride, FeCl
3
This is the most important Ierric salt. It is known in anhydrous and hydrated Iorms. The
hydrated Iorm consists oI six water molecles, FeCl
3
.6H
2
O.
Preparation: (i) Anhydrous Ierric chloride is obtained by passing dry chlorine gas over heated
iron Iillings AS shown in Iigure.
The vapours are condensed in a bottle attached to the outlet oI the tube.
2Fe 3Cl
2
2FeCl
3
(ii) Hydrated Ierric chloride is obtained by the action oI hydrochloric acid on Ierric carbonate,
Ierric hydroxide or Ierric oxide.
Fe
2
(CO
3
)
3
6HCl 2FeCl
3
3H
2
O 3CO
2
Fe(OH)
3
3HCl FeCl
3
3H
2
O

Fe
2
O
3
6HCl 2FeCl
3
3H
2
O
The solution on evaporation and cooling deposits yellow crystals oI hydrated Ierric chloride,
FeCl
3
.6H
2
O.
Properties: (i) Anhydrous Ierric chloride is a dark red deliquescent solid. It is sublimed at about
300
o
C and its vapour density corresponds to dimeric Iormula, Fe
2
Cl
6
. The dimer dissociates
at high temperatures to FeCl
3
. The dissociation into FeCl
3
is complete at 750
o
C. Above this
temperature it breaks into Ierrous chloride and chlorine.
Fe
2
Cl
6
2FeCl
3
2FeCl
2
Cl
2
(ii) Anhydrous Ierric chloride behaves as a covalent compound as it is soluble in non-polar solvents
like ether, alchol, etc. It is represented by chlorine bridge structure.
(iii) It dissolves in water. The solution is acidic in nature due to its hydrolysis as shown below:
FeCl
3
3HOH Fe(OH)
3
3HCl
The solution is stabilised by the addition oI hydrochloric acid to prevent hydrolysis.
(iv) Anhydrous Ierric chloride absorvs absorbs ammonia.
FeCl
3
6NH
3
FeCl
3
.6NH
3
(v) Ferric chloride acts as an oxidising agent.
(a) It oxidises stannous chloride to stannic chloride.
2FeCl
3
SnCl
2
2FeCl
2
SnCl
4
(b) It oxidises SO
2
To H
2
SO
4
.
2FeCl
3
SO
2
2H
2
O 2FeCl
2
H
2
SO
4
2HCl
(c) It oxidises H
2
S to S.
2FeCl
3
H
2
S 2FeCl
2
2HCl S
(d) It liberates iodine Irom KI.
2FeCl
3
2KI 2FeCl
2
2KCl I
2
(e) Nascent hydrogen reduces FeCl
3
into FeCl
2
.
FeCl
3
H FeCl
2
HCl
(vi) When ammonium hydroxide is added to the solution oI Ierric chloride, a reddish - brown
precipitate oI Ierric hydroxide is Iormed.
FeCl
3
3NH
4
OH Fe(OH)
3
3NH
4
Cl
(vii) When a solution oI thiocyanate ions is added to Ierric chloride solution, a deep red colouration
is produced due to Iormation oI a complex salt.
FeCl
3
NH
4
CNS Fe(SCN)Cl
2
NH
4
Cl
Or FeCl
3
3NH
4
CNS Fe(SCN)
3
3NH
4
Cl
(viii) Ferric chloride Iorms a complex, prussian blue with potassium Ierrocyanide.
4FeCl
3
3K
4
Fe(CN)
6

de) Ierrocyani (Ferri
blue Prussian
3 6 4
| |Fe(CN) Fe 12KCl
(ix) On heating hydrated Ierric chloride FeCl
3
.6H
2
O, anhydrous Ierric chloride is not obtained. It is
changed to Fe
2
O
3
with evolution oI H
2
O and HCl.
2|FeCl
3
.6H
2
O|

Heat
Fe
2
O
3
6HCl 9H
2
O
Hydrated Ierric chloride may be dehydrated by heating with thionyl chloride.
FeCl
3
.6H
2
O 6SOCl
2
FeCl
3
12HCl 6SO
2
Corrosion of iron:
Corrosion is deIined as the gradual transIormation oI a metal into its combined state because
oI the reaction with the environment. Metals are usually extracted Irom their ores. Nature
tries to convert them again into the ore Iorm. The process by which the metals have the
tendency to go back to their combined state, is termed corrosion.
When iron is exposed to moist air, it is Iound covered with a reddish - brown coating which
can easily be detached. The redish brown coating is called rust`. Thus, the corrosion oI iron
or Iromation oI the rust is called rusting. The composition oI the rust is not certain but it
mainly contains hydrated Ierric oxide, 2Fe
2
O
3
.3H
2
O, together with a small quantity oI Ierrous
carbonate. The rust is Iormed by the action oI water on iron in presence oI dissolved oxygen
and carbon dioxide. It has been observed that impure iron is more prone to rusting.
The Iollowing are the Iavourable conditions Ior the rusting oI iorn:
(i) Presence oI moisture
(ii) Presence oI a weakly acidic atmosphere
(iii) presence oI impurity in the iron.
Various theories have been proposed to explain the phenomenon oI rusting oI iron but the
accepted theory is the modern electrochemical theory. When impure iron comes in contact
with water containing dissolved carbon dioxide, a voltaic cell is set up. The iron and other
impurities act as electrodes while water having dissolved oxygen and carbon dioxide acts as
an electrolyte. Iron atoms pass into solution as Ierrous ions.
Fe Fe
2
2e
Iron, thus, acts as anode.
The impurities act as cathode. At the cathode, the cathode, the electrons are used in Iorming
hydroxyl ions.
H
2
O O 2e 2OH
-
In presence oI dissolved oxygen, Ierrous ions are oxidised to Ierric ions which combine
with hydroxyl ions to Iorm Ierric hydroxide.
Fe
3
3OH
-
Fe(OH)
3
|2Fe
2
H
2
O O 2Fe
3
2OH
-
|
Corrosion or rusting is a surIace phenomenon and thus, the protection oI the surIace prevents
the corrosion. Iron can be protected Irom the rusting by use oI Iollowing methods:
(i) Applying paints, lacquers and enamels on the surIace oI iron.
(iii) By coating a thin Iilm oI zinc, tin, nickel, chromum, aluminium, etc.
Ferric Oxide (Fe
2
O
3
)
Preparation: (i) Hydrolysis oI FeCl
3
actually give red-gelatinous ppt. oI the hydrous oxide
Fe
2
O
3
(H
2
O)
4
which on heating at 200
o
C give red-brown o- Fe
2
O
3
.
(ii) It occur in haematite ore (Fe
2
O
3
).
(iii) On oxidation oI Fe
3
O
4
, - Fe
2
O
3
is Iormed.
(iv) 6Fe
2
O
3


CA 1400
4 Fe
3
O
4
O
2
Fe
3
O
4
is a mixed oxide FeO - Fe
2
O
3
(Occur as magnetite).
Properties:
(a) Freshly precipitate Fe
2
O
3
. (H
2
O)
4
dissolve in acid giving pale violet |Fe(H
2
O)
6
|
3
ion.
(b) |Fe
2
O
3
. (H
2
O)
4
| also dissolve in concentrated NaOH Iorming |Fe(OH)
6
|
3-
.
(v) Fusion oI Fe
2
O
3
with Na
2
CO
3
give NaFeO
2
(Sodium Ierrites) which is hydeolysed to Fe
2
O
3
&
NaOH
Na
2
CO
3
Fe
2
O
3
2NaFeO
2
CO
2
2NaFeO
2
H
2
O 2NaOH Fe
2
O
3
(vi) II Cl
2
gas is passed into an alkaline soultion oI hydrated Ierric oxide, a red purple soultion is
Iormed, containing the Ierrate ion |Fe
iv
O
4
|
2-
.
Fe
2
O
3
2NaOH 2NaFeO
2
H
2
O
2NaFeO
2
H
2
O 2Na
2
FeO
4
2NaCl 2H
2
(vii) Na
2
FeO
4
can also be obtained by oxidation oI Fe
2
O
3
with NaOCl (Sod. hypochloride).
(viii) Na
2
FeO
4
has Fe ( VI) and is a strong oxidizing agent (like KMnO
4
).
Potassium Permanganate, KMnO
4
This is the most important and well known salt oI permanganic acid. It is prepared Irom the
pyrolusite ore. It is prepared by Iusing pyrolusite ore either with KOH or K
2
CO
3
in presence
oI atmospheric oxygen or any other oxidising agent such as KNO
3
. The mass turns green
with the Iormation oI potassium manganate, K
2
MnO
4
.
2MnO
2
4KOH O
2
2K
2
MnO
4
2H
2
O
2MnO
2
2K
2
CO
3
O
2
2K
2
MnO
4
2CO
2
The Iused mass is extracted with water. The solution is now treated with a current oI chlorine
or ozone or carbon dioxide to convert manganate into permanganate.
2K
2
MnO
4
Cl
2
2KMnO
4
2KCl
2K
2
MnO
4
H
2
O O
3
2KMnO
4
2KOH O
2
3K
2
MnO
4
2CO
2
2KMnO
4
MnO
2
2K
2
CO
3
It is purple coloured crystalline compound. It is Iairly soluble in water. When heated alone
or with an alkali, it decomposes evolving oxygen.
2KMnO
4
K
2
MnO
4
MnO
2
O
2
4KMnO
4
4KOH 4K
2
MnO
4
2H
2
O O
2
On treatment with conc. H
2
SO
4
, it Iorms manganese heptoxide via permanganyl sulphate
which decomposes explosively on heating.
2KMnO
4
3H
2
SO
4
2KHSO
4
(MnO
3
)
2
SO
4
2H
2
O
(MnO
3
)
2
SO
4
H
2
O Mn
2
O
7
H
2
SO
4
Mn
2
O
7
2MnO
2

2
O
2
3
Potassium permanganate acts as an oxidising agent in alkaline, neutral or acidic solutions.
(a) In alkaline solution: KMnO
4
is Iirst reduced to manganate and then to insoluble manganese
dioxide. Colour changes Iirst purple to green and Iinally becomes colourless. However
brownish precipitate is Iormed.
2KMnO
4
2KOH 2K
2
MnO
4
H
2
O O
2K
2
MnO
4
2H
2
O 2MnO
2
4KOH 2O

2KMnO
4
H
2
O

Alkaline
2MnO
2
2KOH 3|O|
or

4
2MnO
H
2
O 2MnO
2
2OH
-
3|O|
(b) In neutral solution: MnO
2
is Iormed. Brownish ppt. is present.
2KMnO
4
H
2
O 2MnO
2
2KOH 3|O|
or

4
2MnO
H
2
O 2MnO
2
2OH
-
3|O|
or

4
MnO
2H
2
O 3e
-
MnO
2
4OH
-
(c) In acidic solution (in presence oI dilute H
2
SO
4
): Manganous sulphate is Iormed. The solution
becomes colourless.
2KMnO
4
3H
2
SO
4
K
2
SO
4
2MnSO
4
3H
2
O 5|O|
or 2

4
MnO
6H

2Mn
2
3H
2
O 5|O|
or

4
MnO
8H

5e
-
Mn
2
4H
2
O
This medium is used in quantitative (volumetric) estimations. The equivalent mass oI KMnO
4
in acidic medium is
5
mass Mol.
. The oxidation reactions oI acidiIied KMnO
4
are catalysed
by Mn (ii) ion.
The important oxidation reactions are:
(i) Ferrous salts are oxidised to Ierric salts.
2KMnO
4
3H
2
SO
4
K
2
SO
4
2MnSO
4
3H
2
O 5|O|
|2FeSO
4
H
2
SO
4
|O| Fe
2
(SO
4
)
3
H
2
O| x 5

2KMnO
4
10FeSO
4
8H
2
SO
4
5Fe
2\
(SO
4
)
3
K
2
SO
4
2MnSO
4
8H
2
O
or

4
2MnO
10Fe
2
16H

10Fe
3
2Mn
2
8H
2
O
(ii) Iodine is evolved Irom potassium iodide.
2KMnO
4
3H
2
SO
4
K
2
SO
4
2MnSO
4
3H
2
O 5|O|
|2KI H
2
SO
4
|O| K
2
SO
4
I
2
H
2
O| x 5

2KMnO
4
10 KI 8H
2
SO
4
6K
2
SO
4
2MnSO
4
5I
2
8H
2
O
or

4
2MnO
10I
-
16H

2Mn
2
5I
2
8H
2
O
(iii) H
2
S is oxidised to sulphur.
2KMnO
4
3H
2
SO
4
5H
2
S K
2
SO
4
2MnSO
4
5S 8H
2
O
(iv) SO
2
is oxidised to H
2
SO
4
.
2KMnO
4
5SO
2
2H2
O
K
2
SO
4
2MnSO
4
2H
2
SO
4
(v) Nitrites are oxidised to nitrates.
2KMnO
4
5KNO
2
3H
2
SO
4
K
2
SO
4
2MnSO
4
5KNO
3
3H
2
O
(vi) Oxalic acid is oxidised to CO
2
.
2KMnO
4
3H
2
SO
4
K
2
SO
4
2MnSO
4
10CO
2
8H
2
O
(vii) It oxidises hydrogen halides (HCl, HBr or HI) into X
2
(halogen).
2KMnO
4
3H
2
SO
4
10 HX K
2
SO
4
2MnSO
4
8H
2
O 5X
2
In neutral medium
(i) H
2
S is oxidised to sulphur.
2KMnO
4
H
2
O 2MnO
2
2KOH 3|O|
|H
2
S |O| H
2
O S| x 3

2KMnO
4
3H
2
S 2KOH 2MnO
2
2H
2
O 3S
(ii) Manganese sulpjate is oxidised to MnO
2
.
2KMnO
4
H
2
O 2MnO
2
2KOH 3 |O|
|MnSO
4
H
2
O |O| MnO
2
H
2
SO
4
| x 3
2KOH H
2
SO
4
K
2
SO
4
2H
2
O

2KMnO
4
3MnSO
4
2H
2
O K
2
SO
4
5MnO
2
2H
2
SO
4
(iii) Sodium thisoulphate is oxidised to sulphate and sulphur.
2KMnO
4
3Na
2
S
2
O
3
H
2
O 2KOH 2MnO
2
3Na
2
SO
4
3S
In alkaline medium
(i) It oxidises iodide to iodate.
2KMnO
4
H
2
O 2KOH 2MnO
2
3|O|
KI 3|O| KIO
3

2KMnO
4
KI H
2
O 2KOH 2MnO
2
KIO
(ii) It oxidises ethylene to ethylene glyocl.
H
2
O|O|
In alkaline medium it is called Bayer`s reagent.
Uses: (i) KMnO
4
is used as an oxidising agent in laboratory and industry. In volumetric esrimations,
the solution is Iirst standardised beIore use.
(ii) Alkaline potassium permanganate is called Bayer`s reagent. This reagent is used in organic
chemistry Ior the test oI unsaturation. KMnO
4
is used in the manuIacture os saccharin,
benxoic acid, acetaldehyde, etc.
(iii) KMnO
4
is used in qualitative analysis Ior detecting halides, sulphites, oxalates, etc.
Potassium Dichromate, K
2
Cr
2
O
7
It is the most important compound oI Cr(VI). It is manuIactured Irom chromite ore. is Iirst
converted into sodium dichromate . The hot saturated solution oI sodium dichromate is
mixed with KCl. Sodium chloride oI sodium chloride precipitates out Irom the hot solution
which is Iiltered oII. On cooling the mother liquor, crystals oI potassium dichromate separate
out.
It is orange-red coloured crystalline compound. It is moderately soluble in cold water but
Ireely soluble in hot water. It melts at 398
o
C. On heating strongly, it decomposes liberating
oxygen.
2K
2
Cr
2
O
7
2K
2
CrO
4
Cr
2
O
3

2
O
2
3
On heating with alkalies, it is converted to chromate, i.e., the colour changes Irom orange to
yellow. On acidiIying, yellow colour again changes to orange.
K
2
Cr
2
O
7
2KOH 2K
2
CrO
4
H
2
O
Orange
- 2
7 2
O Cr
2OH
-

Yellow
- 2
4
CrO
H
2
O
Yellow
- 2
4
CrO
2H

Orange
- 2
7 2
O Cr
H
2
O
In alkaline solution, chromate ions are present while in acidic solution, dichromate ions are
present.
Potassium dichromate reacts with hydrochloric acid and evolves chlorine.
K
2
Cr
2
O
7
14HCl 2KCl 2CrCl
3
7H
2
O 3Cl
2
It acts as a powerIul oxidising agent in acidic medium (dilute H
2
SO
4
).
- 2
7 2
O Cr 14H

6e
-
2Cr
3
7H
2
O
The oxidation state oI Cr changes Irom 6 to 3.
Some typical oxidation reactions are given bleow:
(i) Iodine is liberated Irom potassium iodide.
K
2
Cr
2
O
7
4H
2
SO
4
K
2
SO
4
Cr
2
(SO
4
)
3
4H
2
O 3|O|
|2KI H
2
SO
4
|O| K
2
SO
4
I
2
H
2
O| x 3

K
2
Cr
2
O
7
6KI 7H
2
SO
4
4K
2
SO
4
Cr
2
(SO
4
)
3
7H
2
O 3I
2
The equation in terms oI electron method may also be written as :
- 2
7 2
O Cr 14H

6e
-
2Cr
3
3I
2
7H
2
O
6I
-
3I
2
6e
-

- 2
7 2
O Cr 14H

6I
-
2Cr
3
3I
2
7H
2
O
(ii) Ferrous salts are oxidised to Ierric salts.
K
2
Cr
2
O
7
4H
2
SO
4
K
2
SO
4
Cr
2
(SO
4
)
3
4H
2
O 3|O|
|2FeSO
4
H
2
SO
4
|O| Fe
2
(SO
4
)
3
H
2
O| x 3

K
2
Cr
2
O
7
6FeSO
4
7H
2
SO
4
3Fe
2
(SO
4
)
3
Cr
2
(SO
4
)
3
7H
2
O K
2
SO
4
or 6Fe
2

- 2
7 2
O Cr 14H

6Fe
3
2Cr
3
7H
2
O
(iii) Sulphites are oxidised to sulphates.
K
2
Cr
2
O
7
4H
2
SO
4
K
2
SO
4
Cr
2
(SO
4
)
3
4H
2
O 3|O|
|Na
2
SO
3
|O| Na
2
SO
4
| x 3
K
2
Cr
2
O
7
Na
2
SO
3
4H
2
SO
4
3Na
2
SO
4
K
2
SO
4
Cr
2
)SO
4
)
3
4H
2
O
or
- 2
7 2
O Cr
- 2
3
3SO 8H

- 2
4
3SO
2Cr
3
4H
2
O
(iv) H
2
S is oxidised to sulphur.
K
2
Cr
2
O
7
4H
2
SO
4
3H
2
S K
2
SO
4
Cr
2
(SO
4
)
3
7H
2
O 3S
or
- 2
7 2
O Cr 3H
2
S 8H

2Cr
3
7H
2
O 3S
(v) So
2
is oxidised to H
2
SO
4
.
K
2
Cr
2
O
7
4H
2
SO
4
K
2
SO
4
Cr
2
(SO
4
)
3
4H
2
O 3|O|
|SO
2
|O| H
2
O H
2
SO
4
| x 3

K
2
Cr
2
O
7
H
2
SO
4
3SO
2
K
2
SO
4
Cr
2
(SO
4
)
3
H
2
O
or
- 2
7 2
O Cr 3SO
2
2H

2Cr
3

- 2
4
3SO
H
2
O
When the solution is evaporated, chrome-alum is obtained.
(vi) It oxidises ethyl alcohal to acetaldehyde and acetaldehyde to acetic acid.
alcohol Ethyl
5 2
OH H C

|O|
de Acetaldehy
3
CHO CH

|O|
de Acetaldehy
3
COOH CH
It also oxidises nitrites to nitrates, arsenites to arsenates, thiosulphate to sulphate and sulphur
(
2
3 2
O S O
2
4 2
O S
S), HBr to Br
2
, HI to I
2
etc.
Chromyl chloride test: This is a test oI chloride. When a mixture oI a metal chloride and potassium
dichromate is heated with conc. H
2
SO
4
, orange red vapours oI chrymyl chloride are evolved.
K
2
Cr
2
O
7
2H
2
SO
4
2KHSO
4
2CrO
3
H
2
O
|NaCl H
2
SO
4
NaHSO
4
HCl| x 4
|CrO
3
2HCl CrO
2
Cl
2
H
2
O| x 2

K
2
Cr
2
O
7
6H
2
SO
4
4NaCl 2KHSO
4
4NaHSO
4

chloride Chromyl
2 2
Cl CrO 3H
2
O
When chromyl chloride vapours are passed through NaOH solution, yellow coloured solution
is obtained.
4NaOH CrO
2
Cl
2

soln. Yellow
4 2
CrO Na 2NaCl 2H
2
O
Uses: Potassium dichromate is used:
(i) As a volumetric reagent in teh estimation oIreducing agents such as oxalic acid, Ierrous
ions, iodide ions, etc. It is used as a primary standrad.
Catalytic Properties:
Transition metals and their compounds have catalytic propetries in most oI the reactions
due to surIace adsorption.
ORES, MINERALS AND EX1RAC1IJE ME1ALLURCY
Ores and minerals Commonly occurring ores oI iron, copper, lead, magnesium and aluminium.
(Mains Onlv . Tin and silver)
Extractive metallurgy (Chemical principles and reactions only; industrial details excluded):
Carbon reduction method (iron)(Mains Onlv . Tin also),
SelI reduction method (copper and lead),
Electrolytic reduction method (magnesium and aluminium),
(Mains Onlv . cyanide process .Gold and silver)
ORES AND MINERALS
Metals occur in nature in combined Iorm as minerals.
Minerals Irom which a metal can be proIitably extracted is termed as ore. e.g. FeS
2
is a mineral oI
iron, not anore.
IMPORTANT ORES OF SOME METALS (Principal ore is given in bold letters)
Iron: In the combined state, iron occurs in the Iollowing minerals.
Haematite, Fe
2
O
3
Magnetite, Fe
3
O
4
Limonite, 3Fe
2
O
3
3H
2
O Spathic iron ore, FeCO
3
Tin: Cassiterite or tin stone, SnO
2
.
Copper occurs in the native state as well as in the compounds Iorm. The natural ores oI
copper are
Copper pyrites, CuFeS
2
Malachite, Cu(OH)
2
CuCO
3
(green)
Cuprite or ruby copper, Cu
2
O Azurite, Cu(OH)
2
2CuCO
3
Copper glance, Cu
2
S Cu
5
FeS
4
(peacock ore)
Lead:
Calena, PbS Cerussite, PbCO
3
Anglesite, PbSO
4
WulIenite, PbMnO
4
Stolzite, PbWO
4
Magnesium :
Dolomite, MgCO
3
CaCO
3
Carnallite, MgCl
2
KClH
2
O
Magnesite, MgCO
3
Epsomite(epsom salt), MgCO
3
7H
2
O
Kiesserite, MgSO
4
H
2
O Kainite, MgSO
4
KCl3H
2
O
Schonite, MgSO
4
K
2
SO
4
6H
2
O
Magnesium is widely distributed in nature in rocks, spring and seawater. In rocks and silicates it
occurs in mineral like olivine (Mg
2
SiO
4
), spinel (MgAl
2
O
4
),
talc (Mg
3
H
2
(SiO
3
)
4
), asbestos (CaMg
3
(SiO
3
)
4
), etc.
Aluminium: Aluminium is the third most abundant element oI earth`s crust.
Oxides: Corundum, Al
2
O
3
; diaspore, Al
2
O
3
H
2
O and bauxite, Al
2
O
3
2H
2
O.
Fluorides. Cryolite, Na
3
AlF
6
Silicates. Feldspar, KAlSiO
3
O
8
, mica(KAlSi
3
O
10
(OH)
2
) and
kaolinite (Al(OH)
4
, Si
2
O
5
)
Basic Sulphates. Alunite or alumstone, K
2
SO
4
Al
2
(SO
4
)
3
2Al(OH)
3
Basic Phosphates. Turquoise, AlPO
4
Al(OH)
3
H
2
O
Aluminates. Aluminates oI Mg, Fe and Mn.
Silver in the native Iorm is associated with copper and gold. The main ores oI silver are
Argentite or silver glance, Ag
2
S Horn silver, AgCl
Proustite, 3Ag
2
S As
2
S
3
Pyragyrite, 3Ag
2
S Sb
2
S
3
METALLURGICAL PROCESSES
INITIAL TREATMENT
(i) Crushing and Grinding :The ore is Iirst crushed by jaw crushers and ground in various size reduction
equipments like ball mills.
(ii) Concentration (dressing) of Ore: The crushed ore is concentrated either by one oI the Iollowing
methods or by their combination.
(a) Gravity Separation:When the diIIerence in densities oI ore and gangue is considerable, the ore can be
concentrated by a stream oI running water which washes oII the lighter gangue particles.
(b) Magnetic Separation Any ore having magnetic properties can eIIectively be separated by magnetic
separation. e.g.
(c) Froth Floatation: Mostly employed Ior sulphide ores. Water is mixed with 3.5 by weight eucalyptus oil
(or some other cheap oil) and the mixture is stirred by compressed air as shown in Fig.2. Froth is
generated at surIace. Sulphide particles in ores are preIerentially wetted by this Iroth and rise to surIace.
They are skimmed oII by a skimmer. Gangue is preIerentially wetted by water and it sinks to bottom.
Reagents employed in Iroth Iloatation are oI Iour types.
(I) FROTHERS: Which create Iroth e.g. palm oil.
(II) COLLECTORS: Which help in attachment oI ore particle to an air bubble in Iorth. e.g. Sodium xanthates
(III)ACTIVATORS: Simple inorganic compounds which enhance oI Iloating property oI metal sulphide e.g.CuSO
4
(IV) DEPRESSANTS: Which suppress the Iloatation oI a particular particle selectively, e.g. when an ore containing
PbS and ZnS is Iloated in presence oI CN
-
, Iloatation oI ZnS is suppressed and only PbS is
removed. CN
-
is then destroyed by any oxidizing agent and ZnS is Iloated again.
Calcination. When the ore is heated below its melting point in limited supply oI air, chieIly decomposition
reactions occur. This is roasting. It is highly endothermic. During calcination:
* All the volatile impurities are lost
* Water oI crystallizations is lost
Al
2
O
3
2H
2
O Al
2
O
3
2H
2
O(g)
Roasting is done at a temperature slightly higher than that oI calcination in excess oI air. The ore does not melt
during roasting. All the combustible organic matter burns away and the ore becomes more porous.
Exothermic reactions supply much oI the heat and much lesser energy is required in this case.
Sintering: Heating till Iusion oI ore just begins. Helps in converting small places oI ore to a bigger mass. Most oI
the Ieatures are common with roasting.
FURNACES. Furnaces are either powered by Iuel (mostly coal, as in blast Iurnace or reverberatory Iurnace) or
by electricity. Fuel Iired Iurnaces generator maximum temperature oI 1400-1500C while electric Iurnaces
can supply as high as 3000 temperature.
Fig.1
MAGNETIC SEPARATION
ORE
NON-
MAGNETIC
PARTICLES
MAGNETIC
PARTICLES

ELECTRO-
MAGNETIC
WHEEL

FROTH FLOATATION
COMPRESSED AIR
OIL
WATER
MIXTURE

FROTH
SKIMMER
CONCENTRATED
ORE
GANGUE
Fig.2
Kilns. When Iuel and ore are mixed and heated. No reduction occurs. e.g. Lime Kilns.
Blast Furnace.Fuel and ore are mixed and charged Irom the top oI Iurnace and hot air is blown Irom the holes
(tuyers) near the bottom. The ore is reduced as it descends down.
Reverberatory Furnace.Material to be heated is placed on the hearth oI a reverberatory Iurnace. As hot air is
blown in (see Iig.) Ilames rise and hit the concave top oI the Iurnace, thereby turning in and heating the
hearth. Iuel and ore are separate in this case.
GENERAL CLASSIFICATION OF EXTRACTION PROCESSES
An ore to be treated must Iirst be examined. Following methods should be tried (in this sequence).
Mechanical Separation II metal occurs in its native state(e.g. gold), it is simply separated mechanically by
crushing the nuggets or rocks and separating it.
Thermal Decomposition: II a particular compound can simply decompose on heating then the metal is recovered
by simple heating. e.g. Hg Irom HgO. Two interesting processes are described below.
(i) Mond's Process. When nickel oxide is heated with water gas (CO H
2
), H
2
reduces nickel oxide to
nickel, which readily combines with CO to Iorm Ni(CO)
4
, a highly inIlammable, volatile gas. This gas,
when separated out and heated to 180C, decomposes to give pure nickel.
(ii) van Arkel's Process. Many metals (e.g. zirconium) Iorm volatile iodides which, when contacted with
hot tungsten wire, release I
2
and the metal is deposited on the wire. When suIIicient quantity oI metal has
been deposited, tungsten core is bored out. This method is used Ior obtaining small quantities oI highly
pure metal.
Displacement Method : In this method a cheaper metal, which occupies a higher place in electrochemical
series, displaces a costlier metal Irom its salt solution. e.g. displacement oI gold and silver Irom their
solution by scrap zinc in cyanide process. Another example is treatment oI lean ore oI copper (containing
very small amount oI copper). Such ores are dug out and dumped in trenches in open. The rainwater
collects in trenches and dissolves the sulphides when they are oxidised to sulphates by atmospheric
oxygen.
CuS 2O
2
CuSO
4
(aq)
AIter a year or two, dilute solution oI copper sulphate is simply pumped out leaving behind all the mud
and other impurities. This solution, when treated with scrap iron, precipitates copper.
Cu
2
(aq) Fe Fe
2
(aq) Cu
High Temperature Chemical Reduction.
(i) By Carbon. e.g. in metallurgy oI iron and tin (discussed later).
(ii) 1hermite Process : Reduction by aluminium is highly exothermic, so much so that the products are
Iormed in molten state. This is thermite process. e.g. Cr
2
O
3
2Al Al
2
O
3
2Cr heat
(iii) Self Reduction as in the case od copper and lead (discussed later).
ELEC1ROLY1IC REDUC1ION
(i) In aqueous solution and
(ii) In Iused melts, iI the metal is too reactive. It is costly, hence it is resorted to only when no other method
is available. e.g. Ior Na, Mg, Al etc. (discussed later).
Fig. 3

CHIMNEA
AIR
ASHES
HEARTH

EXTRACTIVE METALLURGA
IRON AND TIN
Both iron and tin are extracted by the carbon reduction method.
Extraction of Iron
Iron is extracted Irom its principal ore, haematite. AIter the preliminary washing, concentration and
roasting, the ore is smelted in the presence oI coke and limestone in a blast Iurnace (Iig.1).
Roasted ore (8 parts) with desulphurized coke (4 parts) and limestone pieces (1 part) is Ied into
the blast Iurnace Irom the top. Preheated air is blown in through waterjacketed pipes called
tuyeres Iixed in the lower part oI the Iurnace. There is a temperature gradient as we move Irom the
bottom (temperature about 2000K) to the top (temperature about 500K) oI the blast Iurnace. The
blast Iurnace may be broadly divided into three main parts as described in the Iollowing.
1. Zinc of fusion The lower portion where coke burns and produced carbon dioxide and a lot oI
heating is known as zone oI Iusion:
C O
2
CO
2
H 406 kJ mol
1
Here the temperature is about 1775 K. A little above this, where temperature is above this, where
temperature is about 1475 K 1575 K, iron coming Irom above melts.
2. Zone of heat absorption The middle portion (temperature 1075 K 1275 K), CO
2
rising up
is reduced to CO with the absorption oI heat:
CO
2
C 2CO H 163 kJ mol
1
In this portion, limestone coming Irom above is decomposed and the resultant lime (CaO), which
acts as Ilux, combines with silica (present as impuritygangue) to Iorm calcium silicate (Iusible
slag): CaCO
3
CaO CO
2
CaO SiO
2
CaSiO
3
3. Zone of reduction The upper portion (675K 975K) where iron oxide is reduced to spongy
iron by carbon monoxide rising up the Iurnace:
Fe
2
O
3
3CO 2Fe 3CO
2
Fig.4
BLAST FURNACE
WASTE GASES
FIRE BRICKS
HOT AIR BLAST
SLAG
1SOOK
1HOOK
2OOOK
IRON
HEARTH
SOOK
1OOOK
CHARGE (ORE,LIMESTONE AND COKE)
G
A
S
E
S

R
I
S
E
C+ O
2
CO
2
S
O
L
I
D

C
H
A
R
G
E

D
E
S
C
E
N
D
S
3Fe
2
O
3
+ CO 2Fe
3
O
4
- CO
2
CaCO
3
CaO + CO
2
Fe
3
O
4
+ CO 3FeO + CO
2
Phosphates and Silicates reduced,
Impure iron melts
C+CO
2
2CO
FeO + CO Fe(S) + CO
2
P and S pass into molten iron
Molten slag forms
The reduction is believed to take place in stages:
3Fe
2
O
3
CO 2Fe
3
O
4
CO
2
Fe
3
O
4
CO 3FeO CO
2
FeO CO Fe CO
2
At the bottom oI the Iurnace the molten iron sinks down while above this Iloats the Iusible slag
which protects the molten iron Iorm oxidation. These two can be removed Irom diIIerent holes
(Fig. 4). Waste gases escaping at the top consists oI about 30 CO, 10 CO
2
and the rest
nitrogen.
Iron obtained Irom the blast Iurnace is known as pig iron.
Pig iron contains about 25 carbon as well as other impurities (usually Si, Mn, S and P). Pig iron
is converted into cast iron by remelting in a vertical Iurnace heated by coke. Cast iron expands on
solidiIication and is used Ior casting various articles. Wrought iron, which is the purest Iorm oI iron,
can be obtained by heating cast iron in a reverberatory Iurnace lined with iron oxide. Wrought iron
contains about 0.2 carbon.
Extraction of Tin.
Metallic tin is extracted Irom tin stone which contains about 10 oI the metal as SnO
2
, the rest
being siliceous matter, tungstates oI Fe, Cu and As.
AIter crushing, the ore is concentrated by washing in a current oI water (Gravity process to remove
lighter gangue particles) and by magnetic separator to remove tungstates oI Fe and Mn.
The ore is roasted to remove A and As their oxides. The ore then may be washed to remove
sulphates oI Cu and Fe. This gives black tin.
Finally, the ore is smelted in a reverberatory Iurnace or in a blast Iurnace at 14751575K. The ore
is mixed with oneIiIth oI its mass oI powdered anthracite (coal) and little oI lime or Iluorspar which
is used as Ilux. Tin oxide is reduced to tin:
SnO
2
2C Sn 2CO
The molten metal collected Irom the bottom oI Iurnace contains impurities such as Fe, Pb, S and
As. The metal may be puriIied electrolytically
REFINING OF TIN
(i) Liquation or sweating- When the block oI impure tin is heated on the sloping hearth oI
reverberatory Iurnace tin, alongwith lead and bismuth (all having a much lower melting points than
other metals), run oII leaving dross, an alloy oI Sn, Fe, Cu, W, As.
(ii) Poling (stirring with logs oI green wood) oI this sweated tin is done. Impurities get oxidised &
Iorm scum which is skimmed oII. 99 Sn is obtained.
Scum & dross are repuriIied. Slag contains 1025 Sn as SnSiO
3
because oI amphoteric nature
oI tin. This is recovered by smelting with carbon and CaO Ilux at a much higher temperature.
SnSiO
3
CaO C Sn CaSiO
3
CO
Electrolytic refining : Cathodepure metal, Anode pure tin, Electrolyte SnSO
4
(aq) with sulphuric
acid and hydroIluosilicic acid.
COPPER AND LEAD
Both copper and lead may be extracted by selfreduction method.
Extraction of Copper :Copper is mainly extracted Irom copper pyrites. AIter the concentration oI
its ore by Iroth Ilotation process, the ore is roasted in a current oI air to remove arsenic, antimony
and much oI sulphur. The reactions occurring are
(i) 2CuFeS
2
O
2
Cu
2
S 2FeS SO
2
(major reaction)
(ii) 2Cu
2
S 3O
2
2Cu
2
O 2SO
2
(iii) 2FeS 3O
2
2FeO 2SO
2
(minor reactions)
The ore is then mixed with a little coke and sand and smelted in a waterjacketed blast Iurnace.
The minor reactions that occured during roasting continue here. Ferrous oxide combines with sand
to Iorm a Iusible slag. Cuprous oxide Iormed combines with Ierrous sulphide to give Ierrous oxide
and cuprous sulphide. This is because iron has more aIIinity Ior oxygen than copper.
(iv) FeO SiO
2
FeSiO
3
(v) Cu
2
O FeS Cu
2
S FeO
Molten mass collected Irom the bottom oI Iurnace contains largely cuprous sulphide and a little
Ierrous sulphide. This molten mass is known as matte.
The molten matte is Iinally transIerred to Bessemer converter (Fig. 5). A blast oI sand and air is
blown in the converter through tuyeres which are situated a little above the bottom. This causes
removal oI S and As oxides and Ierrous oxide as slag (reaction iv). At the same time Cu
2
S is
oxidized mostly into Cu
2
O (reaction ii) and partly into CuO and CuSO
4
. All these react with Cu
2
S
giving copper. The reactions are
(ii) 2Cu
2
S 3O
2
2Cu
2
O 2SO
2

2Cu
2
S 5O
2
2CuSO
4
2CuO
2Cu
2
O Cu
2
S 6Cu SO
2

CuSO
4
Cu
2
S 3Cu 2SO
2

Cu
2
S 2 CuO 4Cu SO
2

Finally, copper may be reIined electrolytically (electrolyte; copper sulphate: anode; impure copper
and cathode; pure copper).
Extraction of lead: Lead is mainly extracted Irom galena. AIter the concentration oI the ore by
Iroth Ilotation process, the ore is roasted in a reverberatory Iurnace Ior about six hours at a
moderate temperature in a current oI air. Part oI galena is converted into lead oxide and lead
sulphate. AIter this, the supply oI air is stopped and small quantities oI carbon, quicklime and
cheap iron ore are added along with increase oI temperature. At this stage, unreacted sulphide
reacts with the lead oxide and sulphate giving metallic lead:
PbS 2PbO 3Pb 2SO
2
PbS PbSO
4
2Pb 2SO
2
The obtained lead contains impurities such as Cu, Ag, Bi, Sb and Sn. Silver is removed by Parke`s
process where molten zinc is added to molten impure lead. The Iormer is immiscible with the latter.
Silver is more soluble in molten zinc than in molten lead. Zincsilver alloy solidiIies earlier then
molten lead and thus can be separated. AIter this, crude lead is reIined electrolytically (Electrolyte;
lead silicoIluoride, PbSiF
6
and hydroIluosilicic acid, H
2
SiF
6
with a little gelatin, anode; crude lead
and cathode; pure lead).
Converter
SiO
2
-- air
Molten matte
FIG. S
BESSEMER CONVERTER
MAGNESIUM AND ALUMINIUM
Extraction of magnesium Magnesium is commonly obtained by the electrolysis oI Iused
magnesium chloride containing a little (25) sodium chloride and sodium Iluoride at 700
0
C in an
airtight iron pot which itselI serves as the cathode, the anode being a graphite rod which dips into
the electrolyte. The anode is surrounded by a perIorated porcelain tube Ior the exit oI chlorine. The
electrolysis is carried out in the atmosphere oI coal gas so as to prevent the attack oI atmospheric
oxygen and nitrogen on magnesium. Molten magnesium being lighter then the electrolyte, it Iloats
over the Iused electrolyte and is withdrawn (Fig. 6). Voltage ~ 6V.
In Dow process, magnesium is recovered Irom seawater as magnesium chloride which is then
electrolysed using cell described above (Fig. 6).
Dow`s Sea Water Process. Sea water contains 0.13 Mg ions.
Mg
2
(seawater) Ca(OH)
2
(Irom oyster shells) Mg(OH)
2
CaCl
2
MgCl
2
.
2H
2
O
MgCl
2
.
2H
2
O MgCl
2
.
1.5H
2
O MgCl
2
Dow`s Natural Brine Process.
MgCO
3
.CaCO
3
MgO.CaO CaCl
2
(aq) MgCl
2
(aq) MgCl
2
(aq) CaCO
3
(dolomite) (calcined dolomite)
The reaction is : CaCl
2
.
MgCl
2
(aq) MgO.CaO 2CO
2
MgCl
2
(aq) 2CaCO
3

Electrolysis. Anhydrous carnallite (KClMgCl

2
6H
2
O) may also be employed as the starting
material oI magnesium chloride. The cathode may be a layer oI molten lead on the Iloor oI the
cell and anode may be graphite rods which are suspended above the molten lead. Magnesium
liberated at the cathode dissolves in molten lead. The alloy oI leadmagnesium is subjected to electrolysis
to obtain pure magnesium (electrolyte: Iused carnallite, anodeleadmagnesium alloy and cathodesteel
rods.)
Extraction of Aluminium Aluminium is isolated Irom the electrolysis oI bauxite, Al
2
O
3
2H
2
O. Since it
is diIIicult to puriIy aluminium, bauxite ore is puriIied either by Baeyer's process (or Hall's process) or
Serpek's process depending upon the impurity present in the ore.
II the bauxite contains iron oxide as the impurity, one can use Baeyer's or Hall's process as described
below.
FIG. G
ELECTROLATIC CELL FOR THE
PRODUCTION OF MAGNESIUM
Graphite anode
Porcelain hood
Inert gas
(coal gas)
Iron cathode
Mg
Molten electrolyte
Cl
2
Inert gas
Iron cell
Thickened in
Dorr Thickeners
dil. HCl (10)
spray drying
dry HCl
heat
dil. HCl
heat CO
2
( c a l c i ne d
dol omi t e)
Baeyer's Process: Finally ground ore is roasted to convert Ierrous oxide to Ierric oxide and then digested
with concentrated caustic soda solution at 423K. Al
2
O
3
dissolves while Fe
2
O
3
remains undissolved.
The latter is Iiltered oII and Irom the solution Al(OH)
3
gives Al
2
O
3
.
Al
2
O
3
2OH

3H
2
O 2Al(OH)

4
Aluminate ion dissolves
Al(OH)

4
H

Al(OH)
3
H
2
O
precipitates
2Al(OH)
3
heat

Al
2
O
3
3H
2
O
Hall's Process: In this process the ore is Iused with sodium carbonate when soluble metaaluminate
(NaAlO
2
) is produced. This is extracted with water leaving behind iron oxide. Carbon dioxide at 323
333 K is passed through water extract to get Al(OH)
3
which on heating gives Al
2
O
3
.
Al
2
O
3
Na
2
CO
3
fused

2NaAlO
2
CO
2
extracted with water
2NaAlO
2
3H
2
O CO
2
2Al(OH)
3
Na
2
CO
3
2Al(OH)
3
heat

Al
2
O
3
3H
2
O
II the impurity is silica, the Serpek's process is used to puriIy bauxite.
Serpek's Process : The powdered ore is mixed with coke and heated to 2075K in a current oI
nitrogen. Silica present is reduced to silicon which volatilizes oII and alumina gives aluminium nitride. The
hydrolysis oI the latter gives Al(OH)
3
, heating oI which gives Al
2
O
3
.
SiO
2
2C Si - 2CO2-
Al
2
O
3
3C N
2
2AlN 3CO
AlN 3H
2
O Al(OH)
3
NH
3
2Al(OH)
3
heat

Al
2
O
3
3H
2
O
AIter obtaining pure Al
2
O
3
, it is dissolved in Iused cryollite, Na
3
AlF
6
, with a little Iluorspar, CaF
2
and is
electrolysed in an iron tank lined with blocks oI carbon which serve as the cathode. The anode consists
oI a number oI graphite rods suspended vertically inside the tank (Fig. 7)
Aluminium gets settled at the bottom oI the tank and can be removed. The reactions occurring at the
electrodes are
Cathode Al
3
3e

Al
Anode 2O
2
2
O
2
4e

C O
2
CO
2
Anode is replaced periodically because oI its consumption.
SILVER AND GOLD
Cyanide Process: Silver and gold are extracted by the cyanide process (MacArthurForrest process).
AIter the preliminary crushing and concentration by Iroth Iloatation process, the ore (crushed auriIerous
rocks in the case oI gold)is leached with dilute (0.47) solution oI sodium cyanide made alkaline by
adding lime kept agitated by a current oI air. Silver (or gold) pass into solution as argentocyanide (or
aurocyanide) :
Ag
2
S 4NaCN 2Na|Ag(CN)
2
| Na
2
S
FIG. 7
ELECTROLATIC CELL FORTHE PRODUCTION OF
ALUMINIUM
At the cathode : Al
3+
+ 3e
-
Al
At the anode: C(s) + 2O
2-
CO
2
(g) + 4e
-
The air blown in remove Na
2
S as Na
2
S
2
O
3
and Na
2
SO
4
causing the above reaction to proceed to
completion.
2Na
2
S 2O
2
H
2
O Na
2
S
2
O
3
2NaOH
Na
2
S
2
O
3
2NaOH 2O
2
2Na
2
SO
4
H
2
O
4Au 8NaCN 2H
2
O O
2
4Na|Au(CN)
2
| 4NaOH
The solution obtained above is Iiltered and treated with scrap iron or zinc when silver (or gold) get
precipitated:
2Ag(CN)

2
Zn Zn(CN)
2
4
2Ag
2Na|Au(CN)
2
| Zn Na
2
|Zn(CN)
4
| 2Au
The obtained silver is puriIied electrolytically (electrolyte:silver nitrate solution containing 1 nitric acid,
anode: impure silver and cathode: pure silver). The impurities like zinc and copper pass into the solution
while gold Ialls down as anode mud.
Gold thus obtained is contaminated by zinc which is dissolved out by sulphuric acid. The dried
residue oI gold is then Iused under borax (Ilux) in graphite crucible and the melted down gold
(bullion) which invariably contains silver, is sent Ior reIining.
METALLUHGY AT A GLANCE