(iv) In view of the anomalous behaviour of

Hydrogen hydrogen, it is difficult to assign any definite

(1) Position of hydrogen in the periodic table position to it in the periodic table. Hence it is
Hydrogen is the first element in the periodic customary to place it in group I (Along with alkali
table. Hydrogen is placed in no specific group due to metals) as well as in group VII (Along with halogens).
its property of giving electron (When H  is formed) (2) Discovery and occurrence : It was
and also losing electron (When H  is formed). discovered by Henry Cavendish in 1766. Its name
hydrogen was proposed by Lavoisier. Hydrogen is
(i) Hydrogen is placed in group I (Alkali metals)
the 9th most abundant element in the earth’s crust.
as,
Hydrogen exists in diatomic state but in
(a) It has one electron in its (Outer) shell- 1s 1 triatomicstate it is called as Hyzone. Systematic
like other alkali metals which have (inert gas) ns 1 name of water is oxidane.
configuration. (3) Preparation of Dihydrogen : Dihydrogen
  
(b) It forms monovalent H ion like Li , Na  can be prepared by the following methods,
(c) Its valency is also 1. (i) By action of water with metals
(d) Its oxide (H 2 O) is stable as Li2 O, Na 2 O . (a) Active metals like Na, K react at room
temperature
(e) It is a good reducing agent (In atomic as
2M  2H2O  2MOH  H2 [M = Na, K etc.]
well as molecular state) like Na, Li
(b) Less active metals like Ca, Zn, Mg, Al
(ii) Hydrogen also resembles halogens (Group
liberate hydrogen only on heating.
VII A) as,
2 Al  3 H 2 O  Al2 O3  3 H 2
(a) It is also diatomic (H 2 ) like F2 , Cl 2 
(c) Metals like Fe, Ni, Co, Sn can react only
(b) It also forms anion H like F  , Cl   by gain when steam is passed over red hot metals.
of one electron. 3 Fe  4 H 2O(steam)  Fe3O4  4 H 2
Ferrosofer ric oxide

(c) H has stable inert gas (He) configuration
(ii) By the action of water on alkali and alkaline
as CH 4 , C 2 H 6 like halogens CCl 4 , SF2 Cl 2 etc. earth metals hydrides
(d) H is one electron short of duplet (Stable NaH  H 2O  NaOH  H 2
configuration) like F, Cl, which are also one CaH2  2H 2O  Ca(OH)2  2H 2
electron deficient than octet, F  2s 2
2p 5
; Cl  3 s 3 p
2 5
.
(iii) By reaction of metals like Zn, Sn, Al with
1
(e) (IE) of H(1312 kJ mol ) is of the same order as alkalies (NaOH or KOH)
that of halogens. 
Zn  2 NaOH  Na2 ZnO2  H 2
sod. zincate
(iii) (IE) of H is very high in comparison with 
Al  2 NaOH  H 2 O  2 NaAlO2  2 H 2
alkali metals. Also size of H  is very small compared Sod. meta - aluminate

to that of alkali metal ion. H forms stable hydride 

Si  2 NaOH  2 H 2O  Na2 SiO3  3 H 2
Silicon
only with strongly electropositive metals due to 
Sn  2 NaOH  Na2 SnO2  H 2 
smaller value of its electron affinity (72.8 kJ mol 1 ) . Tin Sod. stannite

1
 (iv) By action of metal with acids : All active
metals which lie above hydrogen in electrochemical
series, can displace hydrogen gas from dilute
mineral acids like HCl, H2SO4 .
Fe  2 HCl  FeCl2  H 2
(v) By the electrolysis of acidified water

H / Electrolysis
2 H 2O   2 H 2   O2 
At cathode At anode
(vi) Laboratory method : In laboratory, it is
obtained by action of granulated zinc with dilute
H2SO4 .
Zn  dil.H 2 SO 4  ZnSO 4  H 2
It must be noted that
(a) Pure zinc is not used for the preparation of
H2 as rate of reaction of pure Zn with dil. H2SO4 is
quite slow.
(b) Conc. H2SO4 is not used because then
gas is evolved instead of H2 .
(vii) Preparation of pure hydrogen: It can be
obtained by
(a) The action of pure dil. H2SO4 on pure
magnesium ribbon.
Mg  H2SO4  MgSO4  H2
(b) Hydrogen of high purity (> 99.95%) is
obtained by electrolysing warm aqueous barium
hydroxide between nickel electrodes.
(c) By the action of water on sodium hydride.
NaH  H2O  NaOH  H2 
(d) By the action of KOH (aq.) on aluminium.
2 Al  2KOH  2H2O  2KAlO2  3 H2 
(viii) Commercial production of dihydrogen
(a) Bosch process : In this method, water gas is
mixed with twice its volume of steam and passed
over heated catalyst Fe2O3 in the presence of a
promoter Cr2O3 or ThO2 at 773 K when CO2 and H 2
are obtained. CO2 is removed by dissolving it in
water under pressure (20-25 atm) and H2 left
undissolved is collected.
1270 K
C  H 2 O  CO  H 2

Water gas
773 K
H 2  CO  H 2 O  CO 2  2 H 2
Fe2O3 , Cr2O3
About 18% of the world’s production of H2 is
obtained from coal.
(b) Lane’s process : By passing steam over
spongy iron at 773-1050 K.
3 Fe  4 H2O  Fe3O4  4 H2
The ferrosoferric oxide (Fe3 O4 ) so produced is
reduced back to iron with water. this reaction is
known as Vivification reactions
Fe3 O4  4 H 2  3 Fe  4 H 2 O
Fe3O4  4 CO  3 Fe  4 CO2
SO2 (c) By electrolysis of water : Electrolysis of
acidified water using platinum electrodes is used for
the bulk preparation of hydrogen.
(d) From hydrocarbons : Hydrocarbons
(alkanes) react with steam at high temperature to
produce carbon monoxide and hydrogen, e.g.,
1270 K
CH 4 (g)  H 2 O(g)   CO(g)  3 H 2 (g)
Catalyst
The mixture of CO and H2 so obtained can be
converted into hydrogen as in Bosch process. About
77% of the world’s production of H 2 is obtained
from hydrocarbons.
(e) It is also produced as a by-product of the
brine electrolysis process for the manufacture of
Cl 2 and NaOH.
(4) Physical properties of dihydrogen : It is a
colourless, tasteless and odourless gas. It is slightly
soluble in water. It is highly combustible. The
Physical constants of atomic hydrogen are,
Atomic radius (pm) – 37
Ionic radius of H ion (pm) – 210
2
 Ionisation energy (kJ mol 1 ) – 1312 As a result, F2 reacts in dark, Cl 2 in the
Electron affinity (kJ mol 1 ) –72.8 presence of sunlight, Br2 reacts only upon heating
Electronegativity – 2.1 while the reaction with I2 occurs in the presence of

(5) Chemical properties of dihydrogen : a catalyst.

Dihydrogen is quite stable and dissociates into (iii) Reaction with unsaturated hydrocarbons :
hydrogen atoms only when heated above 2000 K, H2 reacts with unsaturated hydrocarbons such as
2000 K
H 2   H  H . Its bond dissociation energy is ethylene and acetylene to give saturated
very high, H 2  H  H ; H  435.9 kJ mol 1
. Due to its hydrocarbons.
Ni or Pt or Pd
high bond dissociation energy, it is not very reactive. H 2 C  CH 2  H 2    CH 3  CH 3
Ethylene 473 K Ethane
However, it combines with many elements or HC  CH  2 H 2 Ni or Pt or Pd
 CH 3  CH 3
Acetylene 473 K Ethane
compounds.
This reaction is used in the hydrogenation or
(i) Action with metals : To forms
Heat hardening of oils. The vegetable oils such as
corresponding hydrides. 2 Na  H 2   2 NaH ;
Heat
groundnut oil or cotton-seed oil are unsaturated in
Ca  H 2   CaH 2 .
nature because they contain at least one double
With transition metals (elements of d – block) bond in their molecules. Dihydrogen is passed
such as Pd, Ni, Pt etc. dihydrogen forms interstitial through the oils at about 473 K in the presence of
hydrides in which the small molecules of dihydrogen catalyst to form solid fats. The vegetable ghee such
occupy the interstitial sites in the crystal lattices of as Dalda, Rath, etc. are usually prepared by this
these hydrides. As a result of formation of process.
interstitial hydrides, these metals adsorb large Ni
Vegetableoil H 2  
 Fat
volume of hydrogen on their surface. This property (liquid)
473 K (solid)

of adsorption of a gas by a metal is called occlusion. (6) Uses of Dihydrogen

The occluded hydrogen can be liberated from the
(i) As a reducing agent
metals by strong heating.
(ii) In the hydrogenation of vegetable oils
(ii) Reaction with Non-metals
970 K
2 H 2  O 2  
 2 H 2 O
(iii) As a rocket fuel in the form of liquid H2
Fe, Mo
N 2  3 H 2   2 NH 3 (iv) In the manufacture of synthetic petrol
750 K , Pressure

Dark (v) In the preparation of many compounds

H 2  F2   2 HF
Sunlight
a) Synthesis of Ammonia by Haber's process.
H 2  Cl 2   2 HCl
673 K , Pressure N2(g) + 3H2(g) 2 NH3(g)
H 2  Br2  2HBr b) Preparation of HCl
water
673 K
H 2  I2  
 2 HI H2g  Cl2(g)  2HClg 
 2HClaq 
Pt
acid
The reactivity of halogen towards dihydrogen c) Synthesis of Methyl alcohol:
decreases as, F2  Cl 2  Br2  I2 H2  CO  H2  
ZnO.CrO
3
 CH3OH
water gas catalyst 

3
 d) In the production of vanaspathi or hydrogen. For example, if ordinary hydrogen is
Margarine: passed through acidified KMnO4 (pink in colour), its
colour is not discharged. On the other hand, if zinc
(vi) It is used in the oxy-hydrogen torch for pieces are added to the same solution, bubbles of
welding if temperature around 2500°C is required. It hydrogen rise through the solution and the colour is
is also used in atomic hydrogen torch for welding discharged due to the reduction on KMnO4 by
purposes in which temperature of the order of nascent hydrogen.
4000°C is required. KMnO4  H 2  H 2SO4  No reaction
Molecular
vii) Synthetic petrol is prepared by Fischer-Tropsch
Zn  H 2 SO 4  ZnSO4  2[H ]
process. Here Iron oxide is used to remove sulphur Nascent hydrogen

from a mixture of water gas and Hydrogen. 2KMnO4  3 H 2 SO4  10[H]  K2 SO4  2MnSO4  8 H 2O

(3) Ortho and para hydrogen : A molecule of

Different forms of hydrogen
dihydrogen contains two atoms. The nuclei of both
(1) Atomic hydrogen : It is obtained by the the atoms in each molecule of dihydrogen are
dissociation of hydrogen molecules. The atomic spinning. Depending upon the direction of the spin
hydrogen is stable only for a fraction of a second of the nuclei, the hydrogen is of two types,
and is extremely reactive. It is obtained by passing
dihydrogen gas at atmospheric pressure through an Nuclei
electric arc struck between two tungsten rods.
Ortho hydrogen Para hydrogen
The electric arc maintains a temperature
around 4000 – 4500°C. As the molecules of
dihydrogen gas pass through the electric arc, these
absorb energy and get dissociated into atoms as (i) Molecules of hydrogen in which the spins of
 2 H(g) : H  435.90 KJ mol 1
Electric
H 2 (g)   both the nuclei are in the same directions, called
arc
ortho hydrogen.
This arrangement is also called atomic
(ii) Molecules of hydrogen in which the spins of
hydrogen torch.
both the nuclei are in the opposite directions, called
Tungsten rod para hydrogen.
H
H2 Ordinary dihydrogen is an equilibrium mixture
H
of ortho and para hydrogen. Ortho hydrogen ⇌ Para
Tungsten rod
hydrogen. The amount of ortho and para hydrogen
Atomic hydrogen torch
varies with temperature as,
(a) At 0°K, hydrogen contains mainly para
(2) Nascent hydrogen : The hydrogen gas hydrogen which is more stable.
prepared in the reaction mixture in contact with the (b) At the temperature of liquefaction of air,
substance with which it has to react, is called the ratio of ortho and para hydrogen is 1:1.
nascent hydrogen. It is also called newly born
hydrogen. It is more reactive than ordinary

4
 (c) At the room temperature, the ratio of ortho
to para hydrogen is 3:1.
(d) Even at very high temperatures, the ratio of
ortho to para hydrogen can never be more than 3:1.
Thus, it has been possible to get pure para
hydrogen by cooling ordinary hydrogen gas to a very
low temperature (close to 20 K) but it is never
possible to get a sample of hydrogen containing
more than 75% of ortho hydrogen. i.e., Pure ortho
hydrogen can not be obtained.
(4) Hydrides : Hydrogen forms binary hydrides
of the type MHx or Mm Hn with
(a) All main group elements except noble gases
and probably indium and thallium.
(b) All lanthanoids and actinoids.
(c) Transition metals (Sc, Y, La, Ac, Tc, Zr, Hf
and to a lesser extent V, Nb, Ta, Cr, Cu and Zn). In
group 6 only Cr forms hydride (CrH).
Hydrides are classified into three main
categories.
(i) Saline or ionic hydrides : Most of the s-block
metals form this type of hydrides. These are non-
volatile, non-conducting crystalline solids. However,
BeH2 and MgH2 have covalent polymeric structure.
These ionic hydrides have rock-salt structure.
Thermal stability of 1st and 2nd group hydrides are in
the order;
LiH > NaH > KH > RbH > CsH
CaH2  SrH2  BaH2
BeH 2 , MgH2 and LiH have significant covalent
character.
Electrolysis of solution of saline hydride in
molten alkali halide produces H 2 at anode. Saline
hydrides react explosively with water.
NaH(s)  H2O(aq)  NaOH(aq)  H2 (g)
The fire so produced cannot be extinguished
by CO2 as it gets reduced by the hot metal hydride.
Only sand is useful, as it is a solid.
Alkali metal hydrides are used for making
LiAlH4 , NaBH4 etc. Alkali metal hydrides are also used
for the removal of last traces of water from organic
compounds.
(ii) Metallic or interstitial hydrides : Elements
of groups 3, 4, 5 (d-block) and f-block elements form
metallic hydrides. In group 6, only Cr forms hydride
(CrH). Metals of group 7, 8, 9 do not form hydrides.
This region of periodic table from group 7 to group 9
is known as hydride gap. Examples of hydrides of
group 3 to 5 are,
ScH 2 , YH 2 , YH 3 , LaH2 , LaH3 , TiH2 , ZrH2 , HfH2 , VH,
VH2 , NbH, NbH 2 , TaH
The f-block metals form hydrides of limiting
compositions of MH2 and MH3 . All these hydrides
are non-stoichiometric with variable composition
e.g.,
ZrHx (1.30  x  1.75) , TiHx (1.8  x  2.0) .
Most of these hydrides are good conductors of
electricity in solid state.
Metallic hydrides can be used to store
hydrogen especially in cars working on fuel cells.
(iii) Molecular or covalent hydrides : Hydrogen
form molecular compounds with p-block elements
(B, C, N, O, F; Si, P, S, Cl; Ga, Ge, As, Sb, Br; In, Sn, Sb,
Te, I; Tl, Pb, At). common examples of such hydrides
are CH 4 , NH 3 , H2O, HF etc. The stability of these
5
hydrides decreases down the group. For example, ber nce non-
NH 3  PH3  AsH3  SbH 3  BiH3 . In a period the radioacti
stability increases with increasing electronegativity. ve
For example, CH 4  NH 3  H2O  HF . Molecular Protiu 1
1H or 1 1 99.985 Non-
hydrides are classified as electron rich, electron m or H % radioacti
precise and electron deficient hydrides. Hydro ve
(a) Electron rich molecular hydrides : These gen
hydrides have one or more lone pairs of electrons Deute 2
1H o 1 2 0.015% Non-
around the central more electronegative element. rium rD radioacti
For example ve
   Tritiu 3
1 Ho 1 3 10 15 % Radioact
H  O H , H  N H , H F:
.. | .. m rT ive
H
Physical constants of H2 , D2 and T2
(b) Electron precise molecular hydrides :
Elements of group 14 form such hydrides. The bond Property H2 D2 T2
length increases on going down the group. A Molecular mass 2.016 4.028 6.03
common example of electron precise molecular Melting point (K) 13.8 18.7 20.63
hydrides is CH4 . Boiling point (K) 20.4 23.9 25.0
Heat of fusion (kJ mol -1) 0.117 0.197 0.250
(c) Electron deficient molecular hydrides :
These hydrides have lesser number of electrons Heat of vaporisation 0.994 1.126 1.393
-1
than that required for writing the conventional (kJ mol )

Lewis structure. A common example of such Bond energy (kJ mol -1) 435.9 443.4 446.9
molecular hydride is diborane, B2 H6 . Isotopic effect : In general chemical properties
(d) Systematic names of molecular hydrides : of isotopes are same but quantiative differences are
The systematic names of these hydrides are noticed amongst them. For example, the reaction
obtained from the name of the element and the between H 2 and Cl 2 is 13.4 times faster between
suffix –ane. For example, D2 and Cl 2 under similar conditions. Such
differences in chemical properties, which are due to
PH3 H 2O NH 3
Phosphane oxidane ozane difference in the mass numbers of isotopes is
Isotopes of Hydrogen known as isotopic effect.
Isotopes are the different forms of the same Water
element, which have the same atomic number but Water is the oxide of hydrogen. It is an important
different mass numbers. component of animal and vegetable matter. Water
Isotopes of hydrogen constitutes about 65% of our body. It is the principal
constituent of earth’s surface.
Name Sym Ato Mass Relativ Nature
bol mic num e radioacti (1) Structure : Due to the presence of lone
pairs, the geometry of water is Lone Pair of
num ber abunda ve or .. Electron
..

:O:
H 104.5o H

6
distorted and the H  O  H bond angle is 104.5°, Molecular mass 18.015 20.028
which is less than the normal tetrahedral angle Maximum density 1.000 1.106
(109.5°). The geometry of the molecule is regarded 3
(g cm )
as angular or bent. In water, each O  H bond is
polar because of the high electronegativity of Melting point (K) 273.2 276.8
oxygen (3.5) in comparison to that of hydrogen Boiling point (K) 373.2 374.4
(2.1). The resultant dipole moment of water Heat of 6.01 6.28
molecule is 1.84D. fusion (kJ mol1 ) at
In ice, each oxygen atom is tetrahedrally
273K
surrounded by four hydrogen atoms; two by
Heat of vaporisation 40.66 41.61
covalent bonds and two by hydrogen bonds. The
(kJ mol 1 ) at 373K
resulting structure of ice is open structure having a
number of vacant spaces. Therefore, the density of Heat of formation – 285.9 – 294.6
1
(kJ mol )
ice is less than that of water and ice floats over
water. It may be noted that water has maximum Ionisation constant 1.008  1014 1.95  1015
density (1g cm 3 ) at 4°C (277 K). (4) Chemical properties : Water shows a
(2) Heavy water : Chemically heavy water is versatile chemical behaviour. It behaves as an acid,
deuterium oxide (D2 O) . It was discovered by Urey. a base, an oxidant, a reductant and as ligand to
It is obtained as a by-product in some metals.
industries where H 2 is produced by the electrolysis (i) Dissociation of water : Water is quite stable
of water. and does not dissociate into its elements even at
Heavy water (D2O) is used (a) as a moderator high temperatures. Pure water has a small but
and coolant in nuclear reactors (b) in the study of measurable electrical conductivity and it dissociates
mechanism of chemical reactions (c) as a starting as, H 2 O  H 2 O ⇌ H 3 O   OH 
Hydronium ion
material for the preparation of a number of
deuterium compounds, e.g., KW  1.0  10 14 mol 2 L2 at 298K
SO 3  D2 O  D2 SO 4
Deuteriosulphuric acid (ii) Amphoteric nature : Water can act both as
Al4 C3  12 D2 O  3CD4  4 Al(OD)3 an acid and a base and is said to be amphoteric.
Deuteromethane

CaC2  2 D2 O  C2 D2  Ca(OD)2
However, water is neutral towards litmus and its pH
Deuterioacetylene
is 7.
(3) Physical properties : Water is colourless,
(iii) Oxidising and reducing nature : Water can
odourless and tasteless liquid at ordinary
act both as an oxidising and a reducing agent in its
temperature.
chemical reactions. e.g.
At 273K water is in equilibrium with ice and 2 Na  2H 2 O  2 NaOH  H 2
Oxidi sin g agent
vapour this point is known triple point.
2 F2  2H 2 O  4 HF  O2
Some physical constants of H2O and D2O at 298 K Re ducing agent

Constant Ordinary Heavy (iv) Hydrolytic reactions : Water can hydrolyse

water H2O water D2O many oxides, halides, hydrides, carbides, nitrides,

7
phosphides, carbonates etc. to give an acid or a
base or both as shown below :
SO2  H 2O  H 2 SO3
Mg3 N 2  6 H 2 O  3 Mg(OH)2  2 NH 3
CaH 2  2H 2 O  Ca(OH)2  2H 2
CaO  H 2 O  Ca(OH)2
Na2 CO3  2H 2 O  2 NaOH  H 2 CO3
SiCl4  4 H 2 O  Si(OH)4  4 HCl
Ca3 P2  6 H 2 O  3Ca(OH)2  2PH3
CaC2  2H 2 O  Ca(OH)2  C2 H 2
(v) Water forms hydrates with metal salts :
There are three main types of hydrates.
(a) Compounds in which water molecule are
co-ordinated to the metal ion (complex compounds)
[Ni(OH 2 )](NO 3 )2 , Fe(OH2 )6 ]Cl3 etc.
(b) Compound in which water molecule may be
hydrogen bonded to oxygen to form oxo-anion. For
example in CuSO 4 .5 H 2 O , 4 molecules of water are
co-ordinated to Cu 2 while the fifth molecule is
hydrogen bonded to SO42 ion.
(c) In some compounds, water molecule
occupies, interstitial sites in the crystal lattice e.g.,
BaCl2 .2 H 2 O .
(5) Hard and Soft water
Water which produces lather with soap
solution readily is called soft water. e.g. distilled
water, rain water and demineralised water.
Water which does not produce lather with
soap solution readily is called hard water. e.g. sea
water, river water, well water and tap water.
(i) Cause of hardness of water : The hardness
of water is due to the presence of bicarbonates,
chlorides and sulphates of calcium and magnesium.
Hard water does not produce lather because
the cations (Ca 2 and Mg2 ) present in hard water react
with soap to form insoluble precipitates,
M 2  2C17 H 35 COONa  (C17 H 35 COO)2 M  2 Na 
From hard water Sodium stearate(soap ) Metal stearate(PPt.)
Where M = Ca or Mg
Therefore, no lather is produced until all the
calcium and magnesium ions are precipitated. This
also results into wastage of lot of soap.
(ii) Type of hardness of water : The hardness
of water is of two types,
(a) Temporary hardness : This is due to the
presence of bicarbonates of calcium and
magnesium. It is also called carbonate hardness.
(b) Permanent hardness : This is due to the
presence of chlorides and sulphates of calcium and
magnesium. It is also called non-carbonate
hardness.
(iii) Softening of water : The process of the
removal of hardness from water is called softening
of water.
(a) Removal of temporary hardness : It can be
removed by the following methods,
• By boiling : During boiling, the bicarbonates
of Ca and Mg decompose into insoluble carbonates
and give CO2 . The insoluble carbonates can be
removed by filtration.
Heat
Ca(HCO 3 )2   CaCO 3  CO 2  H 2 O
Cal. bicarbonate PPt.
Heat
Mg(HCO 3 )2   MgCO3  CO 2  H 2 O
Mag. bicarbonate PPt.
• Clark’s method : This process is used on a
commercial scale. In this process, calculated amount
of lime Ca(OH)2 is added to temporary hard water.
Ca(HCO 3 )2  Ca(OH)2  2CaCO 3  2 H 2 O
Soluble Lime Insoluble
Mg(HCO 3 )2  Ca(OH 2 )  MgCO3  CaCO 3  2 H 2 O
Soluble Lime (Insoluble)
(b) Removal of permanent hardness :
Permanent hardness can be removed by the
following methods,
8
 • By washing soda method : In this method, Na 2 O2  H 2 SO 4  Na 2 SO 4  H 2 O2

water is treated with a calculated amount of
washing soda (Na 2 CO 3 ) which converts the chlorides
and sulphates of Ca and Mg into their respective
carbonates which get precipitated.
(ii) By the action of sulphuric acid or
phosphoric acid on hydrated barium peroxide
BaO2 .8 H 2O
(a) BaO2 .8 H2O  H2SO4  BaSO4  H2O2  8 H2O

CaCl2  Na 2 CO 3  CaCO3  2 NaCl

ppt .
MgSO4  Na 2 CO 3  MgCO3  Na 2 SO 4
ppt.
• Permutit method : This is a modern method
employed for the softening of hard water. hydrated
sodium aluminium silicate (Na 2 Al2 Si2 O8 .xH 2 O) is
called permutit. These complex salts are also known
as zeolites.
The permutit as loosely packed in a big tank
over a layer of coarse sand. Hard water is
introduced into the tank from the top. Water
reaches the bottom of the tank and then slowly
rises through the permutit layer in the tank. The
cations present in hard water are exchanged for
sodium ions. Therefore this method is also called
ion exchange method.
Na 2 Z  Ca 2  CaZ 2 Na 
Sodium (From hard Cal
zeolite water) zeolite
It must be noted that anhydrous barium
peroxide does not react readily with sulphuric acid
(because a coating of insoluble barium sulphate is
formed on its surface which stops further action of
the acid). Therefore, hydrated barium peroxide,
BaO2 .8 H 2O must be used.
(b) 3 BaO2  2H3 PO4  Ba3 (PO4 )2  3 H2O2
Ba3 (PO4 )2  3 H2SO4  3 BaSO4  2H3 PO4
Phosphoric acid is preferred to H2SO4 because
soluble impurities like barium persulphate (from
BaO2 .8 H2O  H2SO4 ) tends to decompose H2O2 while
H3 PO4 acts as preservative (negative catalyst) for
H2O2 .
(iii) Industrial method : On a commercial scale,
H 2 O2 can be prepared by the electrolysis of 50%
H 2 SO 4 solution. In a cell, peroxy disulphuric acid is
formed at the anode.
2 H 2 SO 4    H 2 S 2 O8 (aq.) H 2 (g)
Elecrolysis
Peroxy disulphuric
acid

Na 2 Z  Mg2  MgZ  2 Na  This is drawn off from the cell and hydrolysed
Sodium (From hard Magnesium
zeolite water) zeolite with water to give H 2 O2 .
where Z  Al2 Si 2 O8 . xH 2 O H 2 S 2 O8  2 H 2 O  2 H 2 SO 4  H 2 O2 The resulting
solution is distilled under reduced pressure when
H 2 O2 gets distilled while H2SO4 with high boiling
Hydrogen peroxide
point, remains undistilled.
(iv) By redox process : Industrially H2O2 is
Hydrogen peroxide (H 2 O2 ) was discovered by
prepared by the auto-oxidation of 2-
French chemist Thenard.
alkylanthraquinols. The process involves a cycle of
(1) Preparation : It is prepared by reactions. The net reaction is the catalytic union of
(i) Laboratory method : In laboratory, H 2 O2 is H 2 and O 2 to give H2O2 .
prepared by Merck’s process. It is prepared by OH O
adding calculated amounts of sodium peroxide to C2H5 C2H5
O2
ice cold dilute (20%) solution of H 2 SO 4 . + H2O2

OH O
2-Ethylanthraquinol 2-Ethylanthraquinone
H2/Pd

9
 (iv) Bleaching action : H 2 O2 acts as a
bleaching agent due to the release of nascent
oxygen.
H 2 O2  H 2 O  O
The H2O2 formed (about 1%) is extracted with
Thus, the bleaching action of H 2 O2 is due to
water and concentrated.
oxidation. It oxidises the colouring matter to a
(2) Physical properties
colourless product, Colouring matter +O  Colour
(i) Pure hydrogen peroxide is a pale blue
less matter.
syrupy liquid.
H 2 O2 is used to bleach delicate materials like
(ii) It freezes at – 0.5°C and has a density of 1.4
ivory, silk, wool, leather etc.
in pure state.
(v) Acidic nature : Anhydrous hydrogen
(iii) Hydrogen peroxide is diamagnetic.
peroxide is acidic in character (Ka  1.55 1012 at 298
(iv) It is more highly associated via hydrogen
K). its dissociation in aqueous solution may be given
bonding than water.
as
(v) Although it is a better polar solvent than H2O2  H2O  H3O  HO2
H2O . However, it can’t be used as such because of
It forms two types of salts
strong autooxidation ability. NaOH  H 2O2  NaHO2  H 2O
(vi) Dipole moment of H2O2 is 2.1 D. Sod. hydroperox ide
(Acidicsalt)

(3) Chemical properties 2 NaOH  H 2O2  Na2O2  2 H 2O

Sod. peroxide
(Normal salt)
(i) Decomposition : Pure H 2 O2 is an unstable
liquid and decomposes into water and O 2 either (vi) Addition reactions : Hydrogen peroxide is
capable of adding itself to ethylenic linkage.
upon standing or upon heating,
CH 2 CH 2OH
2 H 2 O2  2 H 2 O  O2 ; H  196.0 kJ ||  H 2 O2  |
CH 2 CH 2OH
(ii) Oxidising nature : It is a powerful oxidising Ethylene Ethylene glycol

agent. It acts as an oxidising agent in neutral, acidic (4) Structure of H2O2 : Hydrogen peroxide is
or in alkaline medium. e.g. 2KI  H 2 O2  2KOH  I2 non-linear, non-planar molecule. It has a open book
[In neutral medium] structure. The O  O  linkage is called peroxy
2 FeSO4  H 2 SO 4  H 2 O2  Fe2 (SO 4 )3  2H 2 O [In linkage. The structure is shown below.
(111.5)° (90.2)°
acidic medium]
H H
MnSO4  H 2 O2  2 NaOH  MnO2  Na 2 SO 4  2 H 2 O O O
147.5 pm (94.8)° 145.8 pm (101.9)°
[In alkaline medium]
H H
(iii) Reducing nature : H 2 O2 has tendency to 95.0 pm O 98.8 pm O

take up oxygen from strong oxidising agents and In gas phase In solid phase (110 K)

thus, acts as a reducing agent,

H 2 O 2  O  H 2 O  O 2 . It can act as a reducing agent
From oxidising
agent
(5) Concentration of H2O2 : Dilute H2O2 is
in acidic, basic or even neutral medium. concentrated to about 50% by slow evaporation on
In acidic medium, H 2 O2  2H   O2  2e  a water bath. It is further concentrated to 90% in a
vacuum desiccator using conc. H2SO4 as dehydrating
In alkaline medium,
agent. Further concentration to 99% is obtained by
H 2 O2  2OH   2H 2 O  O2  2e 

10
distillation under reduced pressure. Last traces of containing CN  ions. H 2O2 oxidises CN  ions to
moisture in 99% of H2O2 are removed or anhydrous harmless products.
H2O2 is obtained by cooling it to 263 K in a cold bath
of ether and dry ice followed by seeding with a few
 Hydrogen forms more compounds than even
crystals of solid H2O2 when needle-shaped crystals
of 100% H2O2 separate out. These crystals are carbon.
removed, dried and melted to get 100% H2O2 .  Metals like Pd, Pt, Au etc., have the property of
(6) Storage of H2O2 : H2O2 is not stored in glass absorbing large quantity of hydrogen at normal or
bottles since the alkali metal oxides present in glass higher temperature. Colloidal Pd can absorb 2950
catalyse its decomposition. It is, therefore, stored in times its own volume of hydrogen and Pd metal can
paraffin wax coated glass, plastic or teflon bottles.
absorb 900 times its own volume of hydrogen.
Small amounts of acid, glycerol, alcohol, acetanilide
and H3 PO4 are often used as stablizers to check its This phenomenon is known as occlusion of
decomposition. hydrogen. the occlusion property of these metals is
Uses of hydrogen peroxide in the order
(i) For bleaching delicate articles like wool,
hair, feather, ivory, etc. Colloidal Palladium > Palladium > Platinum > Gold >
(ii) For restoring colour of old lead paintings Nickel.
whose white lead has blackened due to formation  In solids, water molecules can also be present
of PbS by H2S of atmosphere. Hydrogen peroxide
as zeolite water and clathrate water.
converts the black lead sulphide to white lead
sulphate  Ice is a good thermal insulator.
(iii) As an aerating agent in production of  30% H2O2 is called perhydrol. Its volume
spong rubber. strength is 100 and molarity is 8.8.
(iv) As an antiseptic and germicide for washing
wounds, teeth and ears, under the name of
perhydrol.
(v) In the manufacture of sodium perborate,
sodium percarbonate. These are used in high quality
detergents.
(vi) As an antichlor.
(vii) As an oxidant for rocket fuel.
(viii) In the detection of Ti, V and Cr ions with
which it forms peroxides of characteristics colours.
(ix) In the production of epoxides, propylene
oxide and polyurethanes.
(x) In the synthesis of hydroquinone,
pharmaceuticals (cephalosoporin) and food
products like tartaric acid.
(xi) For pollution control of domestic effluents
where it restores the aerobic conditions of sewage
wastes. For pollution control of industrial effluents

11