INORGANIC CHEMISTRY

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.
Na2O2 + 2H2O  2NaOH + H2O2
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.
Na2O2 + H2SO4  Na2SO4 + H2O2
The crystals of hydrated sodium sulphate (Na2SO4·10H2O) are removed by cooling the solution. The
solution of hydrogen peroxide obtained always consists some dissolved sodium sulphate. The concentration
of H2O2 is about 3%.
BaO2·8H2O + H2SO4 = BaSO4 + H2O2 + 8H2O
The barium sulphate formed is filtered off and a solution of H2O2 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
H2O2 which goes into the solution.
3BaO2 + 2H3PO4  Ba3(PO4)2 + 3H2O2
ppt.
Insoluble barium phosphate is filtered off. The filterate consists of hydrogen peroxide.
The barium phosphate is decomposed by dilute sulphuric acid.
Ba3(PO4)2 + 3H2SO4  3BaSO4 + 2H3PO4
BaSO4 is removed by filtration and orthophosphoric acid is used again.

Merck’s process: H2O2 can be obtained by passing a current of CO2 through a cold pasty solution of
barium peroxide in water.
BaO2 + CO2 + H2O  BaCO3 + H2O2
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.
2H2SO4 2H+ + 2HSO4–
2HSO4–  H2S2O8 + 2e (anode)
peroxy
disulphuric acid
Peroxy disulphuric acid is distilled. Hydrolysis occurs and a distillate containing about 30% H2O2 is obtained.
H2S2O8 + 2H2O  2H2SO4 + H2O2
In place of 50% H2SO4, ammonium hydrogen sulphate dissolved in excess of sulphuric acid can be used
for electrolysis.
NH4HSO4 NH4SO4– + H+
At anode 2NH4SO4–  (NH4)S2O8 + 2e
Ammonium peroxy
disulphate
At cathode 2H+ + 2e  H2(g)
The solution containing ammonium peroxy disulphate is heated at 43 mm pressure when its hydrolysis
occurs forming hydrogen peroxide.
(NH4)2S2O8 + 2H2O  2NH4·HSO4 + H2O2
Hydrogen peroxide along with water distils over. Ammonium bisulphate can be used again. This method
gives 30–40% aq. solution of hydrogen peroxide.

Properties of H2 O2
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.
2H2O2 = 2H2O + O2
(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.
H2O2 + 2NaOH = Na2O2 + 2H2O
H2O2 + Ba(OH)2 = BaO2 + 2H2O
H2O2 + Na2CO3 = Na2O2 + CO2 + H2O
(iii) Oxidising nature: It is a powerful oxidising agent. It is a electron acceptor in acidic and alkaline
solutions.
H2O2 + 2H+ + 2e = 2H2O (In acidic solutions)
H2O2 + 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,
H2O2  H2O + O
the following examples show the oxidising nature of H2O2:
(a) It oxidises black lead sulphide (PbS) to which lead sulphate (PbSO4).
PbS + 4H2O2  PbSO4 + 4H2O
(b) It oxidises nitrites to nitrates.
NaNO2 + H2O2  NaNO3 + H2O
(c) It oxidises sulphites into sulphates.
Na2SO3 + H2O2  Na2SO4 + H2O
(d) It oxidises arsenites into arsenates
Na3AsO3 + H2O2  Na3AsO4 + H2O
(e) It liberates iodine from potassium iodide
2KI + H2O2  2KOH + I2
(f) It oxidises H2S into sulphur
H2S + H2O2  2H2O + S
(g) It oxidises acidified ferrous sulphate to ferric sulphate
2FeSO4 + H2SO4 + H2O2  Fe2(SO4)3 + 2H2O
(h) It oxidises acidified potassium ferrocyanide to potassium ferricyanide
2K4Fe(CN)6 + H2SO4 + H2O2  2K3Fe(CN)6 + K2SO4 + 2H2O
(i) It oxidises formaldehyde to formic acid. This oxidation occurs in presence of pyrogallol and in alkaline
medium.
HCHO + H2O2  HCOOH + H2O
or HCHO + H2O2  2HCOOH + H2
(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 + 3H2O2  2Na2CrO4 + 8H2O
(l) A solution of chromic acid in sulphuric acid or acidified potassium dichromate is oxidised to blue peroxide
of chromium (CrO5) which is unstable, however, it is soluble in ether and produces blue coloured solution.
K2Cr2O7 + H2SO4 + 4H2O2  2CrO5 + K2SO4 + 5H2O
Peroxide of chromium decomposes to form chromic sulphate and oxygen.
4CrO5 + 6H2SO4  2Cr2(SO4)3 + 6H2O + 7O2
Peroxide of chromium is represented as

(m) In acidic solution, mercury is oxidised to mercuric oxide.

Hg + H2O2 H  HgO + H2O
2 SO 4

(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.
H2O2  2H+ + O2 + 2e–
In alkaline solution, however, its reducing action is more effective.
H2O2 + 2OH–  2H2O + O2 + 2e–
The potential equation when H2O2 acts as a reducing agent can be expressed as,
H2O2 + O  H2O + O2
(a) Ag2O is reduced to silver
Ag2O + H2O2  2Ag + H2O + O2
(b) It reduces ozone to oxygen.
H2O2 + O3  H2O + 2O2
(c) Manganese dioxide in acidic medium is reduced to manganous salt.
MnO2 + H2SO4  PbO + H2O + O2
(e) Red lead in presence of HNO3 is reduced to plumbous salt.
Pb3O4 + 6HNO3 + H2O2  3Pb(NO3)2 + 4H2O + O2
(f) Chlorine and bromine are reduced to corresponding hydracids.
Cl2 + H2O2  2HCl + O2
This reaction can be shown in following steps:
Cl2 + H2O2  2HCl + O2
Similarly, Br2 + 2O2  2HBr + O2
(g) It reduces acidified KMnO4 solution, i.e., acidified KMnO4 is decolorised by H2O2.
2KMnO4 + 3H2SO4 + 5H2O 2  K2SO4 + 2MnSO4 + 8H2O + 5O2
(h) Potassium ferricyanide (alk. solution) is reduced to potassium ferrocyanide.
2K3Fe(CN)6 + 2KOH + H2O2  2K4Fe(CN)6 + 2H2O + O2
(i) Hypohalites are reduced to halides
NaOCl + H2O2  NaCl + H2O + O2
(j) KIO4 is reduced to KIO3
KIO4 + H2O2  KIO3 + H2O + O2
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 H2O2 is used to oxidise petrol, alcohol, and hydrozine
hydrate for the propelling of rockets and torpedoes.
NH2·NH2 + 2H2O2  N2 + 4H2O

Compounds of Sodium
1. Sodium Oxide, Na2 O :
It is prepared by heating sodium nitrate or sodium nitrite with sodium.
2NaNO3 + 10Na  6Na2O + N2
2NaNO2 + 6Na  4Na2O + N2
Pure sodium oxide is formed when the mixture of sodium azide and sodium nitrite is heated.
3NaN2 + NaNO2  2Na2O + 5N2
Na2O + H2O  2NaOH + heat
0
On heating at 400 C, it disproportionates forming sodium peroxide and metallic sodium vapour.
0
2Na2O 400C Na2O2 + 2Na
Sodamide is formed when it reacts with liquid ammonia
Na2O + NH3  NaNH2 + NaOH
It is used as dehydrating and polymerising agent in organic chemistry.

2. Sodium Peroxide, Na2 O2 :

It is formed by heating sodium in excess of air free from moisture and carbon dioxide or in excess of pure
oxygen .
0
2Na + O2(excess) 350
C Na2O2
It is a pale yellow powder. On exposure, it becomes white moisture and carbon dioxide
2Na2O2 + 2H2O  4NaOH + O2
2Na2O2 + 2CO2  2Na2CO3 + O2
At low temperature, it forms H2O2 with water and acids.
It combines with CO and CO2
Na2O2 + CO  Na2CO3
2Na2O2 + 2CO2  2Na2CO3 + O2
It acts as a powerful oxidising agent.
(a) Chromic compounds are oxidised to chromates
2Cr(OH)3 + 3Na2O2  2Na2CrO4 + 2NaOH + 2H2O
(b) Manganous salt is oxidised to sodium manganate.
MnSO4 + 2Na2O2  Na2NO4 + Na2SO4
(c) Sulphides are oxidised to corresponding sulphates
Na2S + 4O  Na2SO4
Benzoyl peroxide (bleaching agent) is formed when C6H5COCl reacts with Na2O2
2C6H5COCl + Na2O2  (C6H5CO)2O2 + 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.
Na2CO3 + Ca(OH)2 CaCO3 + 2NaOH
Na2CO3 + Fe2O3  2NaFeO2 + CO2
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.
 2Na2FeO2 + H2O  2NaOH + Fe2O3
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 2O H+ + OH–
Hydrogen is liberated at cathode, Cl2 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 + Cl2  NaCl + NaClO + H2O
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  Cl2
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 2H2O + 2e  H2  + 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 + CO2  Na2CO3 + H2O

(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 + H2O
2NaOH + H2SO4  Na2SO4 + 2H2O
NaOH + HNO3  NaNO3 + H2O
3NaOH + H3PO4  Na3PO4 + 3H2O
NaOH + CH3COOH  CH3COONa + H2O
(ii) It combines with acidic oxides to form salts.
2NaOH + CO2  Na2CO3 + H2O
Sodium
carbonate
2NaOH + SO2 Na2SO3 + H2O
Sodium
sulphide
2NaOH + 2NO2  NaNO3 + NaNO2 + H2O
Sodium Sodium
Nitrate Nitrite

(iii) Amphoteric oxides of aluminium, zinc, tin and lead dissolve in sodium hydroxide forming corresponding
salts.
Al2O3 + 2NaOH  2NaAlO2 + H2O
Sodium meta
aluminate
ZnO + 2NaOH  Na2ZnO2 + H2O
Sodium zincate
SnO + 2NaOH  NaSnO2 + H2O
Sodium stannite
SnO2 + 2NaOH  NaSnO3 + H2O
Sodium stannate
PbO + 2NaOH  NaPbO2 + H2O
Sodium plumbite
PbO2 + 2NaOH  NaPbO3 + H2O
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.
Cl2 + 2NaOH  NaCl + NaClO + H2O
(cold and dilute) Sodium
hypo chlorite
Br2 + 2NaOH  NaBr + NaBrO + H 2O
(cold and dilute) Sodium
hypo bromite
I2 + 2NaOH  NaI + NaIO + H 2O
(cold and dilute) Sodium
hypo iodate
Halogens form helates and halides with hot and concentrated solution of NaOH.
3Cl2 + 6NaOH  5NaCl + NaClO3 + 3H2O
(hot and conc.) Sodium chlorate
3r2 + 6NaOH  5NaBr + NabrO3 + 3H2O
(hot and conc.) Sodium bromate
3I2 + 6NaOH  5NaI + NaIO3 + 3H2O
(hot and conc.) Sodium iodate

(ii) Yellow phosphorus (white) when heated with NaOH solution evolves phosphine gas (PH3) alongwith
the formation of sodium hypophosphite.
P4 + 3NaOH + 3H2O  3NaH2PO2 + PH3
Sodium Phosphine
hypophosphite
(iii) Sulphur on heating with sodium hydroxide solution forms sodium thiosulphate
4S + 6NaOH  Na2S2O3 + 2Na2S + 3H2O
Sodium sodium
thio sulphate sulphide
(iv) Silicon evolves hydrogen when heated with NaOH solution
2NaOH + Si + H2O  Na2SiO3 + 2H2
Sodium silicate
(v) Boron also evolves hydrogen when fused with NaOH.
2B + 6NaOH  2Na3BO3 + 3H2
Sodium borate

(d) Action on metals: Metals like Zn, Al, Sn, Pb react with sodium hydroxide solution and evolve hydrogen.
Zn + 2NaOH  Na2ZnO2 + H2
2Al + 2NaOH + 2H2O  2NaAlO2 + 3H2
Sn + 2NaOH + H2O  Na2SnO3 + 2H2
Pb + 2NaOH + H2O  Na2PbO3 + 2H2
[However, Sn and Pb when fused with NaOH form Na2SnO2 and Na2PbO2, respectively.
Sn + 2NaOH  Na2SnO2 + H2
Pb + 2NaOH  Na2PbO2 + H2]
(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(NO3)2 + 2NaOH  Ni(OH)2 + 2NaNO3
FeSO4 + 2NaOH  Fe(OH)2 + Na2SO4
FeCl3 + 3NaOH  Fe(OH)3 + 3NaCl
Red ppt.
CrCl3 + 3NaOH  Cr(OH)3 + 3NaCl
Green ppt.
MnSO4 + 2NaOH  Mn(OH)2 + Na2SO4
Buff coloured ppt.
CuSO4 + 2NaOH  Cu(OH)2 + Na2SO4
Blue coloured ppt.
(ii) Insoluble hydroxides which dissolve in excess of NaOH.
ZnSO4 + 2NaOH  Zn(OH)2 + Na2SO4
White insoluble
Zn(OH)2 + 2NaOH  Na2ZnO2 + 2H2O
Sodium zincate
(soluble)
AlCl3 + 3NaOH  Al(OH)3 + 3NaCl
White ppt.
Al(OH)3 + NaOH  NaAlO2 + 2H2O
Sodium meta
aluminate(soluble)
SnCl2 + 2NaOH  Sn(OH)2 + 2NaCl
White ppt.
Sn(OH)2 + 2NaOH  Na2SnO2 + 2H2O
Sodium stannite
(Soluble)

(iii) Unstable hydroxides

2AgNO3 + 2NaOH  2AgOH + 2NaNO3
2AgOH  Ag2O + H2O
(Brown)
 HgCl2 + 2NaOH  Hg(OH)2 + 2NaCl
Hg(OH)2  HgO + H2O
(Yellow)

(f) Action of ammonium salts: Ammonium salts are decomposed on heating with sodium hydroxide
solution with the evolution of ammonia gas.
NH4Cl + NaOH  NH3 + NaCl + H2O
(NH4)2SO4 + 2NaOH  Na2SO4 + 2NH3 + H2O
(g) Action of carbon monoxide:
NaOH reacts with carbon monoxide under pressure at 150–2000C to form sodium formate.
150  2000 C
NaOH + CO    HCOONa
510 atm
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 (Na2 CO3 .10H2 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 (CaCO3). It involves the following steps:

(i) Conversion of NaCl into Na2 SO4 : The common salt a heated with calculated quantity of sulphuric
acid (concentrated) in the furnace.
NaCl + H2SO4  NaHSO4 + HCl
Sodium hydrogen
sulphate
The paste is heated at higher temperature when sodium hydrogen sulphate is converted into sodium sulphate.
NaHSO4 + NaCl  Na2SO4 + 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 Na2 CO3 : 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.
NH3 + H2O + CO2  NH4HCO3
Ammonium bicarbonate
NaCl + NH4HCO3  NaHCO3 + NH4Cl
Sodium
bicarbonate
2NaHCO3 
  Na2CO3 + H2O + CO2
(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 + CO2  Na2CO3 + H2O
Physical Properties: The common form is decahydrate, Na2CO3.10H2O. This form is called washing
soda. The decahydrate form on standing in air effloresces and crumbles to powder. It is the monohydrate
form,
Na2CO3.H2O. It also forms a heptahydrate, Na2CO3.7H2O.

Chemical Properties: (a) Action of acids: It is readily decomposed by acids with evolution of carbon
dioxide. The reaction occurs in two steps.
Na2CO3 + HCl  NaHCO3 + NaCl
NaHCO3 + HCl  NaCl + H2O + CO2
(b) Action of CO2 : On passing CO2 through the concentrated solution of sodium carbonate, sodium
bicarbonate gets precipitated.
Na2CO3 + H2O + CO2  2NaHCO3
(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.
Na2CO3 + SiO2  Na2SiO3 + CO2
(d) Action of slaked lime: Sodium hydroxide is formed when the solution of sodium carbonate and
slaked lime is heated.
Na2CO3 + Ca(OH)2  2NaOH + CaCO3
(e) Action with sulphur and sulphur dioxide: When aqueous solution of sodium carbonate containing
sulphur is treated with sulphur dioxide, sodium thiosulphate (Na2S2O3) is formed.
Na2CO3 + SO2 H 2O
  Na2SO3 + CO2
Na2SO3 + S  Na2S2O3
(f) Action on salts of non-alkali metals: Sodium carbonate reacts with metal salts (except alkali metal
salts) to form insoluble or basic carbonates.
CaCl2 + Na2CO3  CaCO3 + 2NaCl
BaCl2 + Na2CO3  BaCO3 + 2NaCl
2MgCl2 + 2Na2CO3 + H2O  MgCO3·Mg(OH) + 4NaCl + CO2
Basic Magnesium Carbonate
5ZnSO4 + 5Na2CO3 + 4H2O  [2ZnCO3·3Zn(OH)2]·H2O + 5Na2SO4 + 3CO2
Basic zinc Carbonate
CuSO4 + Na2CO3  CuCO3 + Na2SO4
 2CuSO4 + 2Na2CO3 + H2O  Cu(OH)2·CuCO3 + CO2 + Na2SO4
Basic copper Carbonate
3(CH3COO)2Pb + 3Na2CO3 + H2O  2PbCO3Pb(OH)2 + CO2 + 6CH3COONa
Basic lead Carbonate
2AgNO3 + Na2CO3  Ag2CO3 + 2NaNO3
Carbonates of metals like Fe, Al, Sn, etc., When formed are immediately hydrolysed to hydroxides.
Fe2(SO4)3 + 3Na2CO3  Fe2(CO3)3 + 3Na2SO4
Fe2(CO3)3 + 3H2O  2Fe(OH)3 + 3CO2
Uses: As a laboratory reagent. The mixture of Na2CO3 and K2CO3 is used as a fusion mixture.

5. Sodium Bicarbonate (Baking Soda), NaHCO3

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.
Na2CO3 + CO2 + H2O  2NaHCO3
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.
NaHCO3 + H2O NaOH + H2CO3
The solution gives yellow colour with methyl orange but no colour with phenolphthalein.
On heating, it loses carbon dioxide and water forming sodium carbonate.
2NaHCO3  Na2CO3 + H2O+ CO2
The metal salt which forms basic carbonate with sodium carbonate, gives normal carbonate with sodium
bicarbonate
ZnSO4 + 2NaHCO3  ZnCO3 + Na2CO3 + H2O+ CO2

6. Sodium Thiosulphate, Na2 S2 O3 .5H2O

It is the sodium salt of an unstable acid, thiosulphuric acid (H2S2O3). 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.
Na2SO3 + S  Na2S2O3
The unreacted sulphur is filtered off and the filtrate is evaporated to crystallization.

(ii) Spring’s reaction: The mixture of sodium sulphite and sodium sulphide is treated with calculated
quantity of iodine.
Na2S + I2 + Na2SO3  Na2S2O3 + 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.
2Na2S + Na2CO3 + 4SO2  3Na2S2O3 + CO2

(iv) Sodium thiosulphate is formed when sulphur is heated with caustic soda solution.
4S + 6NaOH  Na2S2O3 + 2Na2S + 3H2O
With excess of sulphur, sodium pentasulphide is formed,
Na2S + 4S  Na2S5

(v) On passing SO2 gas through the solution of Na2CO3 in presence of sulphur we get sodium thiosulphate.
Na2CO3 + SO2  Na2SO3 + CO2
Na2SO3 + S  Na2S2O3
Properties: (i) It is a colourless crystalline solid consisting of 5 molecules of water as water of crystallization.
It has the formula, Na2S2O3·5H2O. It is soluble in water. It melts at 480C.
(ii) Action of heat: It is efflorescent substance. The water molecules are completely lost when heated at
2150C.
0
Na2S2O3·5H2O 215 C Na2S2O3 + 5H2O
When strongly heated above 2230C, it decomposes forming sodium sulphate and sodium pentasulphide.
4Na2S2O3  3Na2SO4 + Na2S5
(iii)Action of acids: Dilute acids decompose it with evolution of SO2 and precipitation of sulphur.
Na2S2O3 + 2HCl  2NaCl + SO2 + S + H2O
Na2S2O3 + H2SO4  Na2SO4 + SO2 + S + H2O
(iv) Oxidation : It is oxidised by iodine quantitatively
2Na2S2O3 + I2  2NaI + Na2S4O6
Sodium tetrathionate
Colour of iodine disappears.

(v) Reducing action: It is oxidised by chlorine and bromine water. Sulphur is precipiated.
Na2S2O3 + Cl2 + H2O  Na2SO4 + 2HCl + S
It reduces FeCl3 to FeCl2
2Na2S2O3 + 2FeCl3  Na2S4O6 + 2FeCl2 + 2NaCl

(vi) Action of AgNO3 : A white precipitate of silver thiosulphate is obtained which changes to yellow,
brown and finally black due to the formation of silver sulphide.
2AgNO3 + Na2S2O3  Ag2S2O3 + 2NaNO3
Ag2S2O3 + H2O  Ag2S + H2SO4

(vii) Action of silver halides: Halides form complexes with sodium thiosulphate. Silver bromide forms
argento thiosulphate complex.
AgBr + 2Na2S2O3  Na3[Ag(S2O3)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.
CuSO4 + Na2S2O3  CuS2O3 + Na2SO4
Cupric thiosulphate
2Cu2S2O3 + Na2S2O3  Cu2S2O3 + Na2S4O6
Cuprous thiosulphate
3Cu2S2O3 + 2Na2S2O3  Na4[Cu6(S2O3)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, KCl·MgCl2·6H2O, by fractional crystallisation. The
carnalities ground and extracted with a 20 percent solution of MgCl2. The carnallite dissolves while NaCl
and MgSO4 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, K2O
(b) Potassium dioxide (tetraoxide or superoxide), KO2 or K2O4
(c) Potassium sesquioxide, K2O3

KO2 is prepared by burning potassium in excess of oxygen free from moisture.

K + O2  KO2
It is also obtained by reacting dry potassium hydroxide with ozone.
2KOH + O3  2KO2 + H2O

K2O3 is obtained when oxygen is passed through liquid ammonia containing potassium.
4K (dissolved in liquid NH3) 3 O2
 2K2O3
Potassium superoxide, KO2, is a chrome yellow powder. it dissolves in water giving H2O2 and O2.
2KO2 + 2H2O  2KOH + H2O2 + O2
It reacts directly with CO and CO2.
2KO2 + CO  K2CO3 + O2
2KO2 + CO2  K2CO3 + (3/2)O2
On heating with sulphur, it forms potassium sulphate.
2KO2 + S  K2SO4
KO2 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 CO2, SO2, 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.
C2H5Br + KOH(alc.)  C2H4 + KBr + H2O

Potassium carbonate, K2CO3

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 K2SO4·K2SO4 is then heated with CaCO3 and carbon.
KCl + K2SO4  KHSO4 + HCl
KHSO4 + KCl  K2SO4 + HCl
K2SO4 + CaCO3 + 2C  K2CO3 + CaS + 2CO2
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 K2Co 3 adn Na2CO3 is used as a fusion mixture in
laboratory.

COMPOUNDS OF MAGNESIUM
Magnesium Oxide, MgO, (Magnesia)
Preparation: It can be prepared by following reactions.
2Mg + O2 Burning
 2MgO
Mg(OH)2 Heated
 MgO + H2O
2Mg(NO3)2 Heated
 2MgO + 4NO2 + O2
MgCO3 Heated
 MgO + CO2

Properties: It is a light infusible white powder. It fuses at 2800oC. It is slightly soluble in water and forms
magnesium hydroxide.
MgO + H2O  Mg(OH)2

It is basic in nature. It reacts with acids to form corresponding salts.

MgO + 2HCl  MgCl2 + H2O
MgO + H2SO4  MgSO4 + H2O
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 sorel’s cement. The composition is MgCl2.5MgO.xH2O.
Magnesium Hydroxide, Mg(OH)2
Preparation: It is prepared by dissolving magnesium oxide in water or by treating magnesium salt with an
alkali.
MgO + H2O  Mg(OH)2
MgCl2 + Ca(OH)2  Mg(OH)2 + CaCl2
MgCl2 + 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 NH4Cl.

Mg(OH)2 + 2NH4Cl  MgCl2 + 2NH4OH

Uses: A suspension of Mg(OH)2 in water is used in medicine as an antacid under the name, milk of
magnesia.

Magnesium Carbonate, MgCO3

It is found in nature as magnesite (MgCO3) and dolomite (MgCO3.CaCO3).

Preparation: It can be prepared by adding sodium bicarbonate to a hot solution of magnesium salt.
MgSO4 + 2NaHCO3  MgCO3 + Na2SO4 + H2O + CO2

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 3MgCO3.Mg(OH)2.2H2O is
obtained. It is known as magnesia alva. It is suspended in water and CO2 is passed when magnesium
bicarbonates known as fluid imagines is formed. The solution is boiled when normal magnesium carbonate
separates out.
2MgSO4 + 2Na2CO3 + H2O  MgCO3.Mg(OH)2 + 2Na2SO4 + CO2
MgCO3.Mg(OH)2 + 3CO2 + H2O  2Mg(HCO3)2
Mg(HCO3)2  MgCO3 + CO2 + H2O

Properties: It is a white powder, insoluble in water. It dissolves readily in water containing excess of
carbon dioxide.
MgCO3 + CO2 + H2O  Mg(HCO3)2
It dissolves in acids foming salts with evolution of CO2.
MgCO3 + 2HCl  MgCl2 + H2O + CO2
MgCO3 + H2SO4  MgSO4 + H2O + CO2
On heating, it decomposes with evolution of CO2.
MgCO3  MgO + CO2
It forms double carbonates with alkali carbonates.
MgCO3 + Na2CO3  Na 2 Mg (CO 3 ) 2
So lub le

Magnesium chloride, MgCl2 .6H2O

It occurs as mineral carnallite, KCl.MgCl2.6H2O and bischrofite, MgCl2.H2O. It is found in sea water,
mineral springs, etc.

Preparation: (a) It is extracted from carnallite mineral. The mineral is fused and cooled to 176oC when
whole of KCl is deposited while MgCl2.6H2O remains in the fused state.
(b) It can also be obtained by dissolving Mg, MgO, Mg(OH)2 or MgCO3 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, MgSO4 .7H2O

It occurs in nature as minerals kiesserite (MgSO4 .H2O), epsom salt (MgSO4.7H2O) and kainite
(KCl.MgSO4.3H2O).

Preparation: It is formed by reacting magnesite (MgCO3) or dolomite with dilute sulphuric acid.
MgCO3 + H2SO4  MgSO4 + H2O + CO2
MgCO 3 .CaCO 3 + 2H SO  MgSO + CaSO 4 + 2CO + 2H O
Dolomite 2 4 4 ( Inso lub le ) 2 2

It is commercially prepared by boiling kiesserite mineral in water. The crystals are obtained when the
solution is cooled.
MgSO4.H2O + 6H2O  MgSO4.7H2O

Properties: It is a colourless crystalline compound, soluble in water. The crystals are efflorescent and
bitter in taste. It is isomorphous with ZnSO4.7H2O. It forms double sulphates with alkali metal sulphates,
K2SO4.MgSO4.6H2O (Schonite).

Heating effect: When heated to 150oC, it changes to monohydrate. On further heating, it becomes anhdrous
at 200oC. On strong heating, it decomposes into MgO.

MgSO4.7H2O 150 o
C MgSO .H O 200o C MgSO  MgO + SO + 1 O 2
Strong
 4 2   4 heating 2
2
o
Magnesium sulphate is reduced by lampblack at 800 C.
2MgSO4 + C  2MgO + 2SO2 + CO2
CALCIUM
COMPOUND OF CALCIUM
Quick Lime, Slaked Lime and Lime Water
Preparation: CaCO3 CaO + CO2.
The reaction moves towards right hand direction if CO2 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 1000oC 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 + H O  Ca (OH) + Heat energy
Quick lim e 2 2
Slaked lim e
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.
0
Limestone 1000
 C
 Quick Lime  
 Slaked Lime
H 2O
( CaCO 3 ) ( CaO ) [ Ca ( OH ) 2 ]


Suspension  Suspended in water
( Milk of Lime )
Ca ( OH ) 2

 Filter
Clear Solution
( Lime water )
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 + CO2 CaCO3 + H2O
CaCl2 + Na2CO3 CaCO3 + 2NaCl
The precipitate of CaCO3 thus obtained is known as precipitated chalk.
It is a white powder, insoluble in water. It dissolves in presence of CO2 due to formation of calcium
bicarbonate.
CaCO3 + H2O + CO2  Ca(HCO3)2
Calcium Sulphate, CaSO4 ·2H2 O (Gypsum)
It is found in nature as anhydride (CaSO4) and gypsum (CaSO4·2H2O).
It can be prepared by reacting any calcium salt with either sulphuric acid or a soluble sulphate.
CaCl2 + H2SO4  CaSO4 + 2HCl
CaCl2 + Na2SO4  CaSO4 + 2NaCl

Plaster of Paris, 2CaSO4 ·H2 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 CaSO4·2H2O (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).
Setting
2CaSO 4  H 2 O   CaSO 4  2 H 2 O Hardening
  CaSO 4  2 H 2 O
Plaster of Paris H 2O
Otho  r hom bic Monoclinic

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 Keene’s cement.
(iii) When Plaster of Paris is heated at 2000C, it forms anhydrous calcium sulphate which is known as dead
plaster. It has no setting property as it takes up water only very slowly.