"manishkumarphysics.

in"
1
CHEMISTRY
Mole Concept-2
Oxidation & Reduction
Let us do a comparative study of oxidation and reduction :
Oxidation Reduction
1. Addition of Oxygen 1. Removal of Oxygen
e.g. 2Mg + O
2
2MgO e.g. CuO + C Cu + CO
2. Removal of Hydrogen 2. Addition of Hydrogen
e.g. H
2
S + Cl
2
2HCl + S e.g. S + H
2
H
2
S
3. Increase in positive charge 3. Decrease in positive charge
e.g. Fe
2+
Fe
3+
+ e

e.g. Fe
3+
+ e

Fe
2+
4. Increase in oxidation number 4. Decrease in oxidation number
(+2) (+4) (+7) (+2)
e.g. SnCl
2
SnCl
4
e.g. MnO
4

Mn
2+
5. Removal of electron 5. Addition of electron
e.g. Sn
2+
Sn
4+
+ 2e

e.g. Fe
3+
+ e

Fe
2+
Oxidation Number
It is an imaginary or apparent charge developed over atom of an element when it goes from its
elemental free state to combined state in molecules.
It is calculated on basis of an arbitrary set of rules.
It is a relative charge in a particular bonded state.
In order to keep track of electron-shifts in chemical reactions involving formation of compounds, a
more practical method of using oxidation number has been developed.
In this method, it is always assumed that there is a complete transfer of electron from a less
electronegative atom to a more electronegative atom.
Rules governing oxidation number
The following rules are helpful in calculating oxidation number of the elements in their different
compounds. It is to be remembered that the basis of these rule is the electronegativity of the
element .
Fluorine atom :
Fluorine is most electronegative atom(known). It always has oxidation number equal to 1 in all its
compounds
Oxygen atom :
In general and as well as in its oxides , oxygen atom has oxidation number equal to 2.
In case of (i) peroxide (e.g. H
2
O
2,
, Na
2
O
2
) is 1,
(ii) super oxide (e.g. KO
2
) is 1/2
(iii) ozonide (e.g. KO
3
) is 1/3
(iv) in OF
2
is + 2 & in O
2
F
2
is +1
Hydrogen atom :
In general, Hatomhas oxidation number equal to +1. But in metallic hydrides ( e.g. NaH, KH), it is 1.
Halogen atom :
In general, all halogen atoms (Cl, Br , I) have oxidation number equal to 1.
But if halogen atom is attached with a more electronegative atom than halogen atom, then it will
showpositive oxidation numbers.
e.g.
3
5
ClO K
+
,
3
5
O HI
+
,
4
7
O HCI
+
,
5
3
KBrO
+
"manishkumarphysics.in"
2
CHEMISTRY
Metals :
(a) Alkali metal (Li , Na, K, Rb, .......) always have oxidation number +1
(b) Alkaline earth metal (Be , Mg , Ca .......) always have oxidation number +2.
(c) Aluminium always has +3 oxidation number
Note: Metal may havenegativeor zero oxidation number
Oxidation number of an element in free state or in allotropic forms is always zero
e.g.
0
3
0
4
0
8
0
2
O , P , S , O
Sum of the oxidation numbers of atoms of all elements in a molecule is zero.
Sum of the oxidation numbers of atoms of all elements in an ion is equal to the charge on the ion .
If the group number of an element in modern periodic table is n, then its oxidation number may vary
from
(n 10) to (n 18) (but it is mainly applicable for p-block elements )
e.g. N- atom belongs to 15
th
group in the periodic table, therefore as per rule, its oxidation number
may vary from
3 to +5 (
2
3
3
NO , H N
+
,
3
2
3
O N
+
,
2
4
O N
+
,
5
2
5
O N
+
)
The maximum possible oxidation number of any element in a compound is never more than the
number of electrons in valence shell.(but it is mainly applicable for p-block elements )
Calculation of average oxidation number :
Example-1 Calculateoxidation number of underlined element :
(a) Na
2
S
2
O
3
(b) Na
2
S
4
O
6
Solution. (a) Let oxidation number of S-atom is x. Now work accordingly with the rules given before .
(+1) 2 + (x) 2 + (2) 3 =0
x = + 2
(b) Let oxidation number of S-atom is x
(+1) 2 + (x) 4 + (2) 6 = 0
x = + 2.5
It is important to note here that Na
2
S
2
O
3
have two S-atoms and there are four S-atom in Na
2
S
4
O
6
.
However none of the sulphur atoms in both the compounds have + 2 or + 2.5 oxidation number, it is
the average of oxidation number, which reside on each sulphur atom. Therefore, we should work to
calculate the individual oxidation number of each sulphur atom in these compounds.
Calculation of individual oxidation number
It is important to note that to calculate individual oxidation number of the element in its compound one should
knowthe structure of the compound and use the following guidelines.
Formula :
Oxidation Number = Number of electrons in the valence shell Number of electrons taken up after bonding
Guidelines : It is based on electronegativity of elements.
1. If there is a bond between similar type of atom and each atom has same type of hybridisation, then
bonded pair electrons are equally shared by each element.
Example : Calculate oxidation number of each Cl-atom in Cl
2
molecule
Structure :
"manishkumarphysics.in"
3
CHEMISTRY
I : Number of electrons in the valence shell = 7.
Number of electrons taken up after bonding = 7.
oxidation number = 7 7 = 0.
II : similarly, oxidation number = 7 7 = 0
2. If there is a bond between different type of atoms :
e.g. A B (if B is more electronegative than A)
Then after bonding, bonded pair of electrons are counted with B - atom .
Example : Calculate oxidation number of each atom in HCl molecule
Structure :
Note : Electron of H-atomis nowcounted with Cl-atom, because Cl-atomis more electronegative
thanH-atom
H : Number of electrons in the valence shell = 1
Number of electrons taken up after bonding = 0
Oxidation number of H = 1 0 = + 1
Cl : Number of electrons in the valence shell = 7
Number of electrons taken up after bonding = 8
Oxidation number of Cl = 7 8 = 1
Example-2 Calculate individual oxidation number of each S-atom in Na
2
S
2
O
3
(sodium thiosulphate) with the
help of its structure .
Solution. Structure:
Note : I (central S-atom) is sp
3
hybridised (25% s-character) and II (terminal S-atom) is sp
2
hydbridised (33%s-character). Therefore, terminal sulphur atomis moreelectronegative
than central sulphur atom. Now, thesharedpair of electrons arecountedwithterminal S-
atom.
I, S-atom : Number of electrons in the valence shell = 6
Number of electrons left after bonding = 0
Oxidation number of central S-atom = 6 0 = + 6
II, S-atom : Number of electrons in the valence shell = 6
Number of electrons left after bonding = 8
Oxidation number of terminal S-atom = 6 8 = 2
Now, you can also calculateAverage Oxidation number of S=
2
) 2 ( 6 +
= + 2 (as we have calculated before)
"manishkumarphysics.in"
4
CHEMISTRY
Miscellaneous Examples :
In order to determine the exact or individual oxidation number we need to take help from
the structures of the molecules. Some special cases are discussed as follows:
The structure of CrO
5
is
O O
O O
Cr
||
O
From the structure, it is evident that in CrO
5
there are two peroxide linkages and one double bond. The
contribution of each peroxide linkage is 2. Let the oxidation number of Cr is x.
x + (2)2 + (2) = 0 or x = 6
Oxidation number of Cr = + 6 Ans
The structure of H
2
SO
5
is
H O O S
O
O
O H
From the structure, it is evident that in H
2
SO
5
, there is one peroxide linkage, two sulphur-oxygen double
bonds and one OH group. Let the oxidation number of S = x.
(+ 1) + ( 2) + x + (2) 2+ (2) + 1 = 0
or x + 2 8 = 0 or x 6 = 0 or x = 6
Oxidation number of S in H
2
SO
5
is + 6 Ans.
Paradox of fractional oxidation number
Fractional oxidation number is the average of oxidation state of all atoms of element under examination and
the structural parameters reveal that the atoms of element for whom fractional oxidation state is realised a
actually present in different oxidation states. Structure of the species C
3
O
2
, Br
3
O
8
and S
4
O
6
2
reveal the
following bonding situations :
The element marked with asterisk (*) in each species is exhibiting different oxidation number from
rest of the atoms of the same element in each of the species. This reveals that in C
3
O
2
, two carbon
atoms are present in +2 oxidation state each whereas the third one is present in zero oxidation state
and the average is + 4/3. However, the realistic picture is +2 for two terminal carbons and zero for
the middle carbon.
O C * C C O
2 0 2
= = = =
+ +
Structure of C
3
O
2
(Carbonsuboxide)
LikewiseinBr
3
O
8
, eachof thetwoterminal bromineatoms arepresent in+6oxidationstateandthemiddle
bromine is present in +4 oxidation state. Once again the average, that is different fromreality, is + 16/3.
In the same fashion, in the species S
4
O
6
2
, average oxidation number of S is + 2.5, whereas the
reality being +5,0,0 and +5 oxidation number respectively for respective sulphur atoms.
In general, the conclusion is that the idea of fractional oxidation state should be taken with care
and the reality is revealed by the structures only.
"manishkumarphysics.in"
5
CHEMISTRY
Oxidisingandreducingagent
Oxidising agent or Oxidant :
Oxidisingagents arethose compounds which canoxidise others andreduce itself during the chemical
reaction. Those reagents in which for an element, oxidation number decreases or which undergoes
gain of electrons in a redox reaction are termed as oxidants.
e.g. KMnO
4
, K
2
Cr
2
O
7
, HNO
3
, conc.H
2
SO
4
etc are powerful oxidising agents .
Reducing agent or Reductant :
Reducing agents are those compounds which can reduce other andoxidise itself during the chemical
reaction. Those reagents in which for an element, oxidation number increases or which undergoes
loss of electrons in a redox reaction are termed as reductants.
e.g. KI , Na
2
S
2
O
3
etc are the powerful reducing agents.
Note : Therearesomecompounds also whichcan workbothas oxidisingagent andreducingagent
e.g. H
2
O
2
, NO
2

HOWTOIDENTIFY WHETHERAPARTICULARSUBSTANCE ISANOXIDISINGORAREDUCINGAGENT

Redox reaction
A reaction in which oxidation and reduction simultaneously take place is called a redox reaction
In all redox reactions, the total increase in oxidation number must be equal to the total decrease in oxidation
number.
e.g. 10
4
2
SO Fe
+
+
5
4
KMnO 2
+
+ 8H
2
SO
4

( )
3 4
2
3
SO Fe 5
+
+
4
2
SO Mn 2
+
+ K
2
SO
4
+ 8H
2
O
Disproportionation Reaction :
A redox reaction in which same element present in a particular compound in a definite oxidation state is
oxidized as well as reduced simultaneously is a disproportionation reaction.
Disproportionation reactions are a special type of redox reactions. One of the reactants in a disproportionation
reaction always contains an element that can exist in at least three oxidation states. The element in
the form of reacting substance is in the intermediate oxidation state and both higher and lower oxidation
states of that element are formed in the reaction. For example :
) aq ( O H 2
1
2 2

) ( O H 2
2
2

+
) g ( O2
0
) s ( S
0
8
+ 12OH(aq)

) aq ( S 4
2
2

+
) aq ( O S 2
2
2
3 2
+

+ 6H
2
O ()
) g ( Cl
0
2
+ 2OH(aq)

) aq ( ClO
1 +

+
) aq ( Cl
1

+ H
2
O ()
Consider the following reactions :
(a) 2KClO
3
2KCl + 3O
2
KClO
3
plays a role of oxidant and reductant both. Here, Cl present in KClO
3
is reduced and O
present in KClO
3
is oxidized. Since same element is not oxidized and reduced, so it is not a
disproportionation reaction, although it looks like one.
"manishkumarphysics.in"
6
CHEMISTRY
(b) NH
4
NO
2
N
2
+ 2H
2
O
Nitrogen in this compound has -3 and +3 oxidation number, which is not a definite value. So it is not
a disproportionation reaction. It is an example of comproportionation reaction, which is a class of
redox reaction in which an element from two different oxidation state gets converted into a single
oxidation state.
(c)
5
3
KClO 4
+

7
4
KClO 3
+
+
1
KCl
It is a case of disproportionation reaction and Cl atom is disproportionating.
List of some important disproportionation reactions
1. H
2
O
2
H
2
O+ O
2
2. X
2
+ OH

(dil.) X + XO (X = Cl, Br, I)

3. X
2
+ OH

(conc.) X +XO
3

F
2
does not undergo disproportionation as it is the most electronegative element.
F
2
+ NaOH(dil.) F

+ OF
2
F
2
+ NaOH(conc.) F

+ O
2
4. (CN)
2
+ OH

CN

+ OCN

5. P
4
+ OH

PH
3
+ H
2
PO
2

6. S
8
+ OH

S
2
+ S
2
O
3
2
7. MnO
4
2
MnO
4
+ MnO
2
8. NH
2
OH N
2
O + NH
3
NH
2
OH N
2
+ NH
3
9. Oxyacids of Phosphorus ( +1, +3 oxidation number)
H
3
PO
2
PH
3
+ H
3
PO
3
H
3
PO
3
PH
3
+ H
3
PO
4
10. Oxyacids of Chlorine( Halogens)( +1, +3, +5 Oxidation number)
ClO

Cl

+ ClO
2

ClO
2

Cl

+ ClO
3

ClO
3

Cl

+ ClO
4

11. HNO
2
NO + HNO
3
Reverse of disproportionation is called Comproportionation. In some of the disproportionation
reactions, by changing the medium(from acidic to basic or reverse), the reaction goes in backward
direction and can be taken as an example of Comproportionation reaction.
I + IO
3
+ H
+
I
2
+ H
2
O
Balancing of redox reactions
All balanced equations must satisfy two criteria.
1. Atom balance (mass balance ) :
There should be the same number of atoms of each kind on reactant and product side.
2. Charge balance :
The sum of actual charges on both sides of the equation must be equal.
There are two methods for balancing the redox equations :
1. Oxidation - number change method
2. Ion electron method or half cell method
Since First method is not very much fruitful for the balancing of redox reactions, students are advised
to use second method (Ion electron method ) to balance the redox reactions
"manishkumarphysics.in"
7
CHEMISTRY
Ion electron method :
By this method redox equations are balanced in two different medium.
(a) Acidic medium (b) Basic medium
Balancing in acidic medium
Students are adviced to follow the following steps to balance the redox reactions by Ion electron
method in acidic medium
Example-3 Balance the following redox reaction :
FeSO
4
+ KMnO
4
+ H
2
SO
4

Fe
2
(SO
4
)
3
+ MnSO
4
+ H
2
O + K
2
SO
4
Solution. StepI Assign the oxidation number to each element present in the reaction.
4
2 6 2
O S Fe
+ +
+
4
2 7 1
MnO K
+ +
+ 4
2 6
2
1
O S H
+ +

3
4
2 6
2
3
) O S ( Fe
+ +
+ 4
2 6 2
O S Mn
+ +
+
2
2
1
O H
+
Step II :
Nowconvert thereactioninIonic formbyeliminatingtheelements or species, whicharenot undergoing
either oxidation or reduction.
Fe
2+
+

+
4
7
O Mn
Fe
3+
+ Mn
2+
Step III :
Now identify the oxidation / reduction occuring in the reaction
Step IV : Spilt the Ionic reaction in two half, one for oxidation and other for reduction.
Fe
2+

oxidation
Fe
3+ +

2 duction Re
4
Mn MnO
Step V :
Balance the atom other than oxygen and hydrogen atom in both half reactions
Fe
2+

Fe
3+
MnO
4


Mn
2+
Fe & Mn atoms are balanced on both side.
Step VI :
Now balance O & H atom by H
2
O & H
+
respectively by the following way : For one excess oxygen
atom, add one H
2
O on the other side and two H
+
on the same side.
Fe
2+

Fe
3+
(no oxygen atom ) .................(i)
8H
+
+ MnO
4

Mn
2+
+ 4H
2
O ................(ii)
Step VII :
Equation (i) & (ii) are balanced atomwise. Nowbalance both equations chargewise. To balance the
charge, add electrons to the electrically positive side.
Fe
2+

oxidation
Fe
3+
+ e

............(1)
5e

+ 8H
+
+ MnO
4

duction Re
Mn
2+
+ 4H
2
O ............(2)
Step VIII :
The number of electrons gained and lost in each half -reaction are equalised by multiplying both the
half reactions with a suitablefactor and finally the half reactions areadded to give the overall balanced
reaction.
Here, we multiply equation (1) by 5 and (2) by 1 and add them :
Fe
2+

Fe
3+
+ e

..........(1) 5
"manishkumarphysics.in"
8
CHEMISTRY
O H 4 Mn Fe 5 MnO H 8 Fe 5
1 ) 2 .........( O H 4 Mn MnO H 8 e 5
2
2 3
4
2
2
2
4
+ + + +
+ + +
+ + + +
+ +
(Here, at his stage, you will get balanced redox reaction in Ionic form)
Step IX :
Now convert the Ionic reaction into molecular form by adding the elements or species, which are
removed in step (2).
Now, by some manipulation, you will get :
5 FeSO
4
+ KMnO
4
+ 4H
2
SO
4

2
5
Fe
2
(SO
4
)
3
+ MnSO
4
+ 4H
2
O +
2
1
K
2
SO
4
or
10FeSO
4
+ 2KMnO
4
+ 8H
2
SO
4

5Fe
2
(SO
4
)
3
+ 2MnSO
4
+ 8H
2
O + K
2
SO
4
.
Balancing in basic medium :
In this case, except step VI, all the steps are same. We can understand it by the following example:
Example-4 Balance the following redox reaction in basic medium :
ClO

+ CrO
2

+ OH

Cl

+ CrO
4
2
+ H
2
O
Solution. By using upto step V, we will get :

+

2
4
6
Oxidation
2
3
duction Re
1
O Cr O Cr Cl O Cl
Now, students are advised to follow step VI to balance O and H atom.
2H
+
+ ClO

Cl

+ H
2
O | 2H
2
O+ CrO
2

CrO
4
2
+ 4H
+
Now, since we are balancing in basic medium, therefore add as many as OH

on both side of
equation as there are H
+
ions in the equation.
2OH

+ 2H
+
+ ClO

Cl

+ H
2
O +2OH

4OH

+2H
2
O+CrO
2

CrO
4
2
+4H
+
+4OH

Finally you will get Finally you will get

H
2
O + ClO

Cl

+ 2OH

...........(i) 4OH

+ CrO
2

CrO
4
2
+ 2H
2
O ........... (ii)
Now see equation (i) and (ii) in which O and H atoms are balanced by OH

and H
2
O
Nowfrom step VIII
2e

+ H
2
O + ClO

Cl

+ 2OH

............. (i) 3
4OH

+ CrO
2

CrO
4
2
+ 2H
2
O + 3e

............. (ii) 2

Adding : 3ClO

+ 2CrO
2

+ 2OH

3Cl

+ 2CrO
4
2
+ H
2
O
Concept of equivalents
Equivalent mass of element
Number of parts by mass of an element which reacts or displaces from a compound 1.008 parts by
mass of hydrogen, 8 parts by mass of oxygen and 35.5 parts by mass of chlorine, is known as the
equivalent weight of that element.
e.g. 2Mg + O
2

2MgO
48g 32g
12g 8g
32 g of O
2
reacts with 48 g of Mg
8 g of O
2
=
32
8 48
= 12 g
Equivalent weight of Mg = 12
"manishkumarphysics.in"
9
CHEMISTRY
Similarly, Zn + H
2
SO
4
ZnSO
4
+ H
2
65.5 g 32.75
Equivalent weight of Zn =
2
5 . 65
= 32.75 g
Al +
2
3
Cl
2
AlCl
3
27 g
2
3
71 g
111.5 g chlorine reacts with 27 g of Al.
35.5 chlorine reacts with
5 . 111
5 . 35 27
= 9.0 g of Al
Equivalent weight of aluminium =
3
27
= 9.0
As we can see from the above examples that equivalent weight is the ratio of atomic weight and a factor
(say n-factor or valency factor) which is in above three cases is their respective valencies.
Equivalent weight (E) :
In general, Eq. wt. (E) =
x
M
factor n
. wt . Mol
) f . v ( factor valency
weight Molecular or weight Atomic
=

=
Number of Equivalents =
species that of . wt . eq
species of mass
For a solution, Number of equivalents = N
1
V
1
, where Nis the normality and Vis the volume in litres
Equivalent mass is a pure number which, when expressed in gram, is called gram equivalent mass.
The equivalent mass of substance may have different values under different conditions.
There in no hard and fast rule that equivalent weight will be always less than the molecular
mass.
Valency factor calculation :
For Elements :
Valency factor = valency of the element.
For Acids :
Valency factor = number of replaceable H
+
ions per acid molecule
Example-5 HCl , H
2
SO
4
H
3
PO
4
H
3
PO
3
{see there are only two replaceable H
+
ions}
Solution. Valency factor 1 2 3 2
(assume 100% dissicoiation)
Eq. wt. (E)
1
M
2
M
3
M
2
M
Replaceable hydrogen atoms are those hydrogen atoms which are attached with the atoms of group
VI and group VII i.e. O,S,Se,Te, & F, Cl ,Br ,I.
"manishkumarphysics.in"
10
CHEMISTRY
For Bases :
Valency factor = number of replacable OH

ions per base molecule.

Example-6 NaOH, KOH
Solution. v .f. 1 1
Eq. wt.
1
M
1
M
Bases may be defined as the substances in which OH group is/are directly attached with group I
elements (Li,Na, K,Rb,Cs), group II elements (Be, Mg,Ca,Ba ) or group III elements (Al, Ga,In,Tl),
transition metals, non-metallic cations like PH
4
+
, NH
4
+
etc.
Acid - base reaction :
In case of acid base reaction, the valence factor is the actual number of H
+
or OH

replaced in the
reaction. The acid or base may contain more number of replaceble H
+
or OH

than actually replaced

in reaction.
v. f. for base is the number of H
+
ion from the acid replaced by each molecule of the base
Example-7 2NaOH + H
2
SO
4

Na
2
SO
4
+ 2H
2
O
Base Acid
Solution. Valency factor of base = 1
Here, two molecule of NaOH replaced 2H
+
ion from the H
2
SO
4
. Therefore, each molecule of NaOH
replaced only one H
+
ion of acid, so v.f. = 1.
v. f. for acid is the number of OH

replaced from the base by each molecule of acid

Example-8 NaOH + H
2
SO
4

NaHSO
4
+ H
2
O
Base Acid
Solution. Valency factor of acid = 1
Here, one of molecule of H
2
SO
4
replaced one OH

fromNaOH. Therefore, valency factor for H

2
SO
4
is one
Eq. wt. of H
2
SO
4
=
1
wt . Mol
Salts :
(a) In non-reacting condition
Valency factor = Total number of positive charge or negative charge present in the compound.
Example-9 Na
2
CO
3
, Fe
2
(SO
4
)
3
FeSO
4
.7H
2
O
Solution. V.f. 2 23 = 6 2
Eq.wt.
2
M
6
M
2
M
Note: Incaseof hydratedsalt, positive/negativechargeof water moleculeis not counted.
(b) In reacting condition
Example-10 Na
2
CO
3
+ HCl

NaHCO
3
+ NaCl
Base Acid
"manishkumarphysics.in"
11
CHEMISTRY
Solution. It is an acid base reaction, therefore valency factor for Na
2
CO
3
is one while in non-reacting condition,
it will be two.
(c) Equivalent weight of oxidising / reducing agents in a redox reaction
In case of redox change , v.f. = Total change in oxidation number per molecule .
Example-11 KMnO
4
+ H
2
O
2

Mn
2+
+ O
2
Solution. Mn in KMnO
4
is going from+7 to +2 , so change in oxidation number per molecule of KMnO
4
is 5. So
the valency factor of KMnO
4
is 5 and equivalent weight is
5
M
.
Normality :
Normality of a solution is defined as the number of equivalents of solute present in one litre (1000 mL)
solution.
Let V mL of a solution is prepared by dissolving W g of solute of equivalent weight E in water.
Number of equivalents of solute =
E
W
VmL of solution contain
E
W
equivalents of solute
1000 mL solution will contain
V E
1000 W

equivalents of solute.
Normality (N) =
V E
1000 W

Normality (N) = Molarity x Valency factor

N V (in mL) = M V (in mL) n
or
milliequivalents = millimoles n
Example-12 Calculate the normality of a solution containing 15.8 g of KMnO
4
in 50 mL acidic solution.
Solution. Normality (N) =
V E
1000 W

Here W = 15.8 g , V = 50 mL E =
factor Valency
KMnO of mass molar
4
= 158/5 = 31.6
So, normality = 10 N
Example-13 Calculate the normality of a solution containing 50 mL of 5 M solution of K
2
Cr
2
O
7
in acidic
medium.
Solution. Normality (N) = Molarity valency factor
= 5 x 6 = 30 N
Law of Equivalence
The law states that one equivalent of an element combine with one equivalent of the other. In a chemical
reaction, equivalents andmilli equivalents of reactants react inequal amount togivesamenumber of equivalents
or milli equivalents of products separately.
Accordingly
(i) aA + bB mM + nN
meq of A= meq of B = meq of M = m.eq. of N
(ii) In a compound M
x
N
y
meq of M
x
N
y
= meq of M = meq of N
"manishkumarphysics.in"
12
CHEMISTRY
Example-14 Find the number of moles of KMnO
4
needed to oxidise one mole Cu
2
S in acidic medium.
The reaction is KMnO
4
+ Cu
2
S Mn
2+
+ Cu
2+
+ SO
2
Solution. Fromlawof equivalence,
equivalents of Cu
2
S= equivalents of KMnO
4
moles of Cu
2
S v.f. = moles of kMnO
4
v.f.
1 8 = moles of KMnO
4
5 moles of KMnO
4
= 8/5
( v.f. of Cu
2
S = 2 (2 1) + 1 (4 (2))) = 8 and v.f. of KMnO
4
= 1 (7 2) = 5)
Example-15 The number of moles of oxalate ions oxidized by one mole of MnO
4

ion in acidic medium are :

(A)
2
5
(B)
5
2
(C)
5
3
(D)
3
5
Solution. Equivalents of C
2
O
4
2
= equivalents of MnO
4

x(mole) 2 = 1 5
( v.f. of C
2
O
4
2
= 2 (4 3) = 2 and v.f. of MnO
4

= 1 (7 2) = 5).
x =
2
5
mole of C
2
O
4
2
ions.
Drawbacks of Equivalent concept
Since equivalent weight of a substance (for example oxidising or reducing agent) may be variable
hence it is better to use mole concept.
e.g. 5e

+ 8H
+
+ MnO
4

Mn
2+
+2H
2
O
Eq.wt of MnO
4

=
5
MnO of . wt . Mol

4
e.g. 3e

+2H
2
O+ MnO
4

MnO
2
+4OH

Eq.wt of MnO
4

=
3
MnO of . wt . Mol
4

Thus, the number of equivalents of MnO

4

will be different in the above two cases but

number of moles will be same.
Normality of any solution depends on reaction while molarity does not.
For example :
Consider 0.1mol KMnO
4
dissolved in water to make 1L solution. Molarity of this solution is 0.1 M.
However, its normality is NOT fixed. It will depend upon the reaction in which KMnO
4
participates.
e.g. if KMnO
4
forms Mn
2+
, normality = 0.1 x 5 = 0.5 N. This same sample of KMnO
4
, if employed in
a reaction giving MnO
2
as product (Mn in +4 state), will have normality 0.1 3 = 0.3 N.
The concept of equivalents is handy, but it should be used with care. One must never equate
equivalents in a sequence which involves same element in more than two oxidation states. Consider
an example, KIO
3
reacts with KI to liberate iodine and liberated Iodine is titrated with standard hypo
solution. The reactions are :
(i) IO
3

+ I

I
2
(ii) I
2
+ S
2
O
3
2
S
4
O
6
2
+ I
meq of hypo = meq of I
2
= meq of IO
3

= meq of I

meq of hypo = meq of IO

3

.
This is wrong. Note that I
2
formed by equation (i) has v.f. = 5/3 & in equation (ii) has v.f. = 2.
v.f. of I
2
in boththe equation are different, thereforewe cannot equatemilli equivalents insequence.
In this type of case, students are advised to use mole concept.
"manishkumarphysics.in"
13
CHEMISTRY
Example-16 How many millilitres of 0.02 M KMnO
4
solution would be required to exactly titrate 25 mL of 0.2 M
Fe(NO
3
)
2
solution in acidic medium ?
Solution. Method -1 : Mole concept method
Starting with 25 mL of 0.2 M Fe
2+
, we can write :
Millimoles of Fe
2+
= 25 x 0.2 ........(1)
and in volume V (in milliliters) of the KMnO
4
,
Millimoles of MnO
4
= V (0.02) ........(2)
The balanced reaction is :
MnO
4
+ 5Fe
2+
+ 8H
+
Mn
2+
+ 5Fe
3+
+ 4H
2
O
This requires that at the equivalent point,
1
MnO of moles . m

4
=
5
Fe of moles . m
2+

1
) 02 . 0 ( V
=
5
) 2 . 0 )( 25 (
(from(1) &(2))
V = 50 mL.
Method -2 : Equivalent Method :
At the equivalence point,
milliequivalents of MnO
4
= milliequivalents of Fe
2+
M
1
vf
1
V
1
= M
2
vf
2
V
2
0.02 5 V
1
= 0.2 1 25 ( MnO
4

Mn
2+
; v.f. = 5, Fe
2+

Fe
3+
; v.f. = 1)
V
1
= 50 mL.
Titrations
Titration is a procedure for determining the concentration of a solution by allowing a carefully measured
volume to react with a standard solution of another substance, whose concentration is known.
Standard solution - It is a solution whose concentration is known and is taken in burette. It is also called
Titrant.
There are two type of titrants :
Primary titrants/standard - These reagents can be accurately weighed and their solutions are not
to be standardised before use.
Ex : Oxalic acid, K
2
Cr
2
O
7
, AgNO
3
, CuSO
4
, ferrous ammonium sulphate, hypo etc.
Secondary titrants/standard : These reagents cannot be accurately weighed and their solutions
are to be standardised before use.
Ex : NaOH, KOH, HCl, H
2
SO
4
, I
2
, KMnO
4
etc.
Titrate : Solution consisting of substance to be estimated, generally taken in a beaker .
Equivalence point : It is the point when number of equivalents of titrant added becomes equal to number of
equivalents of titrate.
At equivalence point :
n
1
V
1
M
1
= n
2
V
2
M
2
Indicator : An auxiliary substance added for physical detection of completion of titration at equivalence
point. It generally show colour change on completion of titration.
Type of Titrations :
Acid-base titrations (to be studided in Ionic equilibrium)
Redox Titrations
"manishkumarphysics.in"
14
CHEMISTRY
Some Common Redox Titrations
Table of Redox Titrations : (Excluding Iodometric / Iodimetric titrations)

Estimation By titrating Reactions Relation*between

of with OAand RA

1. Fe
2+
MnO
4
Fe
2+
Fe
3+
+ e

5Fe
2+
MnO
4

MnO
4

+ 8H
+
+ 5e

Mn
2+
+ 4H
2
O Eq. wt. of Fe
2+
= M/1
2. Fe
2+
Cr
2
O
7
2
Fe
2+
Fe
3+
+ e

6Fe
2+
Cr
2
O
7
2
Cr
2
O
7
2
+ 14H
+
+ 6e

2Cr
3+
+ 7H
2
O Eq.wt. of Cr
2
O
7
2
= M/6
3. C
2
O
4
2
MnO
4
C
2
O
4
2
2CO
2
+ 2e

5C
2
O
4
2
2MnO
4

MnO
4

+ 8H
+
+ 5e

Mn
2+
+ 4H
2
O Eq. wt. of C
2
O
4
2
= M/2
4. H
2
O
2
MnO
4
H
2
O
2
2H
+
+ O
2
+ 2e

5H
2
O
2
2MnO
4

MnO
4

+ 8H
+
+ 5e

Mn
2+
+ 4H
2
O Eq.wt. of H
2
O
2
= M/2
5. As
2
O
3
MnO
4

As
2
O
3
+ 5H
2
O 2AsO
4
3
+ 10H
+
+ 4e

Eq. wt. of As
2
O
3
= M/4
MnO
4

+ 8H
+
+ 5e

Mn
2+
+ 4H
2
O
6. AsO
3
3
BrO
3

AsO
3
3
+ H
2
O AsO
4
3
+ 2H
+
+ 2e

Eq. wt. of AsO

3
3
= M/2
BrO
3

+ 6H
+
+ 6e

Br

+ 3H
2
O Eq.wt. of BrO
3

= M/6
Permanganate Titrations :
KMnO
4
is generally used as oxidising agent in acidic medium, generally provided by dilute H
2
SO
4
.
KMnO
4
works as self indicator persistent pink color is indication of end point.
Mainly used for estimation of Fe
2+
, oxalic acid ,oxalates, H
2
O
2
etc.
Example-17 Write the balanced reaction of titration of KMnO
4
Vs oxalic acid in presence of H
2
SO
4
.
Solution. Reaction : 2KMnO
4
+ 3H
2
SO
4
+ 5H
2
C
2
O
4
K
2
SO
4
+ 2MnSO
4
+ 8H
2
O + 10CO
2
Redox Changes : C
2
3+
2C
4+
+2e
|
.
|

\
|
=
2
M
E
4 2 2
O C H
5e + Mn
7+
Mn
2+ |
.
|

\
|
=
5
M
E
4
KMnO
Indicator : KMnO
4
acts as self indicator.
Example-18 Write the balanced reaction of titration of KMnO
4
Vs ferrous ammonium sulphate in presence of
H
2
SO
4
.
Solution. Reaction : 2KMnO
4
+ 10[FeSO
4
(NH
4
)
2
SO
4
. 6H
2
O] + 8H
2
SO
4

5Fe
2
(SO
4
)
3
+ 10(NH
4
)
2
SO
4
+ K
2
SO
4
+ 2MnSO
4
+ 68H
2
O
Redox Changes : Fe
2+
Fe
3+
+ e
|
.
|

\
|
=
1
M
E
4
FeSO
Mn
7+
+ 5e Mn
2+ |
.
|

\
|
=
5
M
E
4
KMnO
Indicator : KMnO
4
acts as self indicator
Iodometric/Iodimetric Titrations :
Compound containing iodine are widely used in titrations.
(i) Iodide ions can be oxidised to I
2
by suitable oxidising agent
2I (aq) I
2
(s) + 2e
(ii) Iodine (V) ions, IO
3
, will oxidise I to I
2
IO
3
(aq) + 5I (aq) + 6H
+
(aq) 3I
2
(s) + 3H
2
O ()
"manishkumarphysics.in"
15
CHEMISTRY
(iii) Thiosulphate ions, S
2
O
3
2
, can reduce iodine to iodide ions.
2S
2
O
3
2
(aq) + I
2
(s) S
4
O
6
2
+ 2I

colourless black colourless

Iodometric Titrations (Titration Solution is of Na
2
S
2
O
3
. 5H
2
O)

S.No. Estimation of Reaction Relation between O.A. and R.A.

1. I
2
I
2
+ 2Na
2
S
2
O
3
2NaI + Na
2
S
4
O
6
I
2
2I 2Na
2
S
2
O
3
or I
2
+ 2S
2
O
3
2
2I + S
4
O
6
2
Eq.wt. of Na
2
S
2
O
3
= M/1
2. CuSO
4
2CuSO
4
+ 4KI 2CuI + 2K
2
SO
4
+ I
2
2CuSO
4
I
2
2I = 2Na
2
S
2
O
3
or 2Cu
2+
+ 4I 2CuI + I
2
Eq.wt.of CuSO
4
= M/1
white ppt
3. CaOCl
2
CaOCl
2
+ H
2
O Ca(OH)
2
+ Cl
2
CaOCl
2
Cl
2
I
2
2I
Cl
2
+ 2KI 2KCl + I
2
2Na
2
S
2
O
3
Cl
2
+ 2I 2Cl + I
2
Eq.wt. of CaOCl
2
= M/2
4. MnO
2
MnO
2
+ 4HCl(conc.)

A
MnCl
2
+ Cl
2
+ 2H
2
O MnO
2
Cl
2
I
2
2Na
2
S
2
O
3
Cl
2
+ 2KI 2KCl + I
2
Eq.wt. of MnO
2
= M/2
or MnO
2
+ 4H
+
+ 2Cl Mn
2+
+ 2H
2
O + Cl
2
Cl
2
+ 2I I
2
+ 2Cl
5. IO
3
IO
3
+ 5I + 6H
+
3I
2
+ 3H
2
O IO
3
3I
2
6I 6Na
2
S
2
O
3
Eq.wt. of IO
3
= M/6
6. H
2
O
2
H
2
O
2
+ 2I + 2H
+
I
2
+ 2H
2
O H
2
O
2
I
2
2I 2Na
2
S
2
O
3
Eq.wt. of H
2
O
2
= M/2
7. Cl
2
Cl
2
+ 2I 2Cl + I
2
Cl
2
I
2
2I 2Na
2
S
2
O
3
Eq.wt. of Cl
2
= M/2
8. O
3
O
3
+ 6I + 6H
+
3I
2
+ 3H
2
O O
3
3I
2
6I 6Na
2
S
2
O
3
Eq.wt. of O
3
= M/6
9. ClO ClO + 2I + 2H
+
H
2
O + Cl + I
2
ClO I
2
2I 2Na
2
S
2
O
3
Eq.wt. of OCl

= M/2
10. Cr
2
O
7
2
Cr
2
O
7
2
+ 14H
+
+ 6I 3I
2
+ 2Cr
3+
+ 7H
2
O Cr
2
O
7
2
3I
2
6I
Eq.wt. of Cr
2
O
7
2
= M/6
11. MnO
4

2MnO
4

+ 10I+ 16H
+
2MnO
4

+ 5I
2
+ 8H
2
O 2MnO
4
5I
2
10I
Eq.wt. of MnO
4
= M/5
12. BrO
3

BrO
3

+ 6I + 6H
+
Br

+ 3I
2
+ 3H
2
O BrO
3

3I
2
6I
Eq.wt. of BrO
3

= M/6
13. As(V) H
2
AsO
4
+ 2I+ 3H
+
H
3
AsO
3
+ H
2
O + I
2
H
3
AsO
4
I
2
2I
Eq.wt. of H
3
AsO
4
= M/2
14. HNO
2
2HNO
2
+ 2I I
2
+ 2NO + H
2
O 2HNO
2
I
2
2I
Eq.wt. of HNO
2
= M/1
15. HClO HClO + 2I + H
+
Cl + I
2
+ H
2
O HClOI
2
2Na
2
S
2
O
3
Eq.wt. of HClO = M/2
"manishkumarphysics.in"
16
CHEMISTRY
Iodimetric Titrations

S.No. Estimation of Reaction Relation between O.A. and R.A.

1. H
2
S H
2
S + I
2
S + 2I + 2H
+
H
2
S I
2
2I
(in acidic medium) Eq.wt. of H
2
S = M/2
2. SO
3
2
SO
3
2
+ I
2
+ H
2
O SO
4
2
+ 2I + 2H
+
SO
3
2
I
2
2I
(in acidic medium) Eq.wt. of SO
3
2
= M/2
3. Sn
2+
Sn
2+
+ I
2
Sn
4+
+ 2I Sn
2+
I
2
2I
(in acidic medium) Eq.wt. of Sn
2+
= M/2
4. As(III) (at pH8) H
2
AsO
3
+ I
2
+ H
2
O HAsO
4
2
+ 2I + 3H
+
H
2
AsO
3

I
2
2I
Eq.wt. of H
2
AsO
3
= M/2
5. N
2
H
4
N
2
H
4
+ 2I
2
N
2
+ 4H
+
+ 4I N
2
H
4
= 2I
2
4I
Eq.wt. of N
2
H
4
= M/4
Example-19 The sulphur content of a steel sample is determined by converting it to H
2
S gas, absorbing the H
2
S
in 10 mL of 0.005 MI
2
and then back titrating the excess I
2
with 0.002 MNa
2
S
2
O
3
. If 10 mL Na
2
S
2
O
3
is required for the titration, howmany milligrams of sulphur are contained in the sample?
Reactions :
H
2
S + I
2
S + 2I

+ 2H
+
I
2
+ 2S
2
O
3
2
2I

+ S
4
O
6
2
Solution. Used millimoles of I
2
= (m.moles of I
2
taken initially)
2
used hypo of moles . m
= 0.005 10 0.002
2
10
= 0.04 = millimoles of H
2
S
weight of sulphur = 0.04 10
3
32 10
3
mg = 1.28 mg.
Hydrogen peroxide (H
2
O
2
)
H
2
O
2
can behave both like oxidising and reducing agent in both the mediums (acidic and basic).
Oxidising agent : (H
2
O
2
H
2
O)
(a) Acidic medium : 2e

+ 2H
+
+ H
2
O
2
2H
2
O
v.f. = 2
(b) Basic medium : 2e

+ H
2
O
2
2OH

v.f = 2
Reducing agent : (H
2
O
2
O
2
)
(a) Acidic medium : H
2
O
2
O
2
+ 2H
+
+ 2e

v.f = 2
(b) Basic medium : 2OH

+ H
2
O
2
O
2
+ 2H
2
O+ 2e

v.f = 2
Note : Valency factor of H
2
O
2
is always equal to 2.
Volume strength of H
2
O
2
: Strength of H
2
O
2
is represented as 10V , 20 V , 30 V etc.
20V H
2
O
2
means one litre of this sample of H
2
O
2
on decomposition gives 20L of O
2
gas at STP.
"manishkumarphysics.in"
17
CHEMISTRY
Decomposition of H
2
O
2
is given as :
H
2
O
2
H
2
O +
2
1
O
2
1 mole
2
1
22.4 L O
2
at STP
= 34g = 11.2 L O
2
at STP
To obtain 11.2 litre O
2
at STP, at least 34 g H
2
O
2
must be decomposed.
For 20 L O
2
, we should decompose atleast
2 . 11
34
20 g H
2
O
2
1 L solution of H
2
O
2
contains
2 . 11
34
20 g H
2
O
2
1 L solution of H
2
O
2
contains
2 . 11
34

17
20
equivalents of H
2
O
2
(
2
34
2
M
E
2 2
O H
= = = 17)
Normality of H
2
O
2
=
2 . 11
34

17
20
=
6 . 5
20
Normality of H
2
O
2
(N) =
5.6
O H of strength Volume
2 2

2 2
O H
M
=
. f . v
N
2 2
O H
=
2
N
2 2
O H
Molarity of H
2
O
2
(M) =
11.2
O H of strength Volume
2 2
Strength (in g/L) : Denoted by S
Strength = Molarity Mol. wt = Molarity 34
Strength = Normality Eq. weight = Normality 17
Example-20 20 mL of H
2
O
2
after acidification with dilute H
2
SO
4
required 30 mL of
12
N
KMnO
4
for complete
oxidation. Final the strength of H
2
O
2
solution. [Molar mass of H
2
O
2
= 34]
Solution. meq. of KMnO
4
= meq. of H
2
O
2
30
12
1
= 20 N'
N' =
20 12
30

=
8
1
N
strength = N' equivalent mass =
8
1
17 = 2.12 g/L.
Hardness of water (Hard water does not give lather with soap)
Temporary hardness - due to bicarbonates of Ca & Mg
Permanent hardness - due to chlorides & sulphates of Ca & Mg. There are some method by which we can
soften the water sample.
(a) By boiling : 2HCO
3

H
2
O + CO
2
+ CO
3
2
or
By Slaked lime : Ca(HCO
3
)
2
+ Ca(OH)
2
CaCO
3
+2H
2
O
Ca
2+
+ CO
3
2
CaCO
3
(b) By Washing Soda : CaCl
2
+ Na
2
CO
3
CaCO
3
+ 2NaCl
(c) By ion exchange resins : Na
2
R + Ca
2+
CaR + 2Na
+
(d) By adding chelating agents like (PO
3

)
3
etc.
"manishkumarphysics.in"
18
CHEMISTRY
Parts Per Million (ppm)
When the solute is present in very less amount, then this concentration term is used. It is defined as the
number of parts of the solute present in every 1 million parts of the solution. ppm can both be in terms of
mass or in terms of moles. If nothing has been specified, we take ppmto be in terms of mass. Hence, a 100
ppm solution means that 100 g of solute is present in every 1000000 g of solution.
ppm
A
=
6
10
mass Total
A of mass

= mass fraction 10
6
Measurement of Hardness :
Hardness is measured in terms of ppm (parts per million) of CaCO
3
or equivalent to it.
Hardness in ppm =
6
10
solution of mass Total
3
CaCO of mass

Example-21 0.00012% MgSO

4
and 0.000111% CaCl
2
is present in water. What is the measured hardness of
water and millimoles of washing soda required to purify water 1000 L water ?
Solution. Basis of calculation = 100 g hard water
MgSO
4
= 0.00012g =
120
00012 . 0
mole
CaCl
2
= 0.000111g =
111
000111 . 0
mole
equivalent moles of CaCO
3
=
|
.
|

\
|
+
111
000111 . 0
120
00012 . 0
mole
mass of CaCO
3
=
|
.
|

\
|
+
111
000111 . 0
120
00012 . 0
100 = 2 10
4
g
Hardness (in terms of ppm of CaCO
3
) =
6
4
10
100
10 2

= 2 ppm
CaCl
2
+ Na
2
CO
3

CaCO
3
+ 2NaCl
NaSO
4
+ Na
2
CO
3

MgCO
3
+ Na
2
SO
4
Required Na
2
CO
3
for 100g of water =
|
.
|

\
|
+
111
000111 . 0
120
00012 . 0
mole
= 2 10
6
mole
Required Na
2
CO
3
for 1000 litre water =
100
2
10
100
10 2
6
6
=

mole ( d = 1g/mL)
=
1000
20
mole = 20 m mole
Strength of Oleum :
Oleum is SO
3
dissolved in 100% H
2
SO
4
. Sometimes, oleum is reported as more than 100% by weight, say
y%(where y > 100). This means that (y 100) grams of water, when added to 100 g of given oleumsample,
will combine with all the free SO
3
in the oleum to give 100% sulphuric acid.
Hence, weight % of free SO
3
in oleum = 80(y 100)/18
"manishkumarphysics.in"
19
CHEMISTRY
Example-22 What volume of water is required (in mL) to prepare 1 L of 1 Msolution of H
2
SO
4
(density = 1.5g/mL)
by using 109% oleum and water only (Take density of pure water = 1 g/mL).
Solution. 1 mole H
2
SO
4
in 1L solution = 98 g H
2
SO
4
in 1500 g solution = 98 g H
2
SO
4
in 1402 g water.
Also, in 109% oleum, 9 g H
2
O is required to form 109 g pure H
2
SO
4
& so, to prepare 98 g H
2
SO
4
,
water needed is 9/109 98 = 8.09 g.
Total water needed = 1402 + 8.09 = 1410.09 g = 1410.09 mL
Calculation of Available Chlorine from a sample of Bleaching Powder :
The weight of available Cl
2
released from the given sample of bleaching powder on reaction with
dilute acids or CO
2
is called available chlorine.
2 2 4 4 2 2
Cl O H CaSO SO H CaOCl + + +
2 2 2 2
Cl O H CaCl HCl 2 CaOCl + + +
( )
2 2
2
3 3 2
Cl O H COO CH Ca COOH CH 2 CaOCl + + +
2 3 2 2
Cl CaCO CO CaOCl + +
Method of determination :
CaOCl
2
+ 2CH
3
COOH Ca(CH
3
COO)
2
+ H
2
O + Cl
2
(Sample of bleaching powder)
Cl
2
+ 2KI 2KCl + I
2
I
2
+ 2Na
2
S
2
O
3

indicator as Starch
Na
2
S
4
O
6
+ 2Nal
v.f. = 2 v.f. = 1
End point is indicated by disappearance of blue colour.
Let M = Molarity of hypo (Na
2
S
2
O
3
) solution
millimoles of Cl
2
produced = m.moles of I
2
used by hypo
=
2
V M
where V = vol of hypo solution used in ml.
mass of Cl
2
produced =
2
10 V M
3

71
= 35.5 M V 10
3
% of available chlorine =
W
10 V M 5 . 35
3

100
where W = amount of belaching powder taken in g.
or % of available Cl
2
=
W
V M 3.55
Example-23 3.55 g sample of bleaching powder suspended in H
2
Owas treated with enough acetic acid and KI
solution. Iodine thus liberated required 80 mL of 0.2 Mhypo for titration. Calculate the %of available
chlorine.
Solution. % of Cl
2
=
55 . 3
80 2 . 0 55 . 3
= 16%
"manishkumarphysics.in"
20
CHEMISTRY
MISCELLANEOUSSOLVEDPROBLEMS(MSPS)
1. Calculate individual oxidation number of each S-atom in Na
2
S
4
O
6
(sodium tetrathionate) with the help of its
structure .
Sol.
2. Find the average and individual oxidation number of Fe & Pb in Fe
3
O
4
& Pb
3
O
4
, which are mixed oxides.
Sol. (i) Fe
3
O
4
is mixture of FeO & Fe
2
O
3
in 1 : 1 ratio
so, individual oxidation number of Fe = +2 & +3
& average oxidation number =
3
) 3 ( 2 ) 2 ( 1 + + +
= 8/3
(ii) Pb
3
O
4
is a mixture of PbO & PbO
2
in 2 : 1 molar ratio
so, individual oxidation number of Pb are +2 & +4
& average oxidation number of Pb =
3 / 8
3
) 4 ( 1 ) 2 ( 2
=
+ + +
3. Balance the following equations :
(a) H
2
O
2
+ MnO
4

Mn
+2
+ O
2
(acidic medium)
(b) Zn + HNO
3
(dil)

Zn(NO
3
)
2
+ H
2
O+ NH
4
NO
3
(c) CrI
3
+ KOH + Cl
2

K
2
CrO
4
+ KIO
4
+ KCl + H
2
O.
(d) P
2
H
4

PH
3
+ P
4
(e) Ca
3
(PO
4
)
2
+ SiO
2
+ C

CaSiO
3
+ P
4
+ CO
Ans. (a) 6H
+
+ 5H
2
O
2
+ 2MnO
4

2Mn
+2
+ 5O
2
+ 8H
2
O
(b) 4Zn + 10HNO
3
(dil)

4Zn(NO
3
)
2
+ 3H
2
O+ NH
4
NO
3
(c) 2CrI
3
+ 64KOH + 27Cl
2

2K
2
CrO
4
+ 6KIO
4
+ 54KCl + 32H
2
O.
(d) 6P
2
H
4

8PH
3
+ P
4
(e) 2Ca
3
(PO
4
)
2
+ 6SiO
2
+ 10C

6CaSiO
3
+ P
4
+ 10CO
4. Find the valency factor for following acids
(i) CH
3
COOH (ii) NaH
2
PO
4
(iii) H
3
BO
3
Ans. (i) 1 (ii) 2 (iii) 1
5. Find the valency factor for following bases :
(i) Ca (OH)
2
(ii) CsOH (iii) Al(OH)
3
Ans. (i) 2 (ii) 1 (iii) 3
6. Find the valence factor for following salts :
(i) K
2
SO
4
.Al
2
(SO
4
)
3
.24H
2
O
(ii) CaCO
3
Ans. (i) 8 (ii) 2
7. Find the valency factor for following redox reactions :
(i)
4 2
alkaline
2
neutral
2
acidic
4
MnO K
MnO
Mn
KMnO



+
"manishkumarphysics.in"
21
CHEMISTRY
(ii) K
2
Cr
2
O
7
acidic

Cr
3+
(iii) C
2
O
4
2
CO
2
(iv) Fe
2+
Fe
3+
Ans. (i) 5, 3, 1; (ii) 6 ; (iii) 2 ; (iv) 1
8. Calculate the normality of a solution obtained by mixing 50 mL of 5 M solution of K
2
Cr
2
O
7
and 50 mL of
2 M K
2
Cr
2
O
7
in acidic medium.
Sol. v.f. of K
2
Cr
2
O
7
= 6
so N
f
=
2 1
2 2 1 1
V V
V N V N
+
+
=
50 50
50 6 2 50 6 5
+
+
= 21 N
9. Calculate the normality of a solution containing 13.4 g of Sodium oxalate in 100 mL Sol.
Sol. Normality =
litre in solution of vol
wt . eq / g in . wt
Here, eq. wt. of Na
2
C
2
O
4
= 134/2 = 67
so N =
1000 / 100
67 / 4 . 13
= 2N
10. The number of moles of ferrous oxalate oxidised by one mole of KMnO
4
in acidic medium is :
(A)
2
5
(B)
5
2
(C)
5
3
(D)
3
5
Sol. Eq. of FeC
2
O
4
= Eq. of KMnO
4
moles of FeC
2
O
4
3 = moles of KMnO
4
5
so, moles of FeC
2
O
4
= 5/3 Ans. (D)
11. How many moles of KMnO
4
are needed to oxidise a mixture of 1 mole of each FeSO
4
& FeC
2
O
4
in acidic
medium?
(A)
5
4
(B)
4
5
(C)
4
3
(D)
3
5
Sol. Eq. of KMnO
4
= Eq. of FeSO
4
+ Eq. of FeC
2
O
4
moles of KMnO
4
5 = moles of FeSO
4
1 + moles of FeC
2
O
4
3
moles of KMnO
4
= 4/5 Ans. (A)
12. Asample of hydrazine sulphate [N
2
H
6
SO
4
] was dissolved in 100 mLwater. 10 mLof this solution was treated
with excess of FeCl
3
Sol. Ferrous ions formed were estimated and it required 20 mL of M/50 KMnO
4
solution
in acidic medium.
Fe
3+
+ N
2
H
4
N
2
+ Fe
2+
+ H
+
MnO
4
+ Fe
2+
+ H
+
Mn
2+
+ Fe
3+
+ H
2
O
(a) Write the balanced redox reactions.
(b) Estimate the amount of hydrazine sulphate in one litre of Sol.
Sol. (a) Given 4Fe
3+
+ N
2
H
4
N
2
+ 4Fe
2+
+ 4H
+
MnO
4
+5Fe
2+
+ 8H
+
Mn
2+
+ 5Fe
3+
+ 4H
2
O
(b) In 10 mL solution, eq. of N
2
H
6
SO
4
= Eq. of Fe
2+
= Eq. of KMnO
4
= 20
50
1
5 10
3
= 2 10
3
v.f. of N
2
H
6
SO
4
= 4
so, weight of N
2
H
6
SO
4
in 1 L solution =
10 4
1000 10 2
3

130 = 6.5 g.
"manishkumarphysics.in"
22
CHEMISTRY
13. Write the balanced redox reaction and calculate the equivalent weight of oxidising agent and reducing agent
for titration of K
2
Cr
2
O
7
Vs Ferrous ammonium sulphate.
Ans. The reaction : 6[FeSO
4
(NH
4
)
2
SO
4
. 6H
2
O] + K
2
Cr
2
O
7
+ 7H
2
SO
4

3Fe
2
(SO
4
)
3
+ Cr
2
(SO
4
)
3
+ K
2
SO
4
+ 6(NH
4
)
2
SO
4
+ 43H
2
O
Redox changes :
|
.
|

\
|
=
1
M
E
4
FeSO ;
|
.
|

\
|
=
6
M
E
7 2 2
O Cr K
14. One litre of acidified KMnO
4
solution containing 15.8 g KMnO
4
is decolorized by passing sufficient
SO
2
. If SO
2
is produced by FeS
2
, what is the amount of FeS
2
required to give desired SO
2
?
Ans. 15 g.
Sol. v.f. of KMnO
4
= 5 & v.f. of SO
2
= 2
Now, Eq. of KMnO
4
= Eq. of SO
2
5 / 158
8 . 15
= moles of SO
2
2
so, moles of SO
2
= 1/4
Now, applying POAC on S, we get :
2 mole of FeS
2
= 1 moles of SO
2
so, moles of FeS
2
=
8
1
2
1
4
1
=
so, weight of FeS
2
=
8
1
120 = 15 g.
15. An aqueous solution containing 0.1 g KIO
3
(formula weight = 214) and an excess of KI was acidified with
HCl. The liberated I
2
consumed 45 mL of thiosulphate. The molarity of sodium thiosulphate solution is :
The reaction involved is :
IO
3

+ I

+ H
+

I
2
+ H
2
O
(A) 0.0623 M (B) 0.0313 M (C) 0.126 M (D) 0.252 M
Sol. IO
3

+ 5I

+ H
+
3I
2
+ H
2
O
2Na
2
S
2
O
3
+ I
2
2NaI + Na
2
S
4
O
6
Now, Moles of KIO
3
=
214
1 . 0
So, Moles of I
2
= 3
214
1 . 0
Now, Moles of Na
2
S
2
O
3
= 2 3
214
1 . 0
M V
L
= 2 3
214
1 . 0
M
1000
45
= 2 3
214
1 . 0
Now, Molarity of hypo solution = 2 3
45
1000
214
1 . 0

= 0.0623 M Ans. (A)

16. Afresh H
2
O
2
solution is labelled 11.2 V. This solution has the same concentration as a solution which is :
(A) 3.4% (w / w) (B) 3.4%(v / v) (C) 3.4%(w/ v) (D) None of these
Sol. Molarity of H
2
O
2
=
2 . 11
2 . 11
2 . 11
strength . vol
= = 1
Now, %(w/v) =
mL in solution of . wt
g in solute of . wt
100
= Molarity Mol. wt. of solute
10
1
= 1 34
10
1
= 3.4% Ans. (C)
"manishkumarphysics.in"
23
CHEMISTRY
17. 100 mL each of 1 N H
2
O
2
and 11.2 V H
2
O
2
solution are mixed, then the final solution is equivalent to :
(A) 3 M H
2
O
2
solution (B) 0.5 N H
2
O
2
solution
(C) 25.5 g/L H
2
O
2
solution (D) 2.55 g/L H
2
O
2
Sol.
Sol. N
final
=
100 100
100
6 . 5
2 . 11
100 1
V V
V N V N
2 1
2 2 1 1
+
|
.
|

\
|
+
=
+
+
= 3/2 = 1.5 N
So, Molarity =
2
5 . 1
. f . v
Normality
= = 0.75 M
Strength of solution in g/L = Molarity Mol. wt. = 0.75 34 = 25.5 g/L Ans. (C)
18. Calculate the percentage of available chlorine in a sample of 3.55 g of bleaching powder which was
dissolved in 100 mL of water. 25 mL of this solution, on treatment with KI and dilute acid, required
20 mL of 0.125 N sodium thiosulphate Sol.
Ans. 10 %
Sol. CaOCl
2
+ H
2
O Ca(OH)
2
+ Cl
2
Cl
2
+ 2KI 2KCl + I
2
I
2
+ 2Na
2
S
2
O
3
Na
2
S
2
O
6
+ 2NaI
In 25 mL solution,
moles of Na
2
S
2
O
3
=
1000
20

1
125 . 0
= 25 10
4
So, moles of I
2
=
2
1
moles of Na
2
S
2
O
3
=
2
1
25 10
4
= 12.5 10
4
So, in 100 mL solution, moles of Cl
2
= 4 12.5 10
4
= 50 10
4
So, weight of Cl
2
= 50 10
4
71 g
% of available Cl
2
=
55 . 3
71 10 50
4


100 = 10%