INTRODUCTION

Hydrogen is the first element in the periodic table and is also the lightest element known. Its
atomic form exists only at high temperatures. In the normal elemental form, it exists as a diatomic
molecule, i.e.
2
H
.
Unique Position of Hydrogen in the periodic table
A proper position could not be assigned to hydrogen either in the Mendeleevs periodic table or
Modern periodic table because of the following reason!
In some properties, it resembles alkali metals and in some properties it resembles halogens. "o
hydrogen can be placed both in group # and group #$ with alkali metals and halogen
respectively.
Resemblance ith al!ali metals
"# $lectronic configuration#
Hydrogen contains one electron in the valence shell like alkali metals
H %
#
#s
&i % [ ]
#
He 2s
Na % [ ]
#
%e &s
' % [ ]
#
Ar 's
Rb % [ ]
#
(r )s
(# $lectropositi)e Character
*ike alkali metal, hydrogen also loses its only electron to form hydrogen ion, i.e, H
+
# +
#s #s
H H e
+
+

2 2 , # 2 2 ,
#s 2s 2p &s #s 2s 2p
%a %a e
+
+

*# O+idation state
*ike alkali metals, hydrogen exhibits an oxidation state of -# in its compounds.
Hydrogen chloride "odium chloride .otassium chloride
H /l %a /l ( 0r
+ + +
,# Reducing agent
Alkali metals act as reducing agents because of their tendency to lose valence electron.
Hydrogen is also a very good reducing agent as evident from the following reactions!
& ' 2 2
1e 2 'H &1e 'H 2

+ +
2 2
/u2 H /u H 2

+ +
-# Combination ith electronegati)e elements
3ust like alkali metals hydrogen combines with electronegative elements such as halogen,
oxygen, sulphur, etc to form compounds with similar formulae
2 2
2 2
Halides 2xides "ulphides
H/l H 2 H "
%a/l %a 2 %a "
FIITJEE Ltd. ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Term.), Ne !e"hi # $%, &h ' (%)% *$)(, (%+%*%(%, (%)* ,$-(, (%*$*+,+ .a/ ' (%*$0+,(
Difference from .l!ali /etals
"# Ioni0ation enthalpy
Ioni4ation enthalpy of hydrogen 5#&#2 k3 mol
#
6 is very high in comparison with the ioni4ation
enthalpy of alkali metals.
(# $+istence of H
+
It has been established that H
+
ion does not exist freely in a a7ueous solution. 8his is because of
the fact that has a very small si4e ( )
&
#.) #+ pm

as compared to normal atomic and ionic si4e
5which range from )+ to 22+ pm6. 8hus it exists in a7ueous solution in the form of hydrated proton
with a formula,
9 '
H 2
+
. However, for the sake of simplicity hydrated proton is represented by
hydronium ion,
&
H 2
+
.
2n the other hand, the alkali metal ions mostly exist as hexahydrated ions.
*# Difference in halides
Hydrogen halides are different from the halides of alkali metals although they have similar
molecular formulae. 1or example
5i6 .ure H/l is a covalent compound while %a/l is an ionic compound.
5ii6 H/l is a gaseous compound while %a/l is a solid at ordinary temperature.
Resemblance 1ith Halogens
"# $lectronic configuration#
3ust like halogens, hydrogen needs one electron to attain the configuration of nearest noble gas.
#
H ! #s
2 2 )
1 ! #s 2s 2p
2 2 , 2 )
/l ! #s 2s 2p &s &p
(# .tomicity#
*ike halogens, hydrogen also exists in a diatomic state. 8he atomicity of hydrogen as well as
halogens is two.
*# $lectrochemical nature#
:uring electrolysis of *iH, /aH2, etc, in molten state hydrogen is evolved at the anode indicating
its electronegative nature. In this respect, hydrogen shows resemblance with halogens which are
also liberated at the anode during electrolysis.
,# O+idation state#
3ust like halogens, hydrogen also exhibit state of ;# in some of its compounds such as metal
hydrides.
# #
%a H %a /l
+ +

-# Combination ith al!ali metals#
3ust like halogen, hydrogen also combines with alkali metals to form salts with similar formulae.
2
%aH *iH /aH
2
%a/l *i/l /a/l
2# Combination ith non3metals
3ust like halogens hydrogen also react with non;metals such as carbon, silicon, germanium, etc,
to form covalent compounds.
' ' '
Halides ! //l "i/l <e/l
' ' '
Hydrides ! /H "iH <eH
4# Ioni0ation energy
Ioni4ation energy of hydrogen is comparable to the ioni4ation energies of halogens as shown
below!
=lement ! H 1 /l 0r
Ioni4ation energies 5
#
k3 mol

6 ! #&#2 #,># #2)) ##2#

Difference from halogens
"# &ess tendency of hydride 5 formation#
Although hydrogen forms hydride ion 5H

6 like halogens, yet its tendency to form hydride ion is

very less in comparison with the halogens. It is 7uite clear from the fact that halogens form
halides with very large number of metals but hydrogen form hydrides with only a small number
metals like sodium and calcium, etc.
(# .bsence of unshared electrons
8here is no unshared pair of electron in hydrogen molecule ( )
2
H
whereas halogen molecules
have six unshared electron pairs as shown below!
H H /l /l 1 1

*# Nature of o+ides#
8he oxides of halogen are acidic in nature whereas oxide of hydrogen is neutral
H
2
2
%eutral oxide
/l
2
2
$
,I
2
2
)
Acidic oxides
,# Nature of compounds
8he compounds of hydrogen with halogens, i.e. hydrogen halides 5H1, H/l, H0r, HI6 are low
boiling covalent compounds whereas alkali metal halides 5*i1, %a/l, (0r, /sI6 are high melting
ionic solids.
Conclusion
1rom the above discussion, it is 7uite evident that there is a marked resemblance in the
properties of hydrogen with alkali metals as well as with halogens. 8herefore, it is very difficult to
place it either with the elements of group # or those of group #$. In other words position of
hydrogen in the periodic table is anomalous. It is due to this reason hydrogen is some times
called rogue element.
I6OTOP$6 O7 H8DRO9$N
It has been found by mass spectrograph that hydrogen has three isotopes namely? protium,
deuterium and tritium. 8he relative abundance of three isotopes of hydrogen is as under
# 2 &
# # #
Isotopes H ! H ! H
2 #$
Abundance # ! #.) #+ ! # #+


:a; Protium or hydrogen
It is represented by the symbol H. Its atomic number is # and mass number is also #. It has one
proton 5but no neutron6 in its nucleus and one electron in its #s orbital. %aturally occurring
hydrogen contains 99.9>)@ of this isotopes.
:b; Deuterium or hea)y hydrogen
It is represented by the symbol : or
2
#
H. Its atomic number is # and mass number is 2. It has one
proton and one neutron in its nucleus and one electron in its #s orbital. %aturally occurring
hydrogen has +.+#)@ of this isotopes mostly in the form of H:.
:c; Tritium
It is represented by the symbol 8 or
&
#
H. Its nucleus has one proton and two neutrons and there is
one electron in its #s orbital. It is an extremely rare isotope. 2ut of
#$
#+ molecules of ordinary
hydrogen there is Aust one molecule of tritium. 8his isotope of hydrogen is radioactive in nature
and emits low energy ; particles ( )
#B 2
t #2.&&

PROTIU/
:Non 5 Radioacti)e
<<#<=->

DUT$RIU/
:Non 5 Radioacti)e;
?#?"->

TRITIU/
:Radioacti)e;


It may be noted that three isotopes of hydrogen have same chemical properties because of the
same electronic configuration
#
#s . However due to different mass numbers they have different
rates of chemical reactions. 1or example, reaction between protium and chlorine is #&.' times
faster than that between deuterium and chlorine. "imilarly electrolysis of ordinary water ( )
2
H 2

occurs more rapidly than of heavy water ( )
2
: 2
.:ifference in properties arising due to the
difference in mass number is referred to as isotopic effect.
Uses of Tritium
8ritium is used to make thermonuclear devices and for carrying out researches in fusion reactions
as a means of producing energy. 8ritium gas is usually stored by making
&
C8
, which on heating to
,$& ( releases
2
8
.
Illustration 1. The decay product of tritium is
(A) 1H
1
(B) 1H
2
(C) 2He
3
(D) 2He
4
Solution: 5/6
& & +
# #
2
H He e

+
Exercise 1. Which of the following statements concerning protium, deuterium and
tritium is not true?
(A !he" are isotopes of each other
(# !he" ha$e similar electronic configurations
(% !he" exist in the nature in the ratio 1:&:'
(( !heir atomic masses are in the ratio 1:&:'
DIH8DRO9$N@ H( /O&$CU&$#
5i6 8he term dihydrogen is used for the mixture of diatomic molecules such as
2 2
H , :
and H:
containing H and : atoms with respect to their natural abundance.
5ii6 1or diatomic molecules containing only protium atoms ( )
2
H
the term used is diprotium.
5iii6 1or diatomic molecules containing only deuterium atoms ( )
2
:
, the correct term is
dideuterium.
Occurrence of Hydrogen
Hydrogen is most abundant element in the universe. About half the mass of sun and stars is
accounted for by hydrogen. 3upiter and "aturn mostly consist of hydrogen. 2n earth, it occurs in
free state in small traces in volcanic and natural gases. However in combined state it is widely
distributed as water.
Preparation of Dihydrogen
"ome of the important methods of preparation of dihydrogen are given below!
"# Ay the action of ater on metals#
Darious metals react with water at different temperatures to
displace hydrogen from it. 1or example,
:a; Dery active metals like %a, (, /a react at room temperature to form H2 along with
corresponding hydroxides.
2 2
2%a 2H 2 2%a2H H + +
2 2
2( 2H 2 2(2H H + +
( )
2 2
2
/a 2H 2 /a 2H H + +
Eeaction with these metals is highly vigorous and H2 liberated immediately catches fire which
can cause accident. In order to slow down the reaction, amalgam of these metals with
mercury are used.
:b; Metals like Mg, Al, Fn, etc, react with water at boiling temperature to form
2
H
and
corresponding oxides.
Heat
2 2
Mg H 2 Mg2 H + +
Heat
2 2
Fn H 2 Fn2 H + +
Heat
2 2 & 2
2Al &H 2 Al 2 &H + +
:c; Metals like 1e, "n, etc, react with steam at high temperature.
#+++(
2 & ' 2
Magnetic oxide of iron
&1e 'H 2 1e 2 'H + +
8he reaction between iron and steam is used for the large scale preparation of dihydrogen by
&aneBs Process.
(# Ay the action of acids on metals
Metals lying above hydrogen in the activity series displace hydrogen by reaction with dilute H/l or
dilute
2 '
H "2
.
2 2
1e 2H/l 1e/l H + +
2 2
Mg 2H/l Mg/l H + +
In the laboratory, dihydrogen is prepared by the treatment of 4inc granules with dil.
2 '
H "2
.
*# Ay the action of strong al!alies on metals
Metals like Fn, "n or Al react with strong alkalies such as %a2H or (2H liberating H2 gas
Heat
2 2 2
"odium meta aluminate
2Al 2%a2H 'H 2 2%aAl2 &H + + +

2 2 & 2
"odium stannate
"n 2%a2H 'H 2 %a "n2 2H + + +
2 2 2
"odium4incate
Fn %a2H %a Fn2 H

+ +
,# $lectrolysis of ater
:ihydrogen of high degree of purity is prepared by the electrolysis of water in the presence of
small amount of acid or base.
=lectrolysis
2 2 2
H
2H 2 2H 2
+
+
&aboratory Preparation of Dihydrogen
In the laboratory, dihydrogen is prepared by the action of diluted sulphuric acid on granulated 4inc
according to the arrangement shown in the figure
2 ' ' 2
Fn dil.H "2 Fn"2 H + +
Conc#
gas
Aeehi)e 6helf
9ranulated Cinc
1oulfBs
Aottle
Thistle
7unnel
dil#
1ater
Illustration &. Why conc.
2 '
H "2
and pure n is not used in preparation of dihydro!en"
Solution: 5i6 /oncentrated
2 '
H "2
is not used because it acts as acid as well as oxidi4ing
agent and conse7uently gets reduced during the process to liberated
2
"2

gas
2 ' ' 2 2
Fn 5conc.6H "2 Fn"2 2H 2 "2 + + +
5ii6 .ure 4inc is not used in the preparation of dihydrogen because it is non;
porous in nature, and therefore, the reaction between Fn and
2 '
H "2
is slow.
8he presence of impurities, however, makes 4inc porous, which helps in
constituting electrochemical couple and speeds up the reaction.
Exercise &. )"drogen has three isotopes, the num*er of possi*le diatomic molecules
will *e
(A ' (# +
(% , (( 1&
Commercial Preparation of Dihydrogen
7rom steam and ater gas3 &aneBs process
:ihydrogen is manufactured by passing alternate currents of steam and water gas over red hot
iron at about #+2);#+$) (. 8he method, in fact, consists of two stages.
:a; O+idation stage
It involves passing of super heated steam over iron fillings heated to about #+2)G#+$)(. Iron
gets oxidi4ed to
& '
1e 2
and in turn it reduces water to dihydrogen gas.

( )
2 & ' 2
Magnetic oxide of iron
&1e 'H 2 g 1e 2 'H

+ +

1ater gas
6team
Porous Iron
7urnace


:b; Reduction stage#
Hhen whole of iron is oxidi4ed to
& '
1e 2
, the supply of steam is cut off and stream of water gas
( )
2
/2 H +
is passed so as to cause reduction of
& '
1e 2
to back to iron.
1e
&
2
'
- 2H
2
-/2 &1e - 2H
2
2 - /2
2
Hater gas

8he oxidation and reducing periods are alternatively carries out using two or more furnaces.
AoschBs Process
8he maximum 7uantity of commercial dihydrogen is prepared by this method. It involves the
following steps!
:a; Preparation of ater gas#
It is prepared by the action of steam with red hot coke
( ) ( ) ( )
#2$+
2 2
water gas
/ H 2 g /2 g H g + +
1 4 2 4 3
Hater gas also be obtained by action of steam on hydrocarbons in the presence of catalyst. 8his
process is also called steal reforming of h"drocar*ons
( ) ( )
#2$+(
n 2n 2 2 2
Hater gas
/ H nH 2 g n/2 2n # H
+
+ + +
1 4 44 2 4 4 43
( ) ( ) ( )
#2$+(
& > 2 2 /atalyst
/ H &H 2 g &/2 g $H g + +
:b; 6eparation of Hydrogen#
8he water gas formed by any of the above methods, is mixed with steam and is passed over
heated
2 &
1e 2
and
2 &
/r 2
at $$+( when /2 is oxidi4ed to
2
/2
. <aseous mixture of
2
/2
and
2
H

is then bubbled into cold water under pressure when
2
/2
dissolves leaving behind dihydorgen
gas which escape out.
( )
2 &
2 &
1e 2
2 2 2 2 /r 2
H /2 H 2 g /2 2H + + +
8his reaction is called ater gas3shift reaction.
$lectrolysis of 1ater
8his process involves the electrolysis of acidified or alkalined water. In general, the electrolysis is
carried out using iron as cathode, nickel coated iron as anode and #);2+@ %a2H solution as
electrolyte. 8he reaction taking places are
Cathode% Eeduction of water occurs
2 2
2H 2 2e 2H 22H

+ +
.node% 2xidation of 2H occurs

2 2
#
22H H 2 2 2e
2

+ +
Properties of Dihydrogen
Physical Properties
#. It is colourless, tasteless, odourless gas.
2. It has extremely low solubility in water. "ince its molecules are non;polar.
&. Its density is approximately #B'
th
that of air. "o lightest substance known.
'. It can be li7uefied at high pressures and very low temperature.
). It is highly combustible and should be handled with care.
Chemical Properties
0ecause of high dissociation energy 5'&).9 k3
#
mol

6 dihydrogen is not very reactive. However, it

forms compounds with large number of elements under appropriate experimental conditions.
"ome of the chemical properties are!
"# Neutral character
It is neutral to litmus.
(# Combustibility
It is highly combustible gas. It burns in air with a pale blue flame to form water.
( ) ( ) ( )
2 2 2
2H g 2 g 2H 2 + l
*# Reaction ith metals#
It reacts with metals like %a, /a, *i, etc, to form respective hydrides. In such reactions it ac7uires
the oxidation state of ;# and acts as an oxidi4ing agent.
)2)(
2
2%a H 2%aH +
)2)(
2 2
/a H /aH +
In case of metals like .t, .d, %i, etc, hydrogen forms interstitial hydrides in which hydrogen atoms
occupy the interstitial in the metallic crystals. 8his property is refereed to as occlusion. 8he
occluded hydrogen can be liberated from the metals by strong heating.
,# Reaction ith non3metals
8he chemical reaction of dihydrogen non;metals have been summari4ed as follows!
/arbon !
( ) ( )
#2$)(
2 '
Methane
2H g / g /H +
( ) ( )
=lectronic arc
2 2 2 &&++(
Acetylene
H g 2/ g / H 5g6 +
Halogen !
( ) ( )
2 2
Hydrogen fluoride
H g 1 g 2H1 +
( ) ( ) ( )
"un light
2 2
hydrogen chloride
H g /l g 2H/l g +
:ioxygen !
( ) ( ) ( )
9$+(
2 2 2
2H g 2 g 2H 2 g +
:initrogen !
( ) ( ) ( )
1eB Mo
2 2 & $)+(
2++ atm Ammonia
&H g % g 2%H g +
-# Reaction ith metal o+ide
Eeduces such as iron and metal less active than iron.
( ) ( ) ( )
2 2
/u2 s H g /u" H 2

+ + l
( ) ( )
& ' 2 2
1e 2 'H g &1e 'H 2

+ + l
2# Reaction ith carbon mono+ide
:ihydrogen reacts with carbon monoxide at $++ ( in the presence of a catalyst
2 &
FnB /r 2
to
produce methanol.
( ) ( )
2 &
$++(
2++atm
2 & Fn,/r 2
Methanol
/2 g 2H g /H 2H +
4# Reaction ith unsaturated hydrocarbons
Cnsaturated hydrocarbons like ethene ( )
2 2
/H /H
and ethyne ( ) /H /H
react with dihydrogen
to form saturated hydrocarbons.

H
2
/ /H
2
- H
2
%i or .t
'$& (
H
&
/ /H
&
=thane
=thene
%i or .t
2 & & '$& (
=thyne
=thane
H/ /H 2H H / /H +
=# Hydrogenation of Degetable oils#
Hhen dihydrogen 5under pressure6 is passed through edible vegetable oils such as ground I nut
or cotton seed oil at about '$& ( in presence of finely nickel as a catalyst, they undergo
hardening and change into edible fats known as Danaspati <hee.
( )
'$&(
2 %i
Danaspati <hee
Degetable oil H "emi solid 1at +

8he above process is known as hydrogenation or hardening of oils.
Uses of Dihydrogen
:ihydrogen is used in various industries as listed below!
5i6 In the preparation of ammonia which is a starting material for the manufacture of various
fertili4ers such as urea, ammonium sulphate, calcium ammonium nitrate, etc.
5ii6 In the hydrogenation of vegetable oils.
5iii6 In the manufacture of synthetic petrol.
5iv6 In the oxy;hydrogen torch for welding, if the temperature around 2)++/ is desired.
5v6 In the atomic hydrogen torch for welding, if the temperature around '+++/ is desired.
5vi6 *i7uid hydrogen mixed with li7uid oxygen is used as rocket fuel in space programmes.
Illustration '. The meta# $hich !i%es hydro!en on treatment $ith acid as $e## as sodium
hydro&ide is
(A) 'e (B) n
(C) Cu (D) none of these
Solution:
2 ' ' 2 2 2
Fn H "2 Fn"2 %a Fn2 H + + +
Hence 506

Exercise '. When electric current is passed through an ionic h"dride in the molten
state
(A )"drogen is li*erated at the anode
(# )"drogen is li*erated at the cathode
(% -o reaction ta.es place
(% )"dride ion migrates towards cathode
H8DRID$6
:ihydrogen combines with a number of elements to form binary compounds called hydrides.
8heir general formula being
x
MH
where M represents the element and x the number of hydrogen
atoms. :epending upon the physical and chemical properties, the hydrides have been divided
into the following three broad categories!
#. Ionic or salt;like or saline hydrides
2. Metallic or Interstitial hydrides
&. Molecules or /ovalent hydrides
6aline Hydrides or Ionic hydrides
8hese are binary compounds of hydrogen and elements which are more electropositive than
hydrogen such as alkali metals, alkaline earth metals 5except 0e6, etc. "aline hydrides are
formed by the transference of electron from metal to hydrogen. "ome common examples of this
category are!
2 2
*iH,%aH,/aH ,/rH ,
etc. 8he general characteristic of these hydrides are as
follows!
5i6 8hey are crystalline solids having white or greyish colour.
5ii6 8hey have high melting and boiling points.
5iii6 8hey have high density and high heat of formation.
5iv6 8hey conduct electricity in molten state liberating dihydrogen gas at anode which confirm the
presence of hydride ( )
H

in then.
( )
2
2
/aH melt /a 2H
+
+
At anode!
2
2
2H H 2e ? At anode /a 2e /a
+
+ +
5v6 8hey react vigorously with water and other protonic solvents such as ethanol and ammonia to
liberate dihydrogen gas. 8hus they act as strong bases.

2 2
%aH H 2 %a2H H + +
& & 2
*ithium methoxide
*iH /H 2H *i2/H H + +
& 2 2
"odamide
%aH %H %a%H H + +
( ) ( ) ( ) ( )
2 2 2
2
/aH " 2H 2 /a 2H 2H g + + l
Illustration /. (onic hydrides are fre)uent#y used to remo%e traces of $ater from or!anic
compounds. What is the under#yin! *asis of this process"
Solution: H

is a strong 0ronsted base and thus it reacts with water easily.

Co)alent Hydrides or /olecular Hydrides
8hese are binary compounds of hydrogen and elements of comparatively high electronegativity
such as p; block elements. In these hydrides, H atoms are bonded to the other atoms by covalent
bonds. "ome examples of covalent hydrides are, H/l,
2
H 2
,
&
.H
,
&
%H
etc. 8he general formula
of covalent hydrides can be written as
( ) > n
JH
where n is the number of outershell electrons of J
atom. However, elements of group #& are exception to this formula. 8he elements of group
#& such as 0, <a form polynuclear hydrides which are electron deficient compounds.
2 , & 2
0 H , <a H
, etc, are some examples. "ome of the general characteristic of covalent hydrides
are as follows!
5i6 8hese hydrides consist of individual covalent molecules with relatively weak interparticle forces
5Dander waals force of attraction6. Hence they generally soft, with low melting and boiling
points.
5ii6 8hey are poor conductors of electricity.
5iii6 0eing covalent in nature, they are more soluble in organic solvents.
5iv6 8hey undergo thermal decomposition into their respective elements.
( )
Above )$)(
' 2
"ilane
"iH "i H +
5v6 8hey are covalent in nature, K are more soluble in organic solvents.
5vi6 "ome of them react with water to liberate
2
H
.
( )
2 , 2 2
&
0oricacid
0 H ,H 2 20 2H ,H + +
5vii6 Along any given row of periodic table, the covalent hydrides become increasing acidic in
moving from left to right.
& 2
%H H 2 H1
0asic Amphoteric Acidic
Interstitial Hydride or /etallic Hydrides
8hese are binary compounds of hydrogen and transition elements.
8hese hydrides are generally formed by the
5a6 transition metals of group &, ', ) of d; block?
5b6 /r metal of group , and
5c6 f I block elements.
It may be noted that elements of group $, >, 9 of d I block do not form hydrides at all. 8his
inability of metal, of group $, >, 9 of periodic table to form hydrides is referred to as hydride gap of
d I block.
In these compounds H atoms are supposed to occupy interstitial position in the metal lattices.
"ome scientists consider these compounds as simply solid solutions of hydrogen. 8he
composition of these hydrides may not correspond to simple whole number ratio and therefore,
they are also called non;stoichimotric hydrides. 8heir composition is also found to vary with the
conditions of temperature and pressure. "ome examples of interestial hydrides of elements of
group & to ) are
2
"cH
,
2
LH
,
&
LH
,
&
*iH
, /rH,
2
8iH
,
2
FrH
,
2
HfH
, DH, %bH,
2
%bH
, 8aH etc.
"ome examples of non;stoichimetric hydrides are
+., +.,
.dH , 8i ,
+.+) +.+)
DbH , DH ,
( )
x x
FrH 5J #.&+ #.$)6, 8iH J #.> 2
, etc.
6ome general characteristics are as follos%
5i6 8hey are generally powders or brittle solids having dark or metallic appearances.
5ii6 8hey are good conductors of electricity. 8he conductivity, however, decreases with increase in
temperature.
5iii6 8hey have high thermal conductivity.
5iv6 Most of these hydrides are harder than parent metals.
5v6 8hey generally undergo reversible decomposition into H2 gas and metal.
0esides three main categories of hydrides some other types of hydrides are also known. 8wo of
these are described as follows!
:a; Polymeric Hydrides
8hey are formed by the elements having electronegativity range between #.' and 2.+. 8hey
consist of molecules held together in two or three dimensions by hydrogen bridges. "ome
common examples are
( ) ( ) ( )
2 & '
n n '
0eH , AlH , "iH , etc
8hey are amorphous solids and stable up to )2) (. Above this temperature they begin to evolve
hydrogen gas.
:b; Comple+ Hydrides
8hese are the compounds which contain hydride ions
MM
H
_

,
co;ordinated to metal atom ions.
"ome common examples are
'
*iAlH
5lithium aliminium hydride6,
'
%a0H
5sodium borohydride6
etc. 8hey are generally very good reducing agents.
Exercise /.
Which of the following is an ionic h"dride?
(A
'
As)
(#
/
Si)
(%
&
%a)
((
&
) 0
H8DRO9$N $CONO/8
Hydrogen as fuel
Hydrogen is another proposed alternative energy source. "ome advantages of hydrogen are!
5i6 Hydrogen is aboundantly available in the combined form as water.
5ii6 Cse of hydrogen as fuel provides pollution free atmosphere because its combination product
is water.
5iii6 8ime re7uired for regeneration of hydrogen is much shorter as is clear from the following
diagram!

Combination
Transportation $lectrolysis
1ater in
Ri)ers@ la!e
oceans
H
(

Days and 1ee!s for redistributionn
1ater in
.tomsphere
$nergy
7uel
O( as by product
5iv6 An automobile engine burning hydrogen is about 2) to )+@ more efficient than an automobile
engine burning gasoline.
5v6 Heat of combustion per gram of hydrogen is more than twice that of Aet fuel.
5vi6 Hydrogen I oxygen fuel cells provide other possibilities of powering motor vehicles.
5vii6 Hydrogen is excellent reducing agent and can replace coal in many industrial processes
involving reduction because it produces less atmospheric pollution than carbon.
8he changes in out way of life by adopting widespread uses of hydrogen listed above refer to
hydrogen economy.
Obstacles of Hydrogen $conomy
Although hydrogen looks as very good future fuel but some of the tough problems must be solved
before we adopt hydrogen economy. 8he problems are as described below!
:i; .)ailability#
Hydrogen is not available as much. It does not occur in free state is nature. 8herefore, cheap
production of Hydrogen is basic re7uirement of hydrogen economy. 8he most likely future source
of hydrogen is water. Hydrogen might be generated at an appropriate site by using solar energy
and then transporting it as fuel.
:ii; 6torage and Transportation#
Hydrogen gas has explosive flammability which causes problem to its storage and transportation.
Hydrogen can be stored in vacuum insulated cryogenic tanks 5already in use for space
programmes in C"A6 *i7uid hydrogen can be transported by road and rail tankers. It can also be
stored in underground tanks and transported pipelines. Another promising solution to this
problem is the use of 1e;8i alloy which act like a sponge to absorb hydrogen and results in the
formation of the silvery power. Heating the power safely releases hydrogen gas. 8he other small
storage units are alloys like
)
%a%i
,
2
Mg MgH
,
2
8i 8iH
etc. "uch storage systems are safer
than storage of hydrogen as gas or li7uid.
:iii; Platinum 6carcity
In oxygen;hydrogen fuel cells, a lot of platinum is re7uired as catalyst. In each succeeding year
the demand of platinum exceeds the supply. 8his will cause problems for fuel cells which are
highly energy source for automobiles.
Uses of &iquid Hydrogen .s 7uel
*i7uid hydrogen has already been used as rocket fuel. 8he chemical reaction involved is!
( ) ( ) ( )
2 2 2
#
H 2 g 2 g H 2 2>,k3
2
+ + l
0oth reactions H2 and 22 are stored as li7uid in separated tanks. 8he tank hold
,
#.) #+ * of
li7uid hydrogen. 8he oxygen tank carries
)
).' #+ * of li7uid oxygen. :uring the Nlift offO
operations, these properties power shuttles main engine for about >.) min. Here, li7uid hydrogen
is consumed at the rate of nearly &+++*Bsec.
Illustration 1. Activated hydrogen is obtained by
5A6 electrolysis of heavy water
506 reaction of water with heavy metals
5/6 thermal decomposition of water
5:6 passing silent electric discharge through hydrogen at low pressure
Solution:
electric discharge
2 *ow pressure
Activated hydrogen
H 2H
Hence :D; is correct answer.
1.T$R
Hater ( )
2
H 2
is an important hydride of oxygen, which is principal 5about $)@6 constituent of
earths surface. It is most abundant, omnipresent and easily obtainable of all chemical
compounds. It is a significant component of animal and vegetable matter and play a vital role in
their process. It ranks next to oxygen in importance of out existence. It constitutes about ,)@ of
human body and about 9)@ by weight of some plants. It can be easily transformed from li7uid to
solid or from li7uid to gaseous states and vice versa.
Distribution of 1ater
The distribution of ater o)er the earthBs surface is not uniform
8he desert regions have no permanent surface water while the oceans cover about $>@ of the
earths surface. 8hey contain 9$@ of the available water. 2ut of the total surface water only 2.$@
is fresh water and rest is locked in polar ice caps, glaciers or under the ground and is not readily
available.
6tructure and .ggregation of 1ater /olecules
In water molecule, the two H atoms are bonded to 2 atoms by two covalent bonds. 8he oxygen
atom assumes
&
sp hybrid state. =ach of the covalent bonds are formed by the axial overlap of #s;
orbital of H atom and
&
sp hybrid orbital of 2 atom. 8he two bond pairs and two lone pairs of
electrons around oxygen atom assume tetrahedral arrangement. /onse7uently, the
2
H 2

molecules has a bent structure. :ue to relativity greater repulsive interactions of lone pairs the
bond angle around the 2 atom decreases from #+9.2> to #+'.) as shown in the figure.
2 2
H
H
*one .air
H
#+'.)
H
2
#.+&+
5a6
5b6
5c6
Polar nature of H(O
"ince water molecule has bent shape, therefore bond moments of two
2 I H bond causes the molecule to behave as permanent electrical dipole. 8he dipole moment of
2
H 2
molecule has been found to be #.>' : which confirms its polar nature, as shown in the
figure.
.ggregation of 1ater /olecules
In gaseous state, the individual covalent molecules
2
H 2
exist as such. However in li7uid state,
large aggregates of
2
H 2
units are formed because of their association through intermolecular
hydrogen bonds as shown below
2
H
2
H
2
H
H
H
H
8he extent of association, however, depends upon the conditions of temperature and pressure.
8he intermolecular hydrogen bonding is responsible for the abnormally high free4ing point, boiling
point, heat of fusion and heat of vapori4ation as compared to the hydrides of the other elements
of oxygen family.
In ice, a solid state of water, each
2
H 2
molecule is tetrahedrally surrounded by four neighboring
2
H 2
molecules with their oxygen atoms occupying the corners of tetrahedron. 8here are four H
atoms around each 2 atom. 8wo of the four H atoms are bonded by covalent bonds 5bond length
#++ pm6 whereas the other two are linked through hydrogen bonds 5#$, pm6 as shown in the
figure. 8his gives highly three dimensional structure having large vacant spaces, which may be
compared to open cage.
:ue to open cage like structure, ice has a relatively larger volume for a given mass of li7uid
water. /onse7uently, density of ice is less than water and it floats over water.
As the temperature is raised beyond 2$& (, open cage like structure dismentalling due to
cleavage of some H;bonds and ice melts. 8he breaking of H;bond causes aggregation of
2
H 2

molecules to have closer resulting in the decrease in volume and thereby increase in density.
8his continues till 2$$ (. Hhen the density becomes maximum. 0eyond 2$$ more and H;bonds
cleaves and expansion of li7uid water starts occurring due to increased (.=. of molecules and the
density again starts decreasing however, it remains higher than ice. Hence density of water is
maximum at 2$$ (.
8his property of maximum density at 2$$ ( is a boon for
the survival of a7uatic animals during winter months
because when the upper layer of sea water free4es.
8he fro4en water does not sink to the bottom but keeps
floating at the surface due to its lesser density. 8his
provides thermal insulation to the water below it.
It is very interesting to note that nine different crystalline
forms of ice have been found to be exist under different
pressure conditions. =ach one has different melting point.
At one bar pressure ice has normal hexagonal form.
However at low temperature it adopts cubic form.
2 2
2
H
H
2
H
H
H
H
H
2
H
H
2$,pm
#$,pm
#++pm
Properties of 1ater
Physical properties
Hater has some uni7ue features which arise due to intermolecular H;bonding. "ome important
physical constants of water are given in table.
Property /agnitude
Molecular mass #>.+#)
Melting .oint 5(6 2$&.2
0oiling .oint 5(6 &$&.2
8emperature of maximum :ensity 5(6 2$$.#
Maximum :ensity ( )
&
g cm

#.+++
:ensity ( )
&
g cm

+.99$
Heat of Daporisation 5&$& (65k3B
#
mol

6
'+.,,
Heat of 1usion 5k3B
#
mol

6
,.+#
"pecific Heat ( )
# #
3g (

'.#$$
Ioni4ation /onstant ( )
2 2
H 2H mol *
+
1 1
] ]
#'
#.++> #+

( )
#
f
H k3mol

o
2>).9
"ome of the important physical properties are discussed below!
5i6 8he free4ing point, boiling point, heat of fusion and heat of vapouri4ation water are
abnormally higher than those of the hydrides of the other elements of the same group 5#,6
such as
2 2 2
H ", H "e, H 8e
etc. 8his is due to the presence of intermolecular hydrogen bonding
in
2
H 2
molecules which is, however absent among the molecule of
2 2 2
H ", H "e, H 8e
etc.
5ii6 Hater has a higher specific heat, thermal conductivity and surface tension than most other
li7uids. 8hese properties allow water to play a vital role in the biosphere. 1or example, the
high heat of vapouri4ation and the high heat capacity of water are responsible for moderation
of the climate and body temperature of living organisms.
5iii6 Hater because of its high dielectric constant 5$>.&96 has the ability to dissolve most of the
inorganic 5ionic6 compounds and its, therefore, regarded as a universal solvent. Hhereas
solubility of ionic compounds takes place due to ion;dipole interactions 5i.e. solvation of ions6,
the solubility of covalent compounds such as alcohols, amines, urea, glucose, sugar etc,
takes place due to the tendency of these molecules to form hydrogen bonds with water.
Illustration +. The me#tin! points of most of the so#id su*stances increase $ith an increase of
pressure actin! on them. Ho$e%er+ ice me#ts at a temperature #o$er than its
usua# me#tin! point $hen the pressure is increased. This is *ecause
(A) pressure !enerates heat
(B) the chemica# *onds *rea, under pressure
(C) ice is #ess denser than $ater
(D) ice is not a true so#id
Solution: :C;. 2n increasing pressure, coordination number of ions in solids increases thus
thereby increasing their melting point but in ice pressure does not increase the
coordination number of oxygen K melting point does not increase but decrease
under pressure.
Exercise 1. Water *oils 2 free3es at 144% 2 4% respecti$el", find the reason for it
from the following:
(A water dissol$es an"thing howe$er sparingl" the dissolution ma" *e
(# water is a polar molecule
(% *oiling 2 free3ing temperature of water were used to define
temperature scales.
(( li5uid water is denser than ice
Chemical Properties of 1ater
"# .ction toards litmus
.ure water is neutral to litmus.
(# Decomposition
Hater is 7uite stable and does not dissociate at high temperature. 8he dissociation into its
elements is only +.+2 @ even at #)++(.
( )
2 2 2
#
H 2 H 2
2
+ l
8he small conductivity of pure water reveals its dissociation into
&
H 2
+
and 2H

ion.
( )
#'
2 & w
2H 2 H 2 2H ? k # #+ at 29>(
+
+


*# .cid3base reactions
Hater is amphoteric substance because it can act as acid as well as base as shown ;
2 & '
Acid 0ased
H 2 %H %H 2H
+
+ +


2 &
Acid
0ase
H/l H 2 H 2 /l

+ +


However, the pH of water at 2)
o
is $ and its is neutral towards litmus.
,# Hydrolytic reactions
Hater can hydrolyse many non;metallic oxides, halides and also some metallic phosphides,
carbides and nitrates.
( )
& 2 2 &
2
/alcium phosphide .hosphine
/a . ,H 2 &/a 2H 2.H + +

2 & &
/alcium cyanamide
/a%/% &H 2 /a/2 2%H + +
( ) ( ) ( ) ( )
2
2
/a s H 2 /a 2H a7 + l
( ) ( ) ( )
2 2 2 &
"ulphurous acid
"2 g H 2 H "2 a7 + l
Illustration 6. Hhich of the following is formed by the action of water on sodium peroxideP
(A)
2
H
(B)
2
%
(C)
2
2
(D)
2
/2
Solution: %a222 - H22 2%a2H - #B222
Hence 5/6.
Exercise +. Water is oxidi3ed to ox"gen *"
(A
&
%l0
(#
/
78n0
(%
& &
) 0
((
&
9
H$.D8 1.T$R
Heavy water is the oxide of heavy hydrogen 5deuterium6 and is also called deuterium oxide. It is
represented by the formula
2
: 2
or
2
2
H 2. 8he credit of discovery of heavy water goes to Crey
who first proved that ,+++ parts of ordinary water contains about # part of heavy water. *ewis
and :onald 5#9&&6 were able to isolate a few ml of heavy water by the prolonged electrolysis of
alkaline water.
Preparation of Hea)y 1ater
8he main source of heavy water is ordinary water. 1rom which it is prepared either by prolonged
electrolysis or by fractional distillation.
Prolonged $lectrolysis of Ordinary 1ater
8his method involves multistage electrolysis of
ordinary water containing %a2H. 8he cell used for
electrolysis was designed by 0rown, :aggat and
Crey. It is a cylindrical vessel made of steel which
acts as cathode. 8he anode is a perforated
cylindrical sheet. 8he electrolysis is carried out in
different stage as described below and in actual
practice large number of electrolysis cells are used.

E
9ases
6teel Cathode
Nic!el anode
1ater
$lectrolytic cell for preparation
of hea)y ater
7irst 6tage
In this stage thirty electrolytic cell are used. =ach cell is filled with about &@ solution of %a2H.
8he electrolysis is carried out for about $2 hrs, using a current of ##+ volts. 8he volume reduces
to about #B,
th
of the original volume taken. 8he gases evolved ( )
#
2 2
H and 2
are discard the
volume left contain about 2.)@ of heavy water.
6econd 6tage
8his stage involves the electrolysis of residue left from the first stage using , electrolytic cells.
8he gaseous evolved are burnt and water formed is returned to the first stage cell. 8he residual
li7uid contains about #2@ of heavy water.
Third 6tage
8his involves the electrolysis of residue of second stage. 8he content of heavy water is raised to
about ,+@. 8he gases evolved are burnt to get water that is fed to 2
nd
stage cells.
7ourth 6tage
8his stage involves the electrolysis of residue of third stage and here, nearly 99@ of heavy water
is obtained. 8he gases evolved are burnt as usual, and sent to third stage cells.
7ifth stage
8he 99@ heavy water from fourth stage is made free from alkali and other impurities by
distillation and distillate is electrolysis. Here, the gases evolved are
2
:
and
2
2
which are burnt to
get #++@ pure water. A flow sheet diagram of the process is shown below in the figure.

7IR6T 6T.9$
*? cells
6$COND 6T.9$
2 cells
7I7TH 6T.9$
AURN$R6
AURN$R6
AURN$R6
AURN$R6


7OURTH 6T.9$
THIRD 6T.9$
7lo sheet diagram for producing D(O
Ay 7ractional Distillation of Ordinary 1ater
8his method involves partial separation of heavy water from ordinary water. Advantage is taken
of the small difference in the boiling points of protium oxide 5&$&.2(6 and deuterium oxide
5&$'.&(6. "ince the difference in boiling points is very small, a long fractionating column 5about
#& m6 is used for distillation and the process is repeated several times. 8he lighter fraction ( )
2
H 2

is distilled first while heavier fraction ( )
2
: 2
is left behind. 8he heavier fraction becomes rich in
( )
2
: 2
.
Properties of Hea)y 1ater
5i6 Heavy water is colourless, tasteless and odourless li7uid.
5ii6 All physical constants of heavy water are higher than the corresponding values of ordinary
water. "ome of the physical constants of heavy water are given below in table.
Property 2
H 2
2
: 2
Molecular mass #>.+#) 2+.+2>
Melting .oint 5(6 2$&.2 2$,.>
0oiling .oint 5(6 2$&.2 &$'.'
8emperature of maximum :ensity 5(6 2$$.# 2>'.'
Maximum :ensity ( )
&
g cm

#.+++ #.#+,
:ensity ( )
&
g cm

+.99$ #.#+'
Heat of Daporisation 5&$& (65k3B
#
mol

6
'+.,, '#.,#
Heat of 1usion 5k3B
#
mol

6
,.+# ,.2>
"pecific Heat ( )
# #
3g (

'.#$$ ;
Ioni4ation /onstant ( )
2 2
H 2H mol *
+
1 1
] ]
#'
#.++> #+

#)
#.9) #+

( )
#
f
H k3mol

o
2>).9 29'.,
Chemical Properties of Hea)y 1ater
Heavy water is chemically similar to ordinary water. 8he chemical reactions of heavy water are
slower than those of ordinary water. "ome of the important reactions of heavy water are listed
below!
"# Reaction ith metals
Alkali metals and alkali earth metals reacts with heavy water to form heavy hydrogen ( )
2
:
.
2 2
"odium deutroxide
: 2 2%a 2%a2: : + +
( )
Heat
2 2
2
/alcium deutroxide
: 2 /a /a 2: : + +
Heat
2 & ' 2
Magnetic oxide
or Iron
: 2 1e 1e 2 ': + +
(# Reaction ith metal o+ides
( )
2
: 2
reacts slowly with metal oxides to form corresponding deutroxides
2 2
%a 2 : 2 2%a2: +
( )
2
2
/a2 : 2 /a 2: +
*# Reaction ith non3metallic o+ides
%on;metallic oxides react with ( )
2
: 2
to form corresponding deutro acid,
2 ) 2 &
:eutronitric acid
% 2 : 2 2:%2 +
& 2 2 '
:eutrosulphuric acid
"2 : 2 : "2 +
2 ) 2 & '
:eutrophosphoric acid
. 2 &: 2 2: .2 +
,# Reactions ith carbides@ nitrides@ phosphides@ arsenide etc#
( )
2 2
2
:eutroacetylene
/alcium carbide
/a/ 2: 2 /a 2: :/ /: + +
( )
' & 2 '
&
:eutromethane Aluminium carbide
Al / #2: 2 'Al 2: /: + +
( )
& 2 2 &
2
Magnesium nitride trideuteriated ammonia
Mg % ,: 2 &Mg 2: 2%: + +
( )
& 2 2 &
2
/alcium .hoshide :eutrophosphine
/a . ,: 2 &/a 2: 2.: + +
& 2 &
"odium arsenide :eutroarsene
%a As &: 2 %a2: As: + +
-# $lectrolysis
A solution of heavy water containing
& &
%a /2
, when electrolysed evolve heavy hydrogen at
cathode
( ) ( )
=lectrolysis
2 2 2
At cathode At anode
2: 2 2: 2 +
2# $+change reactions
Hhen compounds having mobile hydrogen react with heavy water, hydrogen is exchanged
by deuterium partially or completely.
2
%a2H : 2 %a2: H:2 + +


( )
2
H/l a7 : 2 :/l H:2 + +


( )
' 2 '
%H /l a7 ': 2 %: /l 'H:2 + +


4# Deutero hydrates
Heavy water like ordinary water may be associated with salts as water of crystalli4ation, giving
deutro hydrates, e.g.,
2 ' 2 ' 2 ' 2
%a "2 .#+: 2, /u"2 .): 2, Mg"2 .$: 2, etc
.
=# Deuterolysis
Hater brings hydrolysis of certain inorganic salts.
2
: 2
gives similar reactions which are termed
deuterolysis.
( )
& 2
&
:euterium
Aluminium cloride
Aliminium deutrero
chloride
hydroxide
Al/l &: 2 Al 2: &:/l + +
( )
2 2
2
0arium
:euterium
0arium deutero
"ulplide
"ulphide
Hydroxide
0a" : 2 0a 2: : " + +
<# Aiological and Physiological effects
It has been established that heavy water of high concentration retards the growth of plants and
animals. It has been confirmed by &eis that tobacco do not grow in heavy water. .ure heavy
water kill small fishes, tadpoles and mice, when fed on with it.
8aylor has shown that heavy water has germicide and bactericide properties. Hater containing
small 7uantity of
2
: 2
acts as a tonic and stimulates vegetable growth. /ertain moulds have
been found to develop better in heavy water in comparison to ordinary water.
Uses of Hea)y 1ater
8he following are the important uses of heavy water!
"# .s a neutron moderator#
1ission in uranium I 2&) is brought in by slow speed neutrons. 8he substances which are used
for slowing down the speed of neutrons are called moderators. Heavy water is used for this
purpose in nuclear reactors.
(# 7or the preparation of deuterium#
Heavy water on electrolysis by its decomposition with metals produces deuterium.
*# .s a tracer compound#
Heavy water is commonly used as a tracer compound for studying various reactions
mechanisms. It has also used for studying the structure of some oxyacids of phosphorus such as
& 2 & &
H .2 and H .2
as to determine the number of ionisable hydrogen atoms.
Production in India
Darious units have been set in India to manufacture heavy water. 8hese are situated at %anital,
8rombay, Eourkel, %amrup and %eyveli.
Illustration ,. Hea%y $ater is a compound of
(A) hydro!en - hea%ier isotope of o&y!en
(B) hea%ier isotope of hydro!en - hea%ier isotope of o&y!en
(C) o&y!en - hea%ier isotope of hydro!en
(D) none of the a*o%e
Solution: :C;# :22 is heavy water.
Exercise 6.
(ielectric constant of (&0 is
(A e5ual to that of water (# slightl" less than that of water
(% slightl" more than that of water (( half of water
H.RD .ND 6O7T 1.T$R
Hater is classified into categories depending upon its behaviour towards soap solution. 8hese
are! soft water and hard water.
:a; 6oft ater
Hater which produces lather with soap solution readily is called soft water. :istilled water and
rain water are common examples of soft water.
:b; Hard 1ater
Hater which does not produce lather with soap solution easily is called hard water. "ea water,
tap water are common examples of hard water.
Cause of Hardness of ater
Hardness of water is due to the dissolved impurities of the salts like bicarbonates, chlorides and
sulphates of calcium and magnesium. Hater gets contaminated by these salts when it passes
through the ground and rocks. Hard water does not produce lather with soap solution readily
because the cations ( )
2 2
/a and Mg
+ +
present in hard water react with soap 5which is a mixture of
sodium salts of higher fatty acids like stearic acid, palmitic acid, oleic acid, etc6 to form a
precipitate of calcium and magnesium salts of fatty acids.
( )
2
#$ &) #$ &)
2
1rom hard water
"odium stereate
Metal stearate
M 2/ H /22%a / H /22 M 2%a
+ +
+ +

:M Q /a or Mg6
8hus, no lather is produced until all the calcium and magnesium ions have been precipitated.
8his leads to the consumption and hence, wastage of lot of soap. Hard water is, therefore, not fit
for washing purposes
Types of Hardness
8he hardness of water is of two types! temporary hardness and permanent hardness.
:i; Temporary hardness#
It is due to the presence of soluble bicarbonates of calcium and magnesium. "uch water is also
said to posses carbonate hardness. 8he term temporary indicates that most of the hardness can
be removed by simply boiling the water. 8he bicarbonates of calcium and magnesium are formed
in water by dissolution of carbonates of calcium and magnesium in the presence of atmospheric
carbon dioxide.
:ii; Permanent hardness#
It is due to the presence of chlorides and sulphates of calcium and magnesium. "uch water is
also said to posses non;carbonate hardness. 8he term permanent indicates that type of hardness
can not be removed by boiling of water.
6oftening of Hard 1ater
8he process of removal of metallic ions ( )
2 2
/a and Mg
+ +
responsible for hardness of water is
known as softening of water. A number of methods are available to soften water depending upon
the nature of dissolved mineral salts as described below!
Remo)al of Temporary Hardness
8emporary hardness can be removed by the following methods!
:i; Aoiling
8emporary hard water is taken in large boilers and boiled for about fifteen minutes.
/onse7uently, the bicarbonate of calcium and magnesium present in the water decompose into
their insoluble carbonates which settle at the bottom of the tank as precipitate which are removed
by filtration or decantation.
( )
( )
( )
( )
Heat
& & 2 2
2
Insoluble
"oluble
M H/2 M/2 H 2 /2
M /a or Mg
+ +

:ii; Calcium hydro+ide :or Clar!eBs; method

/alculated 7uantity of lime 5calcium hydroxide6 is added to temporary hard water. 8he soluble
bicarbonates are converted into insoluble carbonates which settle at the bottom of the tank and
are removed by filtration.
( )
( )
( )
Heat
& 2 & 2
2
Insoluble
"oluble
/a H/2 /a52H6 2/a/2 2H 2 + +
( )
( )
( )
( )
& & & 2
2 2
"oluble
Insoluble
Mg H/2 /a 2H Mg/2 /a/2 2H 2 + + +
E5555555555555F
Remo)al of Permanent Hardness
.ermanent hardness of water can be removed by the following methods!
"# Ay chemical additi)es
:a; .ddition of ashing soda#
In this method,
2 2
/a and Mg
+ +
ions can be precipitated by the addition of calculated amount of
washing soda ( )
2 & 2
%a /2 .#+H 2
( )
2 2
& &
M /2 M/2 ? M /a or Mg
+
+
:b; .ddition of sodium polymetaphosphate :calgon process;
In this method
2 2
/a and Mg
+ +
ions are rendered ineffective by the addition of sodium
polymetaphosphate. 8he trade name of which is calgon 5meaning calcium gone6. 8he general
formula of sodium polymetaphosphate is ( )
&
n
%a.2
, where the value of n is sometime as large as
#+++. However, commonly, calgon is represented by sodium hexametaphosphate ( )
&
,
%a.2
.8he
2 2
/a and Mg
+ +
of hard water reacts with calgon to form soluble complexes.
( )
( ) ( )
2
2 ' & 2 2 &
, ,
Hardness
/algon soluble
2/a %a %a .2 %a /a .2 '%a
+ +
1 1 + +
] ]
( )
( ) ( )
2
2 ' & 2 2 &
, ,
Hardness
/algon soluble
2Mg %a %a .2 %a Mg .2 '%a
+ +
1 1 + +
] ]
8he complexes of calcium and magnesium so formed remain dissolved in water but they do not
cause hindrance in the formation of lather. 8his is because calcium and magnesium ions are not
free to react with soap but these have been tied up in stable complexes. 8his is also known as
se7uestraction of
2 2
/a and Mg
+ +
ions.
(# Ion $+change method
8his is a modern method of softening of water. In this method, the ions present in the hard water
are exchanged for less damaging ions from the exchangers. 8here are two main types of ion;
exchanger as!
:a; Inorganic cation e+changers :Permutit /ethod;
8hese are complex inorganic salts like hydrated sodium;aluminum silicate
2 2 2 > 2
%a Al "i 2 .xH 2

which have interesting property of exchanging cations such as calcium and magnesium ions in
hard water for sodium ions. 8hese complex salts are known as 3eolites which can be either a
naturally occurring or an artificially synthesi4ed substances. 8heir technical name is permutit. 1or
artificial synthesis of permutit, a mixture of soda ash ( )
2 &
%a /2
, sand ( )
2
"i2
and alumina
( )
2 &
Al 2
is fused together. 8he product is washed with water to remove soluble impurities leaving
behind a porous mass of permutit.

Hard
1ater
NaCl
6olution
6oft
1ater Out
Permutit process for softening of hard ater
Coarse 6and
Permutit
8he permutit is loosely packed in a big tank over a layer of coarse sand. Hard water is introduced
into the tank from the top. Hater reaches the bottom of the tank and then slowly rises through the
layer of permutit in the tank. 8he cations present in hard water are exchanged for sodium ions.
( )
2 2
/alcium 4eolite in tank
"odium4eolite 1rom hard water
%a F M/l MF 2%a/l + +
5M Q /a or Mg6
where F Q
2 2 > 2
Al "i 2 .xH 2
As the process is continued, 4eolites gets exhausted because of its conversion into calcium and
magnesium 4eolite. 8he exhausted resin is regenerated allowing about #+@ solution of sodium
chloride to percolate through it when the following reaction occurs.
2 2
=xhausted
Eegnerated
resin
resin
MF 2%a/l %a F Mg/l + +
5M Q /a or Mg6
8he regenerated or reactivated resin can be used again and again for a 7uite longer period.
:b; Organic ion e+changers
8hese are complex organic molecules having giant hydrocarbon frame work with either acidic
group ( )
&
"2 or /22H
or basic group ( )
2
2H or %H

attached to them. 8he resins with acidic
group are capable of exchanging the H
+
ions for the cations and are called cation exchangers.
8hey are represented as H
+
resin. 8he resins with basic group are capable of exchanging their
2
2H or %H

ions for other anions and are called anion exchangers. 8hey are represented as
H2

resin.
/ethod of Remo)al of Hardness Ay Organic $+changers
1irst of all, the hard water is passed through a bed of cation exchange resin. 8he cations present
in hard water are exchanged with H
+
of resin as!

Hard
1ater
Dil# HCl 7or
Regeneration
Cation
$+change
Resin
1aste
1aste
.nion
$+change
Resin
Dil# NaOH 7or
Regeneration

9ra)el
9ra)el
6oft 1ater
Remo)al of hardness by the organic ion 3 e+changes
( ) ( )
( )
2
2
in hard water cation exchanger
/a 2H resin /a resin 2H
+ + +
+ +
( )
( )
( )
2
2
cation exchanger
in hard water
Mg 2H resin Mg resin 2H
+ + +
+ +
8he water which comes out of the bottom of first tank is richer in H
+
ions.
8his water is then passed through a bed of anion exchange resin where anions contained in
water are exchanged with 2H

ions as
( ) ( ) in hard water Anion exchanger
/l H2 resin /l resin 2H

+ +
( )
( )
( )
2 2
' '
2
Anion exchanger
inHard water
"2 2H2 resin "2 resin 22H

+ +
8herefore, the H
+
ions 5formed in the first tank6 combine with the 2H

ions 5formed in the

second tank6 to produce water.
2
H 2H H 2
+
+
8hus, water obtained by this method is free from all types of cations as well as anions. It is known
as deionised or demineralised water.
8his method is particularly suitable for obtaining pure water for laboratory purposes.
Regeneration of resins
8he exhausted resin in the first tank is regenerated by treatment with moderately concentrated
hydrochloric or sulphuric acid.
( )
2
2
Eegenerated resin
=xhausted resin
/a resin 2H/l /a/l 2H resin
+
+ +
"imilarly, the exhausted resin in the second tank is regenerated by treatment with moderately
concentrated solution of sodium hydroxide.
=xhausted resin Eegenerated resin
/l resin %a2H H2 resin %a/l

+ +
Exercise :. 0ne of the following is an incorrect statement point it out
(A permanent hardness can *e remo$ed *" *oiling water
(# hardness of water effects soap consumption
(% temporar" hardness is due to *icar*onates of %a 2 8g.
(( permanent hardness is due to the solu*le
& ; ; ;
/ '
S0 , %l , -0 of %a 2 8g.
Degree of Hardness of 1ater
:egree of hardness of water is defined as number of parts of mass of
&
/a/2
5/alcium
carbonate6, e7uivalent to various calcium and magnesium salts present in one million parts by
mass of water. It is expressed in ppm 5parts per million6.
Illustration 11. Ca#cu#ate the de!ree of hardness of a samp#e of hard $ater $hich is found to
contain 3. m! of
'
Mg"2
per ,! of $ater.
Solutions: 2ur obAective is to find mass of
&
/a/2
e7uivalent to
'
Mg"2
in one million parts
of water.
%ow,
&
#+ g of water contains
'
Mg"2
Q &, mg
,
#+ g of water contains
'
Mg"2
Q &,
&
#+ mg Q &, g
1rom the formula, # mol of
'
Mg"2
Q # mol of
&
/a/2
or #2+ g of
'
Mg"2
Q #++ g of
&
/a/2
or &, g of
'
Mg"2
Q
& &
#++ &,
g of /a/2 &+ g of /a/2
#2+

8hus, degree of hardness Q &+ ppm.

It may be noted degree of hardness up to #++ I #)+ ppm in water re7uired for our daily needs
such as cooking, bathing, washing of clothes, etc, is tolerable. 0ut if degree of hardness exceeds
this limit, then water is not suitable for domestic use.
H8DRO9$N P$ROFID$ H(O(
Hydrogen peroxide is another hydride of oxygen. Cnlike water it is highly unstable, and therefore,
does not exist in nature as such. Its, importance, in recent years has increased due to its use as
rocket fuel.
Preparation of Hydrogen Pero+ide
"# 7rom sodium pero+ide :/erc!Bs method;
/alculated amount of sodium peroxide ( )
2 2
%a 2
is gradually added to an ice;cold solution of 2+@
2 '
H "2
in small lots with constant stiring.
2 2 2 ' 2 ' 2 2
"odium peroxide Hydrogen peroxide
%a 2 H "2 %a "2 H 2 + +
Cpon cooling, crystals of
2 ' 2
%a "2 .#+H 2
separate out and the resulting solution contains about
&+@
2 2
H 2
. 8he solution also contains some dissolved
2 '
%a "2
, but it does not interfere with the
reactions of
2 2
H 2
. A pure sample of
2 2
H 2
may, however, be prepared by vacuum distillation.
(# 7rom barium pero+ide3&aboratory method of preparation#
Hydrogen peroxide is prepared from barium peroxide by the following methods!
5a6 Ay the action of dilute sulphuric acid. A paste of hydrated barium peroxide ( )
2 2
0a2 .>H 2
is
prepared in ice I cold water and then added slowly to an ice;cold solution of 2+@
2 '
H "2
.
( ) ( ) ( ) ( )
2 2 2 ' ' 2 2 2
Hydrogen peroxide Hydrated barium peroxide
0a2 .>H 2 s H "2 a7 0a"2 s H 2 >H 2 + + + l
8he white precipitate of
'
0a"2
is removed by filtration leaving behind a dilute solution 5)@6
of
2 2
H 2
. In this method, anhydrous barium peroxide can not used since the precipitated
'
0a"2
forms a protective layer around unreacted barium peroxide thereby preventing the
further reaction
Illustration 1&. A certain samp#e of hydro!en pero&ide is 1./ 0 so#ution. (t is to *e #a*e##ed as 1
%o#umes. Ca#cu#ate the %a#ue of 1.
Solution:
( ) *
mass of solution
Molarity
mol. mass D

2r mass of
2 2
H 2
per litre Q
#.) &' )#g
2 2 2 2
,>g 22.'*
2H 2 2H 2 2 +
%ow ,> g of give
2
2
at "8. Q 22.' *
2 2
22.' )#
)#g of H 2 give at "8. #,.>
,>

8hus # * of
2 2
H 2
which contains )# g of
2 2
H 2
produces
2
2
at "8. Q #,.> *
Hence value of J is Q #,.> *
2r 8he given sample is #,.> volume
2 2
H 2
.
&imitation
Hydrogen peroxide prepared by this method contains appreciable 7uantities of
2
0a
+
ions 5in the
form of dissolved barium persulphate6 which catalyse the decomposition of
2 2
H 2
.8herefore,
2 2
H 2

prepared by this method cannot be stored for a long time.
1urther,
2 '
H "2
also acts as a catalyst for decomposition of
2 2
H 2
.
5b6 Ay the action of carbon dio+ide or carbonic acid. Hhen a rapid stream of
2
/2
is bubbled
through a thin paste of
2
0a2
in ice;cold water,
2 2
H 2
and
&
0a/2
are produced!
2 2 2 & 2 2
0a2 H 2 /2 0a/2 H 2 + + +
8he insoluble barium carbonate is removed by filtration leaving behind a dilute solution of
2 2
H 2
5c6 Ay the action of phosphoric acid. Hydrogen peroxide can also be prepared by the action of
phosphoric acid on barium peroxide!
( )
2 & ' & ' 2 2
2
0a2 2H .2 0a .2 &H 2 + +
8his method has the advantage over
2 2 '
0a2 H "2
method since almost all the heavy metal
5e.g. .b etc6 impurities present in
2
0a2
and which catalyse the decomposition of
2 2
H 2
are
removed as insoluble phosphates. As a result, the resulting solution of
2 2
H 2
has good
keeping properties.
/anufacture of Hydrogen Pero+ide
"# Ay electrolysis of -?> H(6O,
Hydrogen peroxide is manufactured by the electrolysis of a cold )+@ solutions of
2 '
H "2
in an
electrolytic cell using platinum as anode and graphite as cathode. 8he reactions taking place are!
2 ' '
2H "2 2H 2H"2
+
+
At cathode!
2
2H 2e H
+
+
At anode !
' 2 2 >
.eroxydisulphuric
acid
2H"2 H " 2 2e

+
.eroxydisulphuric acid formed around anode is withdrawn and then distilled with water under
reduced pressure. 8he low boiling
2 2
H 2
distils over along with water leaving behind high boiling
2 '
H "2
which is recovered and recycled.
2 2 > 2 2 ) 2 '
.eroxodisulhuric .eroxomonosulhuric
acid acid
H " 2 H 2 H "2 H "2 + +
2 ) 2 2 ' 2 2
.eroxomonosulhuric
acid
H "2 H 2 H "2 H 2 + +
or,
2 2 > 2 2 2 2 '
H " 2 2H 2 H 2 2H "2 + +
/odification
Eecently, it has been observed that if instead of )+@
2 '
H "2
an e7uimolar mixture of H2"2' and
ammonium sulphate is electrolysed, a more concentrated solution of
2 2
H 2
is obtained.
( )
' ' 2 ' ' '
2
Amm.hydrogen
sulphate
%H "2 H "2 2%H H"2 +
' ' ' '
2%H H"2 2H 2%H "2
+
+
At cathode!
2
2H 2e H
+
+
At Anode!
( )
' ' ' 2 >
2
Amm. persulphate
2%H "2 %H " 2 2e

+
Ammonium persulphate formed around anode is withdrawn and distilled with water to give
2 2
H 2
( )
' 2 > 2 ' ' 2 2
2
%H " 2 2H 2 2%H H"2 H 2 + +
8his process is now used only for the laboratory preparation of
2 2
: 2
, i.e.?
2 2 > 2 ' 2 2
( " 2 2: 2 2(:"2 : 2 + +
:eutroperoxide
(# Ay auto+idation of (3ethylanthraquinol
8his is a new method and is widely used in C.".A. In this process, air is bubbled through a #+@
solution of 2;ethylanthra7uinol in ben4ene and cyclohexane when 2;ethylanthra7uinol is oxidi4ed
to 2;ethylanthra7uinone and
2 2
H 2
is formed according to the following e7uations.
/
2
H
)
2H
2H
2;=thylanthra7uinol
2
2
H
2
B.d
/
2
H
)
2
2
-
H
2
2
2
2;ethylanthra7uinone
8he
2 2
H 2
thus formed 5about #@6 is extracted with water and the a7ueous solution is
concentrated by distillation under reduced pressure to give &+@ 5by weight6
2 2
H 2
solution.
2 I =thylanthra7uinone so produced can be reduced back to the starting to the material i.e., 2;
ethylanthra7uinol by hydrogen using palladium catalyst.
/
2
H
)
2
2
2;=thylanthra7uinone
H
2
.d
/
2
H
)
2H
2H
2;=thylanthra7uinol
8hus, we find that the raw material are
2
H
and
2
2
only.
Concentration of hydrogen Pero+ide 6olution
Hydrogen peroxide produced by any of the above method is in the form of dilute solution. 8he
solution can not be concentrated by simple heating because it readily decomposes below its
boiling point as
2 2 2 2
2H 2 2H 2 2 +
8he dilute solution of hydrogen peroxide is concentrated carefully by the following steps!
:i; 6lo e)aporation on ater bath
8he dilute solution of hydrogen peroxide is taken in evaporating dish which is heated carefully on
water bath. "low evaporation continues causing the escaping of water molecules till
approximately )+@ solution of
2 2
H 2
is obtained.
:ii; $)aporation in )acuum desicator
8he )+@ solution is placed in vacuum desicator over concentrated sulphuric acid. 8he water
vapours are absorbed by sulphuric acid leaving approximately 9+@ solution of
2 2
H 2
.
:iii; Distillation under reduced pressure
8he 9+@ solution of hydrogen peroxide is then subAected to distillation under reduced pressure
5#+ I #)mm6. :uring this process, water distils over at &+& I &#& ( and about 99@ pure
hydrogen peroxide is left behind.
:i); Remo)al of last traces of ater
8he 99@ solution of hydrogen peroxide is cooled in a free4ing mixture of solid carbon dioxide and
ether. As a result of this, crystals of hydrogen peroxide separate out which are removed, dried
and remelted. 8his gives completely pure hydrogen peroxide.
6torage of Hydrogen Pero+ide
:ecomposition of hydrogen peroxide into water oxygen is catalysed by traces of metal impurities,
strong bases and exposure to light. 0ecause of this property of
2 2
H 2
, the concentrated solution of
2 2
H 2
can be dangerous as uncontrolled rapid decomposition can result in an explosion. 8hus,
5i6 It is stored in wax lined coloured bottles as rough glass surface also causes its
decomposition.
5ii6 A small amount of stabili4er like phosphoric acid, or glycerol or acetanilide must to added to
retard its decomposition.
6tructure of Hydrogen Pero+ide
As established by J I ray studies, hydrogen peroxide molecules has a non I planar structure.
8he molecules dimensions in gas phase and that in solid phase have given in figure. 5a6 and 5b6
respectively. In the crystal, the dihedral angle ( )
###.)
o
reduces to 9+.2
o
on account of hydrogen
bonding. 8he two oxygen atoms are Aoined by a single electron I pair bond. 8he 2 I 2 *inkage is
also called peroxide linkage.

H
<- pm
",4#- pm
<,#=
H
H
<=#= pm
",-#= pm
"?"#<
H
:a; 9as phase :b; 6olid phase
<?#(
"""#-
Properties of Hydrogen Pero+ide
"ome of the physical properties of hydrogen peroxide are listed below!
5i6 .ure hydrogen peroxide is a colourless, syrupy li7uid.
5ii6 It has odour like that of nitric acid.
5iii6 Its a7ueous solution has a bitter taste.
5iv6 It is soluble in water, alcohol and ether in all proportions.
5v6 Its density is #.'' g
&
cm

. 8he high density is due to association of its molecules by

intermolecular hydrogen bonds.
5vi6 Its boiling points is '2& ( at ,$+ mm pressure and &)> ( at ,> mm pressure. Its melting point
is 2$2 (.
Chemical Properties
:a; Decomposition
It is a unstable li7uid readily decomposes on heating or on long standing to give water and
dioxygen. It is an example of disproportionation decomposition is suppressed by addition of
glycerol, acetanilide or phosphoric acid.
:b; .cidic beha)iour
.ure hydrogen peroxide is a weak acid 5
#2
a
( #.)) #+

at 29> (6. it ioni4es in water as!

( )
2 2 2
H 2 H H2 hydroperoxide ion
+
+


( )
2
2 2
H2 H 2 peroxide ion
+
+


Its acidic character can be shown its ability to neutrali4e bases such as %a2H,
2 &
%a /2
etc, to
form corresponding peroxides
2 2 2 2 2
2%a2H H 2 %a 2 2H 2 + +
2 & 2 2 2 2 2 2
2%a /2 H 2 %a 2 H 2 /2 + + +
Hydrogen peroxide has an interesting chemistry because of its ability to act as oxidi4ing as well
as reducing agent both in acidic and basic solutions.
O+idising nature of H(O(
2 2
H 2
can acts as oxidi4ing agents in acidic as well as basic medium as described below.
2 2 2
In acidic medium H 2 2H 2e 2H 2
+
+ +
2 2
Inbasic mediumH 2 2e 22H

+

( )
( )
2 2 2
2 & 2 2 2 2
' 2
& & & ' 2
2 & 2 ' 2
2 & 2
' 2 ' 2 ' 2
&
2 2 2 2
'
,
Acidic nature
%a2H %a 2 H 2
%a /2 %a 2 H 2 /2
2xidi sing %ature
.b" .b"2 H 2
%a As2 %a As2 H 2
%a "2 %a "2 H 2
%a%2 %a%2 H 2
1e"2 B H "2 1e "2 H 2
H 2 (I B H/l (/l I H 2
( 1e /% B H/l
+
+ +
+
+
+
+
+
+ +
1
]
( )
( )
& 2
,
ice cold
2 2 $ 2 ' ) 2 ' 2 =ther
0lue
' 2 ' 2 2
& 2 2
' 2 ' ' 2 ' 2
2 2
2 2
&
,
( 1e /% H 2 (/l
( /r 2 B H "2 /r2 ( "2 H 2
Mn"2 B %a2H %a "2 Mn2 H 2
Eeducing .r operties
2 H 2 2
(Mn2 B H "2 Mn"2 ( "2 H 2
Ag 2 2Ag H 2
.b 2 2.b H 2
( 1e /% B (2H
1 + +
]
+ +
+ +
+
+ +
+
+
1
]
( )
' 2
,
( 1e /% H 2

1 +

Illustration 1'. 2Hydro!en pero&ide is a stron! o&idi3in! a!ent *oth in acid and a#,a#ine
medium4. 5ustify !i%in! suita*#e reactions.
Solution: 2xidising agent
( )
2 2 2
H 2 2H 2e 2H 2 acidic medium
+
+ +
( )
2 2
H 2 2e 22H basic medium

+
Eeducing agent
2 2 2
H 2 2H 2 2e
+
+ +
Illustration 1/. Hhat happens when
2 2
H 2
is treated with
5a6 acidified potassium permanganate
5b6 lead sulphide
5c6 alkaline potassium ferrocyanide
5d6 acidified ferrous sulphate
5e6 sulphurous acid.
Solution: 5a6 It reduces acidified
'
(Mn2
solution. 8he pink colour of
'
(Mn2
is
discharged.
5b6
( )
( )
2 2 ' 2
0lack
Hhite
.b" 'H 2 .b"2 'H 2 + +
5c6 It reduces alkaline potassium ferricyanide to potassium ferricyanide.
5d6 It oxidi4es acidified ferrous sulphates to ferric sulphate.
5e6 It oxides sulphurous acid to sulphuric acid
Illustration 11. What happens $hen"
(i) Chromium hydro&ide is treated $ith hydro!en pero&ide in the presence of
6a7H.
(ii) Hydra3inc reacts $ith hydro!en pero&ide.
(iii) Hydro!en pero&ide reacts $ith ( )
2
Ba 7H
.
(i%) 8odium hypoch#orite reacts $ith
2 2
H 7
.
Solution: 5i6 ( )
&
/r 2H
is converted into yellow coloured
2 '
%a /r2
5ii6 Hydra4ine is oxidised to
2
%
and
2
H 2
.
5iii6 ( )
2 2 2 2
2
H 2 0a 2H 0a2 2H 2 + +
5iv6
2 2 2 2
%a2/l H 2 %a/l H 2 2 + + +
Aleaching .ction
8he bleaching action of hydrogen peroxide is due to the nascent oxygen which it liberates on
decomposition.
[ ]
2 2 2
H 2 H 2 2 +
8he nascent oxygen combines with colouring matter which, in turn, gets oxidised. 8hus, the
bleaching action of
2 2
H 2
is due to the oxidation of colouring matter by nascent oxygen. It is used
for the bleaching of delicate materials like ivory, feather silk, wool etc.
[ ]
2
/olouring matter 2 /olourless matter H 2 + +
.ddition reactions
Hydrogen peroxide reacts with alkenes to form glycols.
/H
2
/H
2
-
H
2
2
2
/H
2
2H
/H
2
2H
6trength of Hydrogen Pero+ide
"# .s percentage
"ome time the actual concentration of hydrogen peroxide in a solution in expressed as
percentages of
2 2
H 2
in solution. 8hus, '+@ solution of hydrogen peroxide means '+ grams of
hydrogen peroxide are present in #++ grams of solution.
(# .s )olume strength
8he most common method of expressing the concentration of hydrogen peroxide solution is, in
terms of the volume of oxygen which a solution of hydrogen peroxide gives on decomposition by
heat. 1or example, N#+ volumeO hydrogen peroxide refers to a solution of hydrogen peroxide
whose, # litre will give #+ litre of oxygen at "8..
Calculation of 6trength of H(O(
It is possible to calculate the strength of hydrogen peroxide from its Nvolume strengthO. *et us
calculate the concentration in gBlitre of N&+ volumeO solution of hydrogen peroxide.
A &+ volume solution of hydrogen means that # litre of the solution gives &+ litre of oxygen at
"8.. According to its decomposition reaction.

2 2 2 2
2 &'g 22.' litres at "8.
2H 2 2H 2 2

+
%ow # litre of hydrogen peroxide gives &+ * of oxygen at "8.
1rom the above e7uation
22.' * of oxygen is obtained from
2 2
H 2
Q
2 &'g
&+ * of oxygen at "8. is obtained from
2 2
H 2
Q
2 &' &+
9#.+$g
22.'

8hus, #* of sample contains

2 2
H 2
Q 9#.+$g
or "trength of the &+ volume solution of hydrogen peroxide is 9#.+$
#
g*

Illustration 1+. Ca#cu#ate the stren!th in

91
!: + mo#arity and norma#ity of 4; %o#ume of hydro!en
pero&ide so#ution.
Solution:
2 2 2 2
,>g 22.'* at "8.
2H 2 2H 2 2 +

'+ volume
2 2
H 2
means, #* of the solution produces '+ * of
2
2
at "8.
%ow, 22.' * of
2
2
at "8. is produced from
2 2
H 2
Q ,>
'+ * of oxygen at "8. is obtained from
2 2
H 2
Q
,> '+
#2#.'2g
22.'

#
"trength of the solution #2#.'2g*

( ) *
Mass of solute #2#.'2
Molarity of the solution &.)$M
Mol. mass D &' #


( ) *
Mass of solute
%ormality of the solution
=7. mass D

Q
#2#.'2
$.#'2 %
#$ #

Illustration 16. A7ueous solution of an inorganic compound 5x6 shows the following reactions.
5i6 It decolourises an acidified
'
(Mn2
solution accompanied by the solution of
oxygen.
5ii6 It liberates iodine from an acidified (I solution.
5iii6 It gives a brown precipitate with alkaline
'
(Mn2
solution with evolution
oxygen.
5iv6 It removes black stains from old oil paintings.
Identify 5x6 and give chemical e7uations for the reactions at step 5i6 to 5iv6.
Solution:
' 2 ' 2 2 2 ' ' 2 2
purple colours
soluble, coloursless
(Mn2 &H "2 )H 2 ( "2 2Mn"2 >H 2 )2 + + + + +
1 4 4 4 2 4 4 43
2 ' 2 2 2 ' 2 2
2(I H "2 H 2 ( "2 I 2H 2 + + + +
' 2 2 2 2 2
0rown
2(Mn2 &H 2 2(2H 2Mn2 2H 2 &2 + + + +
2 2 ' 2
black
Hhite
.b" 'H 2 .b"2 'H 2 + +
Exercise ,. )"drogen peroxide solution (&4 ml reacts 5uantitati$el" with a solution
of
/
78n0
(&4 ml with dilute
& /
) S0
. !he same $olume of the
/
78n0

solution is <ust decolori3ed *" 14 ml of
/
8nS0
in neutral medium
simultaneousl" forming a dar. *rown precipitate of h"drated
&
8n0
. !he
*rown ppt. is dissol$ed in 14 ml of 4.& 8 sodium oxalate under *oiling
condition in the presence of dilute
& /
) S0
. %alculate the molarit" of
& &
) 0
.
Exercise 14.
In *asic medium,
& &
) 0
acts as an oxidi3ing agent in its reactions with
(A ( )
& /
'
%r S0
(#
&
Ag 0
(% ( )
1
]
'
+
7 9e %-
((
& & 6
7 %r 0
.N61$R6 TO $F$RCI6$6
Exercise 1: 5/6
Exercise &. 506
Exercise '. 5A6
Exercise /. 5/6
Exercise 1: 5/6
Exercise +. 5:6
Exercise 4% 506
Exercise :. 5A6
Exercise ,. m Q +.#
Exercise "?% 5A6
/I6C$&&.N$OU6 $F$RCI6$6
Exercise 1: Ho$ is dihydro!en o*tained from"
(A) di#ute su#phuric acid
(B) sodium hydro&ide
(C) $ater
<i%e one e)uation in each case.
Exercise &: A#thou!h
2
: 2
resem*#es
2
H 2
chemica##y yet it is a to&ic su*stance. =&p#ain.
Exercise ': What is the difference *et$een hydro#ysis and hydration"
Exercise /: What is meant *y autoproto#ysis of $ater"
Exercise 1: Why
&
H%2
is not used in the #a*oratory preparation of dihydro!en"
Exercise +: What are ad%anta!es of usin! hydro!en as a fue# o%er !aso#ine or coa#"
Exercise 6: Ho$ is a so#ution of
2 2
H 2
concentrated" Why it can not *e concentrated *y
disti##ation at ordinary pressure"
Exercise :: (a) 6ame the *#ue compound formed in the reaction of
2 2
H 2
$ith acidified
2 2 $
( /r 2
in ether" <i%e reaction.
(*) What is the princip#e in the *#eachin! action of
2 2
H 2
"
Exercise ,: The fo##o$in! statements are true under certain conditions. 0ention condition in
each case in a fe$ $ords.
(i) Hydro!en reacts $ith nitro!en to form ammonia.
(ii) Hydro!en can *e prepared from $ater at ordinary temperature.
(iii) A meta# $i## #i*erate hydro!en *y its reaction $ith di#ute
2 '
H "2
Exercise 14: Comp#ete the fo##o$in! reactions
(i) ( ) ( ) l
2
Ca7 s > H 7
(ii) ( ) ( ) l
2 2
6a 7 s > H 7
(iii) ( ) ( )
2
'e s > H 7 !
(i%) ( ) ( )
2
Cu7 s > H !
(%) ( ) ( )
2
C7 ! > H !
.N61$R6 TO /I6C$&&.N$OU6 $F$RCI6$6
Exercise 1: 5a6 More electropositive elements than hydrogen 5eg, Fn, 1e, Mg6 react with
dilute mineral acids 5dil, H/l K H2"2'6 to liberate dihydrogen gas.
2 ' ' 2
Fn H "2 Fn"2 H + +
5b6 Metals like 0e, Fn, "n, Al etc react with boiling alkali solution liberating
dihydrogen.

Heat
2 2 2
0e %a2H %a 0e2 H + +
Heat
2 2 2
Fn %a2H %a Fn2 H + +
5c6 ( )
2 2
2%a 2H 2 cold 2%a2H H + +
( )
Heat
2 2
Fn H 2 boiling Fn2 H + +
( )
2 & ' 2
&1e H 2 stream 1e 2 'H + +
Exercise &: Heavy water is inAurious to human being, plants and animals since it slows down
the rate of reactions occurring in then. 8hus heavy water does not support life so
well as does ordinary water.
Exercise ': Interaction of H
-
and 2H

ions of H22 with anions and cations of the salt

respectively to give the original acid and the original base is called hydrolysis eg.
2 & 2 2 &
%a /2 2H 2 2%a2H H /2 + +
Hydration, on the other hand, means addition of H22 to ions or molecules to form
hydrated ions or hydrated salts for eg.
( ) ( )
2
%a/l H 2 %a a7 /l a7
+
+ +
' 2 ' 2
/u"2 )H 2 /u"2 .)H 2 +
Exercise /: Auto protolysis of water means that two molecules of water reacts with each
other through protons transfer i.e. one acts as the acid while the other acts as the
base. 8he molecule which accepts a proton is converted into H&2
-
while that
which loses a proton is converted into 2H

ion.
( ) ( )
( ) ( )
2 2 &
acid base acid base
H 2 H 2 H 2 a7 2H a7
+
+ +


Exercise 1: H%2& is a strong oxidi4ing agent. It oxidi4es the H2 produced.
Exercise +: Advantages of using as fuel.
5i6 Abundantly available. 5ii6 .ollution free as the product is water.
5iii6 High calorific fuel. 5iv6 =xcellent reducing agent.
5v6 8ime re7uired for regeneration of H2 fuel is short.
Exercise 6: /oncentration of H222 is carried out carefully in a number of stages as follows.
5i6 =vaporation on water bath I slow evaporation of water continues until the
solution contains about )+@ H222.
5ii6 Dehydration in a )accum desiccators
)+@ solution of H222 obtained from above is taken in a disk and placed in a
vaccum desiccator containing conc. H2"2'. 8he inside presence is reduce as a
result of low, water readily evaporates and the water vapours thus produced are
absorbed by conc. H2"2'.8he H222 obtained is 9+@ pure.
5iii6 Distillation under reduced pressure
8he 9+@ solution of H222 as obtained above is subAected to distillation under
reduced pressure 5#+ I #) mm6. :uring this process, water distils over between
&+& I &#& ( leaving behind almost pure 99@ H222.
5iv6 Remo)al of least traces of ater
8he last traces of water in H222 are removed by free4ing it in a free4ing mixture
consisting of dry ice 5solid /226 and ether when crystal of H222 separate out.
8hese crystals are removed, dried and melted to give pure H222.
It can not be concentrated by distillation at ordinary pressure because H222
decomposes much below its boiling point to give H22 K 22.
Exercise :: 5a6 [ ] { }
2 2 2
H 2 H 2 2 ' +
[ ]
2 2 $ 2 ' 2 ' ) 2
( /r 2 H "2 ' 2 ( "2 2/r2 H 2 + + + +
2 2 $ 2 ' 2 2 2 ' ) 2
blue
( /r 2 H "2 'H 2 ( "2 2/r2 )H 2 + + + +

/hromium pentoxide

2
2
/r
2
2
2
5b6 8he bleaching action of H222 is due to the nascent oxygen which it liberate on
decomposition
[ ]
2 2 2
H 2 H 2 2 +
8he nascent oxygen combines with colouring matter which in turn gets
oxidi4ing. 8hus the bleaching of H222 is due to the oxidation of colouring
matter by nascent oxygen.
Exercise ,: 5i6 At high pressure 52++ atm6 and in presence of catalyst 1e, Mo.
5ii6 Dery active metals like %a, (, /a etc can react with H22 at room temperature.
5iii6 Metals which are more electropositive than hydrogen.
Exercise 14: 5i6 /a2 5s6 - H22 ( ) l
/a52H62 5a76
5ii6 %a22 5s6 - H22 ( ) l
2%a2H 5a76
5iii6 &1e 5s6 - 'H22 ( ) g
1e&2' - 'H2
5iv6 ( ) ( )
heat
2 2
/u2 s H g /u H 2 + +
5v6 /o5g6 - H22 5g6
( )
( )
$++(, 2++atm
& /o catalysis
/H 2H l
6O&D$D PROA&$/6
Su*<ecti$e:
Aoard Type Guestion
=ro* 1. Why is hard $ater softened *efore its use in *oi#ers"
Sol. Hard water cannot be used in boilers because on heating it gives precipitates of /a/2&
and Mg/2& alongwith /a"2' which forms scales in boilers. 8o avoid the scales
formation, hard water is softened before its use in boiler.
=ro* &. What %o#ume of o&y!en at 6T? $i## *e o*tained *y the comp#ete decomposition of 1;;
m# of H272 mar,ed 3; %o#ume"
Sol. # ml H222 of &+ volume liberates &+ ml 22 at %8..
#++ ml H222 of &+ volumes liberate &+ #++ ml 22 at %8. or & litre 22 at %8..
=ro* '. /u does not liberate H2 from dil H2"2'. =xplain.
Sol. /u is placed below H in electrochemical series having oxidation potential +.&' D
hence /u can not transfer electron to H
-
ions of H2"2' to liberate H2.
=ro* /. A small amount of phosphoric acid or glycerol or acetanilide is added in H222 during its
storage. =xplain.
Sol. All the three additives act as negative catalyst for the decomposition of H222 and thus
decomposition of H22 is checked off.
=ro* 1. Which isotope of hydro!en is used as a trace in or!anic reactions"
Sol. Hydrogen has three isotopes, Di4, H, : and 8. :ue to difference in masses, the rate
constants of three isotopes with the same substance are different. In other words, both
: and 8 show isotope effect. 0ut since 8 is not only radioactive but is also least
abundant hydrogen isotope. 8herefore : is used as a trace to study the mechanism of
organic reactions.
IIT Type Guestion
=ro* +. H222 is a very good solvent for ionic compounds. =xplain.
Sol. 8he dielectric constant of pure H222 is 9&.$ 5which also increases on dilution 59$ for
9+@ pure? #2+ for ,)@ pure6 which is appreciably high to weaken the electrostatic
forces of attraction among ions and to pass them in solution state.
=ro* 6. Anhydrous
2
0a2
is not used for preparin!
2 2
H 2
$hy"
Sol. Anhydrous
2
0a2
is not used because the
'
0a"2
formed during the reaction forms a
protective layer around the unreacted
2
0a2
and the reaction stops after some time.
=ro* :. 8tatues coated $ith $hite #ead on #on! e&posure to atmosphere turns *#ac, and the
ori!ina# co#our can *e restored on treatment $ith
2 2
H 2
. Why"
Sol. 2n long exposure to atmosphere, white lead is converted into black .b" due to the
action of
2
H "
present in the atmosphere. As a result, statues turn black
2 2 2
.b2 2H " .b" 2H 2 + +
2n treatment of these blackened statues with
2 2
H 2
, the black .b" get oxidi4ed to white
'
.b"2
and the colour is restored
2 2 ' 2
.b" 'H 2 .b"2 'H 2 + +
=ro* ,. 8ho$ $ith suita*#e e&amp#e hydro!en acts as reducin! a!ent as $e## as o&idi3in!
a!ent"
Sol. In the reaction of
2
H
with metals to form metal hydrides, it acts as an oxidi4ing agent.
( ) ( ) ( )
2
2%a s H g 2%a H s
+
+ +
Here %a has been oxidi4ed to %a
-
while
2
H
is reduced to hydride H

ion.
In the reaction of heated cupric oxide with dihydrogen to form
2
H 2
and copper metal,
dihydrogen acts as a reducing agent
( ) ( ) ( ) ( )
2 2
/u2 s H g /u s H 2 g

+ +
Here, /u2 is reduced to /u while dihydrogen is oxidi4ed to
2
H 2
.
=ro* 14. 73one is used for purifyin! air in cro$ded p#ace such as cinema ha##s+ tu*e rai#$ays+
tunne#s etc e&p#ain"
Sol.
&
2
is easily decomposes to produce ( )
2 & 2
2 22 &2
thereby purifying air at
crowed places.
=ro* 11. Why is sodium ch#oride #ess so#u*#e in hea%y $ater than in ordinary $ater"
Sol. 8he dielectric constant of
2
: 2
is less than that of
2
H 2
, therefore ionic compounds like
%a/l are less soluble in
2
: 2
than in
2
H 2
.
=ro* 1&. Why e#ectro#ysis of ordinary $ater occurs faster than hea%y $ater"
Sol. 8his is due to lower bond dissociation energy of protium bonds in H I 2 I H, which is
less than deuterium bonds in : I 2 I :, so electrolysis of
2
H 2
occurs much faster
than that of
2
: 2
.
=ro* 1'. 6ame the c#ass of hydrides to $hich H27+ B2H.+ 6aH and :aH3 *e#on!. What is
understood *y @Hydride <apA"
Sol. H22 covalent hydride, 02H, covalent hydride, %aH ionic hydride, *aH& metallic
hydride.
Hydride <ap! 8he metals of $, >, 9 groups do not form hydride. 8his is called the
hydride gap.
=ro* 1/. Concentrated su#phuric acid can not *e used for dryin!
2
H
. Why"
Sol. 8his is because conc.
2 '
H "2
on absorbing water from moisture
2
H
generates so much
heat that hydrogen catches fire.
=ro* 11. A mi&ture of hydra3ine and
2 2
H 2
$ith Cu((() cata#yst is used as roc,et prope##ant.
Why"
Sol. 8he reaction between hydra4ine and
2 2
H 2
is highly exothermic and is accompanied by
a large increase in the volumes of the product and hence this mixture is used as a
rocket propelled
( ) ( )
( )
( ) ( )
/u II
2 2 2 2 2 2
%H %H 2H 2 % g 'H 2 g + + l l
0*<ecti$e:
=ro*l 1. HC# is added to the fo##o$in! o&ides. Which one $ou#d !i%e
2 2
H 2
"
(A)
2
Mn2
(B)
2
.b2
(C) 0a2 (D) none of the a*o%e
Sol. "ince none of the oxides is a peroxide. Hence none of them would give
2 2
H 2
.
5:6
=ro*l &. When the same amount of 3inc is treated separate#y $ith e&cess of su#phuric acid and
e&cess of sodium hydro&ide+ the ratio of %o#umes of hydro!en e%o#%ed is
(A) 1 B 1 (B) 1 B 2
(C) 2 B 1 (D) C B 4
Sol.
2 ' ' 2
Fn H "2 Fn"2 H + +
2 2 2
Fn 2%a2H %a Fn2 H + +
8he ratio of volumes of
2
H
evolved in both the cases is # ! #.
5A6
=ro*l '. Which of the fo##o$in! is the true structure of H272"
(A)
H 2 2 H (B
)
2 2
H
H
(C)
2 2
H
H
(D
)
2
H
H
2
Sol. 2xygen atom is
&
sp hybridi4ed having two large pair of electrons. 8herefore the
structure of hydrogen peroxide is
2 2
H
H

506
=ro*l /. When e#ectric current is passed throu!h an ionic hydride in the mo#ten state
(A) hydro!en is #i*erated at the anode
(B) hydro!en is #i*erated at the anode
(C) no reaction ta,es p#ace
(D) hydride ion mi!rates to$ards cathode
Sol. Ionic hydride contains H

ion which liberates

2
H
at the anode.
5A6

=ro*l 1. Which of the fo##o$in! can not *e o&idi3ed *y
2 2
H 2
"
(A) D( > HC# (B)
&
2
(C) ?*8 (D)
2 &
%a "2
Sol.
&
2
is more powerful oxidi4ing agent than
2 2
H 2
. "o
2 2
H 2
reduces
&
2
to
2
2
.
& 2 2 2 2
2 H 2 H 2 22 + +
506
=ro*l +. The reaction
A!27 > H272 2A! > H27 > 72 ta,es p#ace in
(A) *asic medium (B) *#eachin! a!ent
(C) neutra# medium (D) *oth in acidic and *asic medium
Sol.
2 2
H 2
on oxidation gives
2
2
only in basic medium
5A6
=ro*l 6. Which of the fo##o$in! compounds turns $hite on treatment $ith
2 2
H 2
.
(A) H!8 (B) ?*8
(C) 6i8 (D) Cu8
Sol. 2 2 ' 2
black
white
.b" 'H 2 .b"2 'H 2 + +

506
=ro*l :. The stron!est *ase is
(A)
&
%H
(B)
&
.H
(C)
&
AsH
(D)
&
"bH
Sol. 0asic character decreases as the si4e of central atom increases in hydrides of group
#) members
5A6
=ro*l ,. 8emi $ater !as is a mi&ture of
(A)
2
/2 H +
(B)
2
/2 % +
(C)
2 2
/2 H % + +
(D) none
Sol. Mixture of /2 -
2
H
-
2
%
is called semi water gas.
5/6
=ro*l 14. A hydride of nitro!en $hich is acidic is
(A)
&
%H
(B)
2 '
% H
(C)
2 2
% H
(D)
&
% H
Sol.
&
% H
5hydra4oic acid6 is the acidic hydride of nitrogen
5:6
TrueH7alse
=ro*l 11. Tritium can *e o*tained from natura# sources.
Sol. 1alse
=ro*l 1&. H272 act as antich#or.
Sol. 8rue
=ro*l 1'. 8odium car*onate can remo%e on#y temporary hardness of $ater.
Sol. 1alse
=ro*l 1/. 7rtho hydro!en has #o$er ener!y and is more sta*#e than para hydro!en.
Sol. 8rue
=ro*l 11. B#eachin! action of H27 is due to its reducin! nature.
Sol. 1alse
7ill in the Alan!s
=ro*l 1+. When hydro!en pero&ide is treated $ith acidified D2Cr27E so#ution+ a FFF.. co#our
appears.
Sol. 0lue green
=ro*l 16. /arbon monoxide combines with hydrogen when heated to #)+ ')+
o
/ in presence of
Fn2 - /u to form RRRR..
Sol. /H&2H
=ro*l 1:. The mi&ture of hydra3ine hydrate and FFFF $ith a copper ((() cata#yst is used as
roc,ed prope##ant.
Sol. H222
=ro*l 1,. Chemica# name for permutit is FFFFF.
Sol. Feolite
=ro*l &4. H272 is used as FFFFF.. in toothpaste.
Sol. Antiseptic
.66I9N/$NT PROA&$/6
Su*<ecti$e:
&e)el 5 O

"# :iscuss briefly the properties and uses of different types of hydrides.
(# Hhat is the meant by water gas shift reactionP
:escribe it use for the preparation of dihydrogen.
*# :ifferentiate between
5a6 hard and soft water
5b6 temporary and permanent hardness of water.
0riefly explain how to remove temporary and permanent hardness of water.
,# =xplain the following
5i6 "oft water lathers with soap but not with hard water.
5ii6 8emporary hard water becomes soft on boiling.
5iii6 Hater can extinguish most fires but not petrol fire.
5iv6 Hard water is softened before use in boilers.
-# =xplain, why the density of ice is less than waterP
2# Hrite short notes on
5i6 2rtho and para hydrogen 5ii6 0oschs process
5iii6 calgon 5iv6 Ion;exchange method for removal of hardness of water.

4# How is heavy water prepared from normal waterP :iscuss the importance of heavy water in
nuclear reactors. Hhat is the action of heavy water on
5i6 "odium 5ii6 %a2H 5iii6
'
%H /l
5iv6
&
"2
=# Hhat is the difference between hydrolysis and hydrationP Hhat are the ways in which water
molecules are bonded to the anhydrous salt to form hydrateP
<# 5a6 Hhat are interstitial hydridesP :iscuss their important uses. How do they differ from
molecular hydrides.
5b6 :istinguish between salt like and covalent hydrides. :iscuss briefly the characteristic of
salt like hydrides.
5c6 Hhat is understood by hydride gap.
"?# :escribe permutit process for softening of hard water.
/alculate the hardness of a water sample which contains +.++# mole of
'
Mg"2
dissolved
per litre of the solution.
""# A solution of ferric chloride acidified with H/l is unaffected when hydrogen is bubbled through
it, but is reduced when 4inc is added to some acidified solution. =xplain.
"(# Hhy should a bottle of H222 be cooled before opening itP
"*# Hhat should be the necessary re7uirements for portable water i.e., water for drinking
purposes.
",# =xplain why hydrogen is best placed separately in the periodic table of elementsP
"-# Hhat is understood by hydrogen economyP
#,. Metals like platinum K palladium can adsorb large volumes of hydrogen under special
conditions. "uch adsorbed hydrogen by the metals is calledP
#$. 1ind out the order of the reaction for the decomposition of hydrogen peroxide
2 2 2 2
2H 2 2H 2 2 + .
#>. Hhen
2 2
H 2
is reacted with
2 2 $
( /r 2
K either, the ethereal layer becomes blue, whyP
#9. Hrite the correct order of the 2 I 2 bond length in
2
2
,
2 2
H 2
and
&
2
.
2+. Hhat would happen when a small 7uantity of H222 is added to a solution of 1e"2'P
&e)el3 I
"# In the preparation of hydrogen in the laboratory from granular 4inc. Hhy the following acids
cannot be used.
5a6 /onc.
2 '
H "2
5b6 conc. H/l 5c6 nitric acid
(# Hydrogen peroxide acts both an oxidi4ing agent and as a reducing agent in alkaline solution
towards certain first row transition metal ions. Illustrate three properties of
2 2
H 2
using
chemical e7uations.
*# 2+ ml of a solution containing +.2 g of impure sample of
2 2
H 2
reacts with +.&#, g of
'
(Mn2

5acidic6. /alculate
5a6 .urity of
2 2
H 2
.
5b6 Dolume of dry
2
2
evolved at +
o
/ and $)+ mm ..
,# 3ustify the statement
NAn a7ueous solution of hydrogen peroxide is weakly acidicO.
-# =xplain. In the preparation of
2 2
H 2
, the use of phosphoric acid has an advantage over dilute
sulphuric acid.
2# <iven reason
5a6 Marine species cannot survive in distilled water.
5b6 :istilled water in called deionised water.
4# <ive ion electron e7uation for the following reactions
5a6 oxidation of ferrous ions to ferric ions by
2 2
H 2
.
5b6 oxidation of iodide ion to iodine by
2 2
H 2
.
5c6 oxidation of acidified per magnate ion
2 2
H 2
.
5d6 reduction of alkaline ferricyanide ions to ferrocyanide ions.
=# Hhat happens whenP
5i6 Hydrolith is treated with water.
5ii6 Heavy water reacts with aluminium carbide.
5iii6 /oncentrated caustic potash solution is spilled on granulated 4inc.
<# 2ne litre of a sample of hard water contains # Mg of /a/l2 and # Mg of Mg/l2. 1ind the total
hardness of in terms of parts of
&
/a/2
per
,
#+ parts of water of mass.
"?# =xplain
5a6
2 2
H 2
act as a bleaching agent.
5b6 /oncentration of hydrogen peroxide is difficult.
##. Hhat happens whenP
5a6 0arium peroxide is treated with cold dilute sulphric acid
5b6 "odium peroxide is treated with cold dilute sulphuric acid and the resulting mixture is
cooled below 2$&(.
5c6 0arium peroxide is treated with phosphoric acid.
5d6 Hydrogen peroxide is treated with sodium carbonate.
5e6 Hydrogen Iodide is added to hydrogen peroxide.
#2. =xplain
5a6 Hhy hydrogen peroxide is stored in coloured plastic bottleP
5b6 H222 prepared from hydrated barium peroxide and dilute sulphuric acid can not be
stored for a long time.
#&. 8wo li7uids 5A6 and 506 are made of same elements and are diamagnetic. *i7uid 5A6 on
treatment with (I and starch gives blue coloured solution, however. *i7uid 506 is neutral to
litmus and does not gives response to starch iodine paper. Identify 5A6
and 506.
#'. )+ ml of an a7ueous solution of H222 was treated with an excess of (I solution in dil. H2"2',
the liberated iodine re7uired 2+ ml of +.# % %a2"2& solution for complete reaction. /alculate
concentration of H222 in gBlitre.
#). /omplete the following
5i6 ( )
2 2
3
Cr 7H > 6a7H> H 7
5ii6

3 2
Ca ? > D 7
5iii6

'entonGs
3 rea!ent
CH CH7H.C77H
&e)el3 II
"# 8he process ( ) ( )
2
#
H g e H g
2

+ is endometric
#
H #)#k3mol

+ .
Let salt like sodium hydride are known. How do you account for thisP
(# 1ind the degree of hardness of a sample of water containing #2 mg of
'
Mg"2
5mol. Mass
#2+6 per kg of water.
*# =xplain the following
5a6 A small of amount of acid or alkali is added before electrolysis of water.
5b6 8he electrolysis of water for manufacturing hydrogen gas is always carries out in the
presence of acid 5
2 '
H "2
6 or alkali 5(2H6. Let no
2
'
"2 or (
+
ions are discharged.
,# =xplain the following
5a6 A solution of ferric chloride acidified with H/l is unaffected when hydrogen is bubbled
through it, but gets reduced when 4inc is added to some acidified solution.
5b6 Hhen sodium hydride is fused state is electrolysed, hydrogen is discharged at anode.
-# =xplain the following
5i6 Hhy are the melting and boiling points of
2
: 2
are higher than those of ordinary waterP
5ii6 .resence of water is avoided in preparation of
2 2
H 2
from
2 2
%a 2
.
5iii6 Hydrogen peroxide gives acidic properties.
2# =xplain the following
5i6 A mixture of hydra4ine and
2 2
H 2
is used as a rocket propellant.
5ii6 Hydrated barium peroxide is used in the preparation of hydrogen peroxide instead of the
anhydrous form.
4# Hhat happens whenP
5a6 Hydrogen peroxide is added to ferrous ammonium sulphate solution.
5b6 "odium hydride reacts with diborane.
5c6 0en4ene is treated with
2 2
H 2
in presence of
'
1e"2
.
=# A ) ml solution of
2 2
H 2
liberates +.)+> g of iodine from an acidified (I solution. /alculate the
strength of
2 2
H 2
solution in terms of volume strength at "8..
<# 8o a 2) ml
2 2
H 2
solution excess of acidify solution of potassium iodide was added. 8he
iodine liberated re7uired 2+ ml of +.& sodium thiosulphate solution. /alculate the volume
strength of
2 2
H 2
solution.
"?# #+ ml of a solution of
2 2
H 2
labeled #+ volume Aust decolourises #+ ml of potassium per
magnate solution acidified with dilute
2 '
H "2
acid. /alculate the amount of potassium per
magnate in the given solution.

0*<ecti$e:
&e)el5 I
"# Dolume of same weight of ice isRRRR.thanBto the same weight of water
5A6 More 506 *ess
5/6 =7ual 5:6 not related
(# Hhich of the following hydrides is covalent compoundP
5A6 *iH 506 %aH
5/6
2
MgH
5:6
2
/aH
*# Hhich of the following hydroxides is amphotericP
5A6 ( )
2
Mg 2H
506 ( )
2
/a 2H
5/6 ( )
2
0e 2H
5:6 ( )
2
"r 2H
,# 8he 2 I 2 I H bond angle in
2 2
H 2
in gas phase is
5A6 #+,
o
506 #+9 2>
o
5/6 #2+
o
5:6 9'.>
o
-# Amongst
2 2 2 2
H 2, H ", H "e and H 8e
the one with the highest boiling point is
5A6
2
H 2
because of hydrogen bonding
506
2
H 8e
because of higher molecular weight
5/6
2
H "
because of hydrogen bonding
5:6
2
H "e
because of lower molecular weight
2# .olyphosphates are used as water softening agents because they
5A6 form soluble complexes with anionic species 506 precipitate anionic species
5/6 form soluble complexes with cationic species 5:6 precipitate cationic species
4# 8he volume strength of #.)
2 2
%H 2
solution is
5A6 '.> 506 ).2
5/6 >.> 5:6 >.'
=# 8he volume of #+ volume
2 2
H 2
solution that decolouri4es 2++ ml of 2%
'
(Mn2
solution in
acidic medium is
5A6 ##2 ml 506 &&, ml
5/6 2++ ml 5:6 22' ml
<# An oxide which gives
2 2
H 2
on treatment with dilute acid is
5A6
2
.b2
506
2 2
%a 2
5/6
2
Mn2
5:6
2
8i2
"?# Acidified solution of chromic acid on treatment with
2 2
H 2
yield
5A6
& 2 2
/r2 H 2 2 + +
506
2 & 2 2
/r 2 H 2 2 + +
5/6
) 2
/r2 H 2 +
5:6
2 2 $ 2 2
H /r 2 H 2 2 + +
""# 8he correct increasing order of the acidity of
2 2 2 2
/2 , H 2 and H 2
is
5A6
2 2 2 2
/2 H 2 H 2 < <
506
2 2 2 2
H 2 H 2 /2 < <
5/6
2 2 2 2
H 2 H 2 /2 < >
5:6
2 2 2 2
H 2 /2 H 2 > >
"(# Ammonium per sulphate on heating under reduced pressure gives
5A6
2 2
H 2
506
2
2
5/6
2
H
5:6 ( )
' '
2
%H "2
"*# 8he hybridi4ation on the oxygen atom in
2 2
H 2
is
5A6
&
sp d 506 sp
5/6
2
sp 5:6
&
sp
",# In
2 2
H 2
proton 5 H
+
6 exist as
5A6
&
H 2
+
506
& '
H 2
+
5/6 ( )
2
n
H H 2
+
5:6 all the above
"-# 8he reactions
2 2 2 2
H " H 2 " 2H 2 + + manifests
5A6 acidic nature of
2 2
H 2
506 alkaline nature of
2 2
H 2
5/6 oxidi4ing action of
2 2
H 2
5:6 reducing nature of
2 2
H 2
.ssertionHReason Type Guestions
Codes%
5a6 0oth A and E are true and E is the correct explanation of A.
5b6 0oth A and E are true but E is not the correct explanation of A.
5c6 A is true but E is false.
5d6 A is false but E is true.
5e6 A and E both are false.
"2# .ssertion :.;% 2n passing H2 gas into a7ueous 1e
&-
solution, resulting solution gives test of
1e
&-
.
Reason :R;% H25g6 reduces 1e
&-
to 1e2- but 1e
2-
I" oxidi4ed to 1e
&-
by atmospheric oxygen.
"4# .ssertion :.;% :rinking of heavy water 5:226 mixed water 5H226 could prove fatal.
Reason :R;% 8here is slower rate of transfer of :
-
compared with that of H
-
ion in acid;base
reaction involved en4yme catalysis.
"=# .ssertion :.;% Hydride 5H

6 is a conAugate base of hydrogen 5H26.

Reason :R;% =very negative ion is an electron;pair donor and is thus, a *ewis base.
"<# .ssertion :.;% Ionic hydrides are the ready;made source of H2.
Reason :R;% *iH is an ionic hydride.
(?# .ssertion :.;% H222 decomposes %a2/2& to give /22.
Reason :R;% H222 has two protons and is thus a strong acid.


&e)el3II
"# Hydrogen will not reduce
5A6 heated cupric oxide 506 heated ferric oxide
5/6 heated stannic oxide 5:6 heated aluminium oxide
(# Hydrolysis of one mole of peroxodisulphuric acid produces
5A6 two moles of sulphuric acid
06 two mole of peroxomonosulphuric acid
5/6 one mole of sulphuric acid and one mole of peroxomonosulphric acid
5:6 one mole of sulphuric acid, one mole of peroxomonosulphuric acid and one mole of
2 2
H 2
*# Hhich contains both polar and non;polar bondsP
5A6
'
%H /l
506 H/%
5/6
2 2
H 2
5:6
'
/H
,# 8he critical temperature of water is higher than that
2
2
because the
2
H 2
molecule has
5A6 fever electrons than oxygen 506 two covalent bonds
5/6 D I shape 5:6 dipole moment
-# Hhen 4eolite which is hydrated sodium aluminium silicate is treated with hard water the
sodium ions are exchanged with
5A6 H ions
+
506 /a ions
+
5/6
2
'
"2

5:6 all of the above

2# Hydrogen gas is liberated by the action of aluminum with a concentrated solution of
5A6 %a2H 506 ( )
2
Mg 2H
5/6 ( )
2
/a 2H
5:6 none
4# Heavy water is obtained by
5A6 boiling water 506 distillation of
2
H 2
5/6 pronged electrolysis of
2
H 2
5:6 heating
2 2
H 2
=# 8he compound that can work both as an oxidi4ing agent and a reducing agent is
5A6
'
(Mn2
506
2
H "
5/6
2
0a2
5:6
2 2
H 2
<# In acidic medium,
2 2
H 2
acts as a reducing agent in its reaction with
5A6
'
1e"2
506
'
(Mn2
5/6
2 '
( Mn2
5:6 ( )
'
,
( 1e /% 1
]
"?# 8he decomposition of
2 2
H 2
can be checked by the addition of
5A6 alkali metal oxides 506 ben4ene
5/6 acetamilide 5:6
2
Mn2
""# 8he metal which displaces hydrogen from a boiling caustic soda solution is
5A6 Mg 506 1e
5/6 A" 5:6 Fn
"(#
2 2
H 2
acts as an oxidi4ing agent in
5A6 neutral medium 506 acidic medium
5/6 alkaline medium 5:6 both acidic K alkaline medium
"*# :ecomposition of
2 2
H 2
is favoured by
5A6 traces of acids 506 alcohol
5/6 acetanilide 5:6 Mn2
",# 8he maximum possible number of hydrogen bonds a water molecule can form in ice is
5A6 # 506 2
5/6 & 5:6 '
"-#
&
%H
and
2
H 2
form
'
%H 2H
by
5A6 electrovalent bond 506 covalent bond
5/6 coordinate bond 5:6 none of these
"2# "elect correct statements!
5A6 H2 is more rapidly adsorbed on Mo surfaces than :2
506 H2 reacts over #& times faster with /l2 than :2 because H2 has lower energy of activation.
5/6 both are true
5:6 none is true
"4# H2 reacts much faster with /l2 than :2, because
5A6 rate of diffusion of H2 is greater than :2
506 H2 has lower energy of activation than :2
5/6 both statements are correct
5:6 none of the statements is correct
"=# Hhich is true statement about :22 and H22P
5A6 :22 has lower dielectric constant than H22
506 %a/l is more soluble in :22 than in H22
5/6 0oth of the above are correct
5:6 none of the above is correct
"<# In the following compounds H is covalent bonded in case of
5A6 0aH2 506 /aH2
5/6 "iH' 5:6 %aH
(?# "elect the correct statement!
5A6 Ammonia is more soluble in a7ueous ammonium chloride than in pure water
506 "olid ammonium fluoride and ice are miscible in all proportions
5/6 both the statements are correct
5:6 none of the statements is correct
.N61$R6 TO .66I9N/$NT PROA&$/6
Su*<ecti$e:
&e)el 3 O
'. 5i6 8he hard water contains bicarbonates cruddy white ppt. chlorides and sulphate of /a and
Mg. Hhen hard water is treated with soap solution, /a
-2
K Mg
-2
ions present in water
react with anions of fatty acids present in soaps to form curdy white ppt. As a result it
does not produce lather with soap.
( )
#$ &) 2 #$ &)
2
cordy whiteppt.
2/ H /22 %a /a/l / H /22 2%a/l
+
+ +
5ii6 Hhen temporary hard water is boiled, bicarbonates of calcium and magnesium
respectively.
8hese insoluble carbonate are removed by filtration and the water is rendered soft.
( )
& & 2 2
2
/a H/2 /a/2 /2 H 2

+ +
( )
& & 2 2
2
Mg H/2 Mg/2 /2 H 2

+ +
5iii6 .etrol being lighter than water, floats over the surface of water. Hence the petrol fire can
not be extinguished by water.
5iv6 8he salt of /a K Mg slowly is long time form a layer on the wall of boilers, making is a
bad conductor of heat. "o making it unsuitable for use.
). Ice has open cage like structure with a number of vacant spaces in the crystal lattice. As a
result, density of ice is lower than that of water.
,. 5i6 Hhen the spins of the nuclei are in the same direction 5parallel spins6, dihydrogen is called
ortho hydrogen and when the spins are in the opposite direction 5anti parallel spins6,
dihydrogen is called para hydrogen.
5iii6 /algon is the trade name for sodium hexametaphosphate %a2S%a'5.2&6,T. It softens hard
water by exchanging its %a
-
ions with /a
-2
ions present in hard water.
$. 5i6 2 2
sodium deutroxide
2%a 2: 2 2%a2: : + +
5ii6
2
%a2H : 2 %a2: H:2 + +


5iii6
' 2 &
%H /l : 2 %H :/l H:2 + +


5iv6
& 2 2 '
:euteurosulphuric acid
"2 : 2 : "2 +
>. Hater has the ability to combine with some metal salts to form compounds known as
hydrates. 8here are three categories of hydrates.
5a6 Hater molecules form complex ions by combining with metal ions through
co I ordinates bonds.
e.g. ( ) ( ) ( ) ( )
2
2 & 2 , & 2 &
, ,
2
%i H 2 %2 ? Al H 2 /l ? /r H 2 /l
+

1 1 1
] ] ]
5b6 Hater molecules may be hydrogen bonded to certain oxygen containing anions.
e.g. /u"2'.)H22 in which four water molecules are coordinated to a central /u
2-
ion
while the fifth water molecules is hydrogen bonded to sulphate groups. 8hus, it can also
be represented as ( )
2 ' 2
'
/u H 2 "2 .H 2 1
]
( )
' 2 ' 2
0lue
/u"2 )H 2 /u"2 .)H 2 s +
5c6 $, > K 9
th
group elements does not form hydride thus it is called as hydride gap
#+. +.# ppm
##. Eeaction of Fn and H/l gives nascent hydrogen which is more powerful reducing agent than
ordinary hydrogen and thus ferric chloride solution is reduced.
#2. H222 being unstable li7uid, decomposes into water and oxygen either on standing or on
heating. 0ottle of H22 is therefore cooled before opening to lower the vapour pressure of
contents in it otherwise bumping of li7uid may take place.
#&. It should be free from suspended impurities, bacterial impurities and also dissolved impurities
which are harmful to body.
#'. It electronic configuration resembles alkali metals 5group I6 and halogen group DII and it
shows reactions and properties similar as well as dissimilar to the elements of these two
groups.
#). 8he production, storage and transportation of energy in the form of li7uid or gaseous
hydrogen as a fuel in view of the facts that fossil fuels are limited, electricity cant be stored
and use of nuclear power is restricted.
#,. 2cclusion
#$. 1irst order reaction
#>. /r52H62
#9. H222 U 2& U 22
2+.
2 &
2 2 2
21e H 2 2H 21e 2H 2
+ + +
+ + +
or
2 &
1e 1e e
+ +
+
&e)el 5 I
#. 5a6 /ons.
2 '
H "2
is not used because a part of the acid gets reduced to
2
"2
.
5b6
2
H
liberated by conc. H/l on Fn will be impure as it contains fumes of volatile H/l.
2
Fn/l
formed is insoluble in conc. H/l and forms coating on 4inc and the reaction stop after
some time.
5c6
&
H%2
acts as an acid well as oxidi4ing agent.
2. /hromium hydroxide is oxidised by
2 2
H 2
in presence of %a2H into sodium chromate.
.otassium ferricyanide is reduced to ferricyanide in presence of (2H by
2 2
H 2
.
&. 5a6 >)@ 5b6 #2'.$9 ml
). Hhen phosphoric acid is used in the preparation of
2 2
H 2
from
2
0a2
, it plays the double role.
It liberates
2 2
H 2
and also acts as preservator by retarding its decomposition.
>. 5i6 Hydrolysis of
2
/aH
occurs with evolution of
2
H
( )
2 2 2
2
/aH 2H 2 /a 2H 2H + +
5ii6 :euteromethane is evolved
( )
2 2 2 '
&
Al / #2: 2 'Al 2: &/: + +
5iii6 Fn dissolves in caustic potash solution evolving hydrogen
2 2 2
pot. 4incate
Fn (2H ( Fn2 H + +
9. #.9) ppm.
#&. A is
2 2
H 2
and 0 is
2
H 2
.
#'. +.,>g litre
#). 5i6 ( )
2 2 2 ' 2
&
2/r 2H '%a2H &H 2 2%a /r2 >H 2 + + +
5ii6
& 2 2 &
/a . ,: 2 &/a52:6 2.: + +
5iii6
'
1e"2
& 2 2 & 2
/H /H2H./22H H 2 /H /2/22H 2H 2 + +
&e)el 3 II
#. 8his is due to the reason that high lattice energy released is more that compensates the
energy needed for the formation of H
+
ions from
2
H
gas.
2. #++ ppm.
&. 5a6 .ure water being a weak electrolyte and feebly ioni4ed K bad conductor of electricity.
5b6 "ulphate K potassium ions are not discharged as the discharge potential of
2
'
"2

is much
higher than 2H

ions and the discharge potential of (

+
ions is much higher than H
+
ions.
'. 5a6 Molecular 5ordinary6 hydrogen is not so reactive as hydrogen at the moment of formation.
Finc reacts with the acid to produce nascent hydrogen. Hhich reduces ferric chloride into
ferrous chloride.
5b6 "odium hydride is an electrovalent compound in which hydrogen is present as an anion,
H on electrolysis it is discharged at anode.
). 5i6
2
: 2
has more molecular mass and greater degree association than
2
H 2
and thus shows
higher mid point and boiling point.
5ii6 Hater reacts with
2 2
%a 2
to produce %a2H which increases decomposition of
2 2
H 2
.
5iii6
2 2
H 2
reacts bases to form peroxides 5salts6 K water
2 2 2 2 2
2%a2H H 2 %a 2 2H 2 + +
( )
2 2 2 2
2
0a 2H H 2 0a2 2H 2 + +
,. 5i6 8he reaction is highly exothermic. It brings large increase in volume also.
( ) ( )
2 ' 2 2 2 2
% H 2H 2 % g 'H 2 g + +
5ii6 If anhydrous barium peroxide is used,
'
0a"2
formed forms an insoluble protective
coating on the surface of solid barium peroxide. 8his prevents further reaction of the acid.
$. 5i6
' 2 ' 2 ' ' 2 2
&(Mn2 &H "2 ( "2 2Mn"2 >H 2 )2 + + + +
5ii6 "odium borohydride is formed
2 , '
0 H 2%a2H 2%a0H +
5iii6 0en4ene in presence of
'
1e"2
is converted into phenol.
>. '.'> volume.
9. #.&''
#+. +.),' g
0*<ecti$e:
&e)el 5 I
#. . 2. C &. C
'. D ). . ,. C
$. D >. D 9. A
#+. C ##. A #2. .
#&. D #'. D #). C
#,. C #$. . #>. A
#9. A 2+. C
&e)el 5 II
#. D 2. C &. C
'. D ). A ,. .
$. C >. D 9. A
#+. C ##. D #2. D
#&. D #'. D #). .
#,. C #$. A #>. .
#9. C 2+. C