CHEMISTRY

Mole Concept-2
Oxidation & Reduction
Let us do a comparative study of oxidation and reduction :
Oxidation
1. Addition of Oxygen
e.g. 2Mg + O2 2MgO

Reduction
1. Removal of Oxygen
e.g. CuO + C Cu + CO

2. Removal of Hydrogen
e.g. H2S + Cl2 2HCl + S

2. Addition of Hydrogen
e.g. S + H2 H2S

3. Increase in positive charge

e.g. Fe2+ Fe3+ + e

3. Decrease in positive charge

e.g. Fe3+ + e Fe2+

4. Increase in oxidation number

(+2)
(+4)
e.g. SnCl2 SnCl4

4. Decrease in oxidation number

(+7)
(+2)

e.g.
MnO4 Mn2+

5. Removal of electron
e.g. Sn2+ Sn4+ + 2e

5. Addition of electron
e.g. Fe3+ + e Fe2+

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. H2O2, , Na2O2 ) is 1,

(ii) super oxide (e.g. KO2) is 1/2
(iii) ozonide (e.g. KO3) is 1/3
(iv) in OF2 is + 2 & in O2F2 is +1

Hydrogen atom :
In general, H atom has 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
show positive oxidation numbers.
5

e.g. K ClO , HI O , HCIO , KBrO

3
3
4
3

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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 have negative or zero oxidation number

Oxidation number of an element in free state or in allotropic forms is always zero

0

e.g. O , S , P , O
2
8
4
3

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 15th group in the periodic table, therefore as per rule, its oxidation number
may vary from
3

3 to +5 ( N H3 ,NO , N 2 O3 , N O2 , N 2 O5 )

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

Calculate oxidation number of underlined element :

(a) Na2 S2O3
(b) Na2 S 4O6

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 Na2S2O3 have two S-atoms and there are four S-atom in Na2S4O6.
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
know the 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 Cl2 molecule

Structure :

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Number of electrons in the valence shell = 7.

Number of electrons taken up after bonding = 7.
oxidation number = 7 7 = 0.

2.

similarly, oxidation number = 7 7 = 0

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-atom is now counted with Cl-atom, because Cl-atom is more electronegative
than H-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 Na2S2O3 (sodium thiosulphate) with the
help of its structure .

Solution.

Structure :

Note : (central S-atom) is sp 3 hybridised (25% s-character) and (terminal S-atom) is sp 2

hydbridised (33% s-character). Therefore, terminal sulphur atom is more electronegative
than central sulphur atom. Now, the shared pair of electrons are counted with terminal Satom.

, 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
, 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 calculate Average Oxidation number of S =

6 ( 2 )
= + 2 (as we have calculated before)
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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 CrO5 is

Cr
||
O O O

From the structure, it is evident that in CrO5 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 H2SO5 is H

From the structure, it is evident that in H2SO5, 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+28=0
or
x6=0
or
x=6

Oxidation number of S in H2SO5 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 C3O2, Br3O8 and S4O62 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 C3O2, 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.
2

O C C* C O
Structure of C3O2
(Carbon suboxide)
Likewise in Br3O8, each of the two terminal bromine atoms are present in +6 oxidation state and the middle
bromine is present in +4 oxidation state. Once again the average, that is different from reality, is + 16/3.

In the same fashion, in the species S4O62, 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.

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Oxidising and reducing agent
Oxidising agent or Oxidant :
Oxidising agents are those compounds which can oxidise others and reduce 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. KMnO4 , K2Cr2O7 , HNO3, conc.H2SO4 etc are powerful oxidising agents .
Reducing agent or Reductant :
Reducing agents are those compounds which can reduce other and oxidise 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. K , Na2S2O3 etc are the powerful reducing agents.
Note : There are some compounds also which can work both as oxidising agent and reducing agent
e.g.
H2O2, NO2
HOW TO IDENTIFY WHETHER A PARTICULAR SUBSTANCE IS AN OXIDISING OR A REDUCING AGENT

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.
5

e.g. 10 Fe SO 4 + 2KMnO4 + 8H2SO4 5 Fe 2 SO 4 3 + 2 Mn SO 4 + K2SO4 + 8H2O

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 :
1

2H2O2 (aq) 2H2O () + O 2 (g)

0

S8 (s) + 12OH(aq) 4S 2 (aq) + 2S 2O 23 (aq) + 6H2O ()

1

Cl2 (g) + 2OH(aq) ClO (aq) + Cl (aq) + H2O ()

Consider the following reactions :
(a)

2KClO3 2KCl + 3O2

KClO3 plays a role of oxidant and reductant both. Here, Cl present in KClO3 is reduced and O
present in KClO3 is oxidized. Since same element is not oxidized and reduced, so it is not a
disproportionation reaction, although it looks like one.

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(b)

NH4NO2 N2 + 2H2O
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)

4KClO3 3KClO 4 + KCl

It is a case of disproportionation reaction and Cl atom is disproportionating.

List of some important disproportionation reactions
1.

H2O2 H2O + O2

2.

X2 + OH(dil.) X + XO

3.

X2 + OH(conc.) X + XO3

(X = Cl, Br, I)

F2 does not undergo disproportionation as it is the most electronegative element.

F2 + NaOH(dil.) F + OF2
F2 + NaOH(conc.) F + O2
4.

(CN)2 + OH CN + OCN

5.

P4 + OH PH3 + H2PO2

6.

S8 + OH S2 + S2O32

7.

MnO42 MnO4 + MnO2

8.

NH2OH N2O + NH3

NH2OH N2 + NH3

9.

Oxyacids of Phosphorus ( +1, +3 oxidation number)

H3PO2 PH3 + H3PO3
H3PO3 PH3 + H3PO4

10.

Oxyacids of Chlorine( Halogens)( +1, +3, +5 Oxidation number)

ClO Cl + ClO2
ClO2 Cl + ClO3
ClO3 Cl + ClO4

11.

HNO2 NO + HNO3
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.
+ O3 + H+ 2 + H2O

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

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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 :

FeSO4 + KMnO4 + H2SO4 Fe2(SO4)3 + MnSO4 + H2O + K2SO4

Solution.

Step Assign the oxidation number to each element present in the reaction.
2 6 2

1 7 2

1 6 2

6 2

2 6 2

1 2

Fe S O 4 + K MnO 4 + H 2 S O 4 Fe 2 (S O 4 )3 + Mn S O 4 + H 2 O

Step :
Now convert the reaction in Ionic form by eliminating the elements or species, which are not undergoing
either oxidation or reduction.
7

Fe2+ + Mn O 4 Fe3+ + Mn2+

Step :
Now identify the oxidation / reduction occuring in the reaction

Step V : Spilt the Ionic reaction in two half, one for oxidation and other for reduction.
Fe2+ Fe3+
oxidation

Re duction
MnO 4

Mn 2

Step V :
Balance the atom other than oxygen and hydrogen atom in both half reactions
Fe2+

Fe3+

MnO4 Mn2+

Fe & Mn atoms are balanced on both side.

Step V :
Now balance O & H atom by H2O & H+ respectively by the following way : For one excess oxygen
atom, add one H2O on the other side and two H+ on the same side.
Fe2+ Fe3+
(no oxygen atom )
.................(i)
+

2+
8H + MnO4 Mn + 4H2O
................(ii)
Step V :
Equation (i) & (ii) are balanced atomwise. Now balance both equations chargewise. To balance the
charge, add electrons to the electrically positive side.
oxidation
Fe2+
............(1)

Fe3+ + e
2+
Re
duction
5e + 8H+ + MnO4
Mn + 4H2O ............(2)

Step V :
The number of electrons gained and lost in each half -reaction are equalised by multiplying both the
half reactions with a suitable factor and finally the half reactions are added to give the overall balanced
reaction.
Here, we multiply equation (1) by 5 and (2) by 1 and add them :
Fe2+ Fe3+ + e

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

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5e 8H MnO 4 Mn 2 4H2O .........( 2) 1

5Fe 2 8H MnO 4 5Fe 3 Mn 2 4H2O

(Here, at his stage, you will get balanced redox reaction in Ionic form)
Step X :
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 FeSO4 + KMnO4 + 4H2SO4

5
1
Fe2 (SO4)3 + MnSO4 + 4H2O +
K SO
2
2 2 4

or

10FeSO4 + 2KMnO4 + 8H2SO4 5Fe2(SO4)3 + 2MnSO4 + 8H2O + K2SO4.

Example-4
Solution.

Balancing in basic medium :

In this case, except step VI, all the steps are same. We can understand it by the following example:
Balance the following redox reaction in basic medium :
ClO + CrO2 + OH Cl + CrO42 + H2O
By using upto step V, we will get :
1

Re duction
Cl O

Cl

Oxidation
Cr O 2

Cr O 24

Now, students are advised to follow step VI to balance O and H atom.

2H+ + ClO Cl + H2O
| 2H2O+ CrO2 CrO42 + 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 + H2O +2OH
Finally you will get
H2O + ClO Cl + 2OH

...........(i)

4OH + 2H2O + CrO2 CrO42 + 4H+ + 4OH

Finally you will get
4OH + CrO2 CrO42 + 2H2O ........... (ii)

Now see equation (i) and (ii) in which O and H atoms are balanced by OH and H2O
Now from step VIII
2e + H2O + ClO Cl + 2OH
4OH + CrO2

CrO42 + 2H2O + 3e

............. (i) 3
............. (ii) 2

Adding : 3ClO + 2CrO2 + 2OH 3Cl + 2CrO42 + H2O

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 O2 reacts with 48 g of Mg

8 g of O2 =

Equivalent weight of Mg = 12

48 8
= 12 g
32

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Similarly,

Zn + H2SO4 ZnSO4 + H2
65.5 g
32.75

Equivalent weight of Zn =
Al

65.5
= 32.75 g
2

3
Cl AlCl3
2 2

3
71 g
2
111.5 g chlorine reacts with 27 g of Al.

27 35.5

35.5 chlorine reacts with

= 9.0 g of Al
111 .5
27

Equivalent weight of aluminium =

= 9.0
3
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.
27 g

Equivalent weight (E) :

In general,

Eq. wt. (E) =

Atomic weight or Molecular weight

valency factor ( v.f )

Mol. wt.
M

n factor
x

mass of species
Number of Equivalents = eq. wt. of that species
For a solution, Number of equivalents = N1V1, where N is the normality and V is 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 ,

Solution.

{see there are only two replaceable H+ions}

1
2
3
2
(assume 100% dissicoiation)

Valency factor

Eq. wt. (E)

M
1

H2SO4

M
2

H3PO4

M
3

H3PO3

M
2

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.

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For Bases :
Valency factor = number of replacable OH ions per base molecule.
Example-6
Solution.

NaOH,
1

v .f.

KOH
1

M
M
1
1
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 PH4+ , NH4+ etc.
Eq. wt.

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

2NaOH + H2 SO4 Na2 SO4 + 2H2O

Example-7
Solution.

Base
Acid
Valency factor of base = 1
Here, two molecule of NaOH replaced 2H+ ion from the H2 SO4. 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
Solution.

NaOH + H2SO4 NaHSO4 + H2O

Base
Acid
Valency factor of acid = 1
Here, one of molecule of H2SO4 replaced one OH from NaOH. Therefore, valency factor for H2SO4
is one

Eq. wt. of H2SO4 =

Mol.wt
1

Salts :
(a) In non-reacting condition

Valency factor = Total number of positive charge or negative charge present in the compound.

Example-9
Solution.

Na2 CO3 ,

Fe2(SO4)3

FeSO4.7H2O
2

V.f.

23 = 6

Eq.wt.

M
2

M
6

M
2

Note : In case of hydrated salt, positive/negative charge of water molecule is not counted.
(b) In reacting condition
Example-10

Na2 CO3 +

HCl NaHCO3 + NaCl

Base

Acid

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Solution.

It is an acid base reaction, therefore valency factor for Na2CO3 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

KMnO4 + H2O2 Mn2+ + O2

Solution.

Mn in KMnO4 is going from +7 to +2 , so change in oxidation number per molecule of KMnO4 is 5. So

the valency factor of KMnO4 is 5 and equivalent weight is

M
.
5

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 =

VmL of solution contain

W
E

W
equivalents of solute
E

W 1000
E V equivalents of solute.

1000 mL solution will contain

Normality (N) =

Normality (N) = Molarity x Valency factor

N V (in mL) = M V (in mL) n

or
milliequivalents = millimoles n

Example-12
Solution.

W 1000
E V

Calculate the normality of a solution containing 15.8 g of KMnO 4 in 50 mL acidic solution.

Normality (N) =

Here

W 1000
E V

W = 15.8 g ,

V = 50 mL

E=

molar mass of KMnO 4

= 158/5 = 31.6
Valency factor

So, normality = 10 N
Example-13
Solution.

Calculate the normality of a solution containing 50 mL of 5 M solution of K2Cr2O7 in acidic

medium.
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 and milli equivalents of reactants react in equal amount to give same number 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 MxNy
meq of MxNy = meq of M = meq of N

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Example-14
Solution.

Example-15

Find the number of moles of KMnO4 needed to oxidise one mole Cu2S in acidic medium.
The reaction is KMnO4 + Cu2S Mn2+ + Cu2+ + SO2
From law of equivalence,
equivalents of Cu2S = equivalents of KMnO4
moles of Cu2S v.f. = moles of kMnO4 v.f.
1 8 = moles of KMnO4 5

moles of KMnO4 = 8/5

( v.f. of Cu2S = 2 (2 1) + 1 (4 (2))) = 8 and v.f. of KMnO4 = 1 (7 2) = 5)
The number of moles of oxalate ions oxidized by one mole of MnO4 ion in acidic medium are :
2
3
5
(B)
(C)
5
5
2
2

Equivalents of C2O4 = equivalents of MnO4

x(mole) 2 = 1 5
( v.f. of C2O42 = 2 (4 3) = 2 and v.f. of MnO4 = 1 (7 2) = 5).

(A)
Solution.

x=

(D)

5
3

5
mole of C2O42 ions.
2

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.

Eq.wt of MnO4 =
e.g.

5e + 8H+ + MnO4 Mn2+ + 2H2O

Mol. wt. of MnO 4
5

3e + 2H2O + MnO4 MnO2 + 4OH

Eq.wt of MnO4 =

Mol. wt. of MnO 4

3

Thus, the number of equivalents of MnO4 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 KMnO4 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 KMnO4 participates.
e.g. if KMnO4 forms Mn2+, normality = 0.1 x 5 = 0.5 N. This same sample of KMnO4, if employed in
a reaction giving MnO2 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, KIO3 reacts with KI to liberate iodine and liberated Iodine is titrated with standard hypo
solution. The reactions are :
(i) O3 + 2
(ii) 2 + S2O32 S4O62 +
meq of hypo = meq of I2 = meq of IO3 = meq of I

meq of hypo = meq of IO3.

This is wrong. Note that I2 formed by equation (i) has v.f. = 5/3 & in equation (ii) has v.f. = 2.
v.f. of I2 in both the equation are different, therefore we cannot equate milli equivalents in sequence.
In this type of case, students are advised to use mole concept.

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Example-16
Solution.

How many millilitres of 0.02 M KMnO4 solution would be required to exactly titrate 25 mL of 0.2 M
Fe(NO3)2 solution in acidic medium ?
Method -1 : Mole concept method
Starting with 25 mL of 0.2 M Fe2+, we can write :
Millimoles of Fe2+ = 25 x 0.2
........(1)
and in volume V (in milliliters) of the KMnO4,
Millimoles of MnO4 = V (0.02)
........(2)
The balanced reaction is :
MnO4 + 5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O
This requires that at the equivalent point,

m.moles of Fe 2
m. moles of MnO 4
=
5
1

( 25 )(0.2)
V(0.02)
=
(from (1) & (2))
5
1
V = 50 mL.
Method -2 : Equivalent Method :
At the equivalence point,
milliequivalents of MnO4 = milliequivalents of Fe2+
M1 vf1 V1 = M2 vf2 V2

0.02 5 V1 = 0.2 1 25

( MnO4 Mn2+ ; v.f. = 5, Fe2+ Fe3+ ; v.f. = 1)

V1 = 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, K2Cr2O7, AgNO3, CuSO4, 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, H2SO4, 2, KMnO4 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 :
n1V1M1 = n2V2M2
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

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CHEMISTRY
Some Common Redox Titrations
Table of Redox Titrations : (Excluding Iodometric / Iodimetric titrations)

Estimation
of

By titrating
with

Reactions

Relation*between
OA and RA

1.

Fe2+

MnO4

Fe2+ Fe3+ + e
MnO4 + 8H+ + 5e Mn2+ + 4H2O

5Fe2+ MnO4
Eq. wt. of Fe2+ = M/1

2.

Fe2+

Cr2O72

Fe2+ Fe3+ + e
Cr2O72 + 14H+ + 6e 2Cr3+ + 7H2O

6Fe2+ Cr2O72
Eq.wt. of Cr2O72 = M/6

3.

C2O42

MnO4

C2O42 2CO2 + 2e
MnO4 + 8H+ + 5e Mn2+ + 4H2O

5C2O42 2MnO4
Eq. wt. of C2O42 = M/2

4.

H2O2

MnO4

H2O2 2H+ + O2 + 2e
MnO4 + 8H+ + 5e Mn2+ + 4H2O

5H2O2 2MnO4
Eq.wt. of H2O2 = M/2

5.

As2O3

MnO4

As2O3 + 5H2O 2AsO43 + 10H+ + 4e Eq. wt. of As2O3 = M/4

MnO4 + 8H+ + 5e Mn2+ + 4H2O

6.

AsO33

BrO3

AsO33 + H2O AsO43 + 2H+ + 2e

BrO3 + 6H+ + 6e Br + 3H2O

Eq. wt. of AsO33 = M/2

Eq.wt. of BrO3 = M/6

Permanganate Titrations :

KMnO4 is generally used as oxidising agent in acidic medium, generally provided by dilute H2SO4 .

KMnO4 works as self indicator persistent pink color is indication of end point.

Mainly used for estimation of Fe2+ , oxalic acid ,oxalates, H2O2 etc.
Example-17

Write the balanced reaction of titration of KMnO4 Vs oxalic acid in presence of H2SO4.

Solution.

Reaction :

2KMnO4 + 3H2SO4 + 5H2C2O4 K2SO4 + 2MnSO4 + 8H2O + 10CO2

Redox Changes :

C23+ 2C4+ +2e

EH2C 2O 4
2

5e + Mn7+ Mn2+

EKMnO 4
5

Indicator :

KMnO4 acts as self indicator.

Example-18

Write the balanced reaction of titration of KMnO4 Vs ferrous ammonium sulphate in presence of
H2SO4.

Solution.

Reaction :

2KMnO4 + 10[FeSO4(NH4)2SO4. 6H2O] + 8H2SO4

5Fe2(SO4)3 + 10(NH4)2SO4 + K2SO4 + 2MnSO4 + 68H2O

Redox Changes :

Fe2+ Fe3+ + e

EFeSO 4
1

Mn7+ + 5e Mn2+

EKMnO 4
5

Indicator : KMnO4 acts as self indicator

Iodometric/Iodimetric Titrations :
Compound containing iodine are widely used in titrations.
(i) Iodide ions can be oxidised to 2 by suitable oxidising agent
2 (aq) 2(s) + 2e
(ii) Iodine (V) ions, O3 , will oxidise to 2
O (aq) + 5 (aq) + 6H+ (aq) 32(s) + 3H2O ()

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CHEMISTRY
(iii) Thiosulphate ions, S2O32 , can reduce iodine to iodide ions.
2S2O (aq) (s) S4 O62 + 2
colourless
black
colourless
Iodometric Titrations (Titration Solution is of Na2S2O3 . 5H2O)

S.No.

Estimation of

Reaction

Relation between O.A. and R.A.

1.

2 + 2Na2S2O3 2Na + Na2S4O6

or 2 + 2S2O32 2 + S4O62

2 2 2Na2S2O3
Eq.wt. of Na2S2O3 = M/1

2.

CuSO4

2CuSO4 + 4K 2Cu + 2K2SO4 + 2

or 2Cu2+ + 4 2Cu + 2
white ppt

2CuSO4 2 2 = 2Na2S2O3
Eq.wt.of CuSO4 = M/1

3.

CaOCl2

CaOCl2 + H2O Ca(OH)2 + Cl2

Cl2 + 2K 2KCl + 2
Cl2 + 2 2Cl + 2

CaOCl2 Cl2 2 2
2Na2S2O3
Eq.wt. of CaOCl2 = M/2

4.

MnO2

MnO2 + 4HCl(conc.)
MnCl2 + Cl2 + 2H2O MnO2 Cl2 2 2Na2S2O3
Cl2 + 2K 2KCl + 2
Eq.wt. of MnO2 = M/2
or MnO2 + 4H+ + 2Cl Mn2+ + 2H2O + Cl2
Cl2 + 2 2 + 2Cl

5.

O3

O3 + 5 + 6H+ 32 + 3H2O

O3 32 6 6Na2S2O3
Eq.wt. of O3 = M/6

6.

H2O2

H2O2 + 2 + 2H+ 2 + 2H2O

H2O2 2 2 2Na2S2O3
Eq.wt. of H2O2 = M/2

7.

Cl2

Cl2 + 2 2Cl + 2

Cl2 2 2 2Na2S2O3
Eq.wt. of Cl2 = M/2

8.

O3

O3 + 6 + 6H+ 32 + 3H2O

O3 32 6 6Na2S2O3
Eq.wt. of O3 = M/6

9.

ClO

ClO + 2 + 2H+ H2O + Cl + 2

ClO 2 2 2Na2S2O3
Eq.wt. of OCl = M/2

10.

Cr2O72

Cr2O72 + 14H+ + 6 32 + 2Cr3+ + 7H2O

Cr2O72 32 6
Eq.wt. of Cr2O72 = M/6

11.

MnO4

2MnO4 + 10+ 16H+ 2MnO4 + 52 + 8H2O

2MnO4 52 10
Eq.wt. of MnO4 = M/5

12.

BrO3

BrO3 + 6 + 6H+ Br + 32 + 3H2O

BrO3 32 6
Eq.wt. of BrO3 = M/6

13.

As(V)

H2AsO4 + 2+ 3H+ H3AsO3 + H2O + 2

H3AsO4 2 2
Eq.wt. of H3AsO4 = M/2

14.

HNO2

2HNO2 + 2 2 + 2NO + H2O

2HNO2 2 2
Eq.wt. of HNO2 = M/1

15.

HClO

HClO + 2 + H+ Cl + 2 + H2O

HClOI22Na2S2O3
Eq.wt. of HClO = M/2

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CHEMISTRY
Iodimetric Titrations

S.No.

Estimation of

Reaction

Relation between O.A. and R.A.

1.

H2S
(in acidic medium)
SO32
(in acidic medium)

2.

H2S + 2 S + 2 + 2H+
SO32 + 2 + H2O SO42 + 2 + 2H+

4.

Sn2+
Sn2+ + 2 Sn4+ + 2
(in acidic medium)
As(III) (at pH 8)
H2AsO3 + 2 + H2O HAsO42 + 2 + 3H+

5.

N2H4

3.

N2H4 + 22 N2 + 4H+ + 4

H2S 2 2
Eq.wt. of H2S = M/2
SO32 2 2
Eq.wt. of SO32 = M/2
Sn2+ 2 2
Eq.wt. of Sn2+ = M/2
H2AsO3 2 2
Eq.wt. of H2AsO3 = M/2
N2H4 = 22 4
Eq.wt. of N2H4 = M/4

Example-19

The sulphur content of a steel sample is determined by converting it to H2S gas, absorbing the H2S
in 10 mL of 0.005 M I2 and then back titrating the excess I2 with 0.002 M Na2S2O3 . If 10 mL Na2 S2O3
is required for the titration, how many milligrams of sulphur are contained in the sample?
Reactions :
H2S + I2 S + 2I + 2H+
I2 + 2S2O32 2I + S4O62

Solution.

Used millimoles of I2 = (m.moles of I2 taken initially)

= 0.005 10 0.002

m. moles of hypo used

2

10
2

= 0.04 = millimoles of H2S

weight of sulphur = 0.04 103 32 103 mg = 1.28 mg.

Hydrogen peroxide (H2O2)

H2O2 can behave both like oxidising and reducing agent in both the mediums (acidic and basic).

Oxidising agent : (H2O2 H2O)

(a) Acidic medium :
2e + 2H+ + H2O2 2H2O
v.f. = 2
(b) Basic medium :
2e + H2O2 2OH
v.f = 2

Reducing agent : (H2O2 O2)

(a) Acidic medium :
H2O2 O2 + 2H+ + 2e
v.f = 2
(b) Basic medium :
2OH + H2O2 O2 + 2H2O + 2e
v.f = 2
Note : Valency factor of H2O2 is always equal to 2.

Volume strength of H2O2 : Strength of H2O2 is represented as 10V , 20 V , 30 V etc.

20V H2O2 means one litre of this sample of H2O2 on decomposition gives 20L of O2 gas at STP.

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CHEMISTRY
Decomposition of H2O2 is given as :
1
H2O2 H2O +
O
2 2
1
1 mole
22.4 L O2 at STP
2
= 34g
= 11.2 L O2 at STP
To obtain 11.2 litre O2 at STP, at least 34 g H2O2 must be decomposed.
34
For 20 L O2 , we should decompose atleast
20 g H2O2
11.2
34

1 L solution of H2O2 contains

20 g H2O2
11.2

1 L solution of H2O2 contains

Normality of H2O2 =

MH2O2 =

M 34

= 17)
2
2

Volume strength of H 2 O 2
5.6

NH2O2
v.f.

NH2O2
2

Volume strength of H 2 O 2
11.2
Strength (in g/L) : Denoted by S
Strength = Molarity Mol. wt = Molarity 34
Strength = Normality Eq. weight = Normality 17
Molarity of H2O2 (M) =

N
KMnO4 for complete
12
oxidation. Final the strength of H2O2 solution. [Molar mass of H2O2 = 34]

Example-20

20 mL of H2O2 after acidification with dilute H2SO4 required 30 mL of

Solution.

meq. of KMnO4 = meq. of H2O2

( EH2O 2

20
34
20

=
5 .6
11.2 17

Normality of H2O2 (N) =

34
20

equivalents of H2O2
11.2 17

30

1
= 20 N
12

N =

30
1
= N
12 20
8

strength = N equivalent mass =

1
17 = 2.12 g/L.
8

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

2HCO3 H2O + CO2 + CO32 or

By Slaked lime

Ca(HCO3)2 + Ca(OH)2 CaCO3 + 2H2O

Ca2+ + CO32 CaCO3

CaCl2 + Na2CO3 CaCO3 + 2NaCl

(b)

By Washing Soda

(c)
(d)

By ion exchange resins :

Na2R + Ca2+ CaR + 2Na+
By adding chelating agents like (PO3)3 etc.

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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 ppm to be in terms of mass. Hence, a 100
ppm solution means that 100 g of solute is present in every 1000000 g of solution.
ppmA =

mass of A
10 6 = mass fraction 106
Total mass

Measurement of Hardness :
Hardness is measured in terms of ppm (parts per million) of CaCO3 or equivalent to it.
Hardness in ppm =

Example-21
Solution.

mass of CaCO
3
10 6
Total mass of solution

0.00012% MgSO4 and 0.000111% CaCl2 is present in water. What is the measured hardness of
water and millimoles of washing soda required to purify water 1000 L water ?
Basis of calculation = 100 g hard water
MgSO4 = 0.00012g =
CaCl2 = 0.000111g =

0.00012
mole
120

0.000111
mole
111

0.00012 0.000111

mole
equivalent moles of CaCO3 =
111
120

0.00012 0.000111

100 = 2 104 g
mass of CaCO3 =
111
120

Hardness (in terms of ppm of CaCO3) =

2 10 4
10 6 = 2 ppm
100

CaCl2 + Na2CO3 CaCO3 + 2NaCl

NaSO4 + Na2CO3 MgCO3 + Na2SO4

0.00012 0.000111

mole
Required Na2CO3 for 100g of water =
111
120

= 2 106 mole

Required Na2CO3 for 1000 litre water =

=

2 10 6
2
10 6
mole
100
100

( d = 1g/mL)

20
mole = 20 m mole
1000

Strength of Oleum :
Oleum is SO3 dissolved in 100% H2SO4. 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 oleum sample,
will combine with all the free SO3 in the oleum to give 100% sulphuric acid.
Hence, weight % of free SO3 in oleum = 80(y 100)/18

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CHEMISTRY
Example-22
Solution.

What volume of water is required (in mL) to prepare 1 L of 1 M solution of H2SO4 (density = 1.5g/mL)
by using 109% oleum and water only (Take density of pure water = 1 g/mL).
1 mole H2SO4 in 1L solution = 98 g H2SO4 in 1500 g solution = 98 g H2SO4 in 1402 g water.
Also, in 109% oleum, 9 g H2O is required to form 109 g pure H2SO4 & so, to prepare 98 g H2SO4,
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 Cl2 released from the given sample of bleaching powder on reaction with
dilute acids or CO2 is called available chlorine.
CaOCl 2 H2 SO 4 CaSO 4 H2 O Cl 2
CaOCl 2 2HCl CaCl 2 H2 O Cl 2

CaOCl2 2CH3 COOH CaCH3COO2 H2O Cl2

CaOCl 2 CO 2 CaCO 3 Cl 2

Method of determination :
CaOCl2

+ 2CH3COOH Ca(CH3COO)2 + H2O + Cl2

(Sample of bleaching powder)

Cl2 + 2KI
I2
+
v.f. = 2

2KCl + I2
Starch as indicator
2Na2S2O3

Na2S4O6 + 2Nal
v.f. = 1

End point is indicated by disappearance of blue colour.

Let
M = Molarity of hypo (Na2S2O3) solution

millimoles of Cl2 produced = m.moles of I2 used by hypo

=

mass of Cl2 produced

or

M V
2

where

V = vol of hypo solution used in ml.

M V 10 3
71
2
= 35.5 M V 103
=

35.5 M V 10 3
100
W
where W = amount of belaching powder taken in g.
3.55 M V
% of available Cl2 =
W
% of available chlorine

Example-23

3.55 g sample of bleaching powder suspended in H2O was treated with enough acetic acid and K
solution. Iodine thus liberated required 80 mL of 0.2 M hypo for titration. Calculate the % of available
chlorine.

Solution.

% of Cl2 =

3.55 0.2 80
= 16%
3.55

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CHEMISTRY
MISCELLANEOUS SOLVED PROBLEMS (MSPS)
1.

Calculate individual oxidation number of each S-atom in Na2S4O6 (sodium tetrathionate) with the help of its
structure .

Sol.

2.
Sol.

Find the average and individual oxidation number of Fe & Pb in Fe3O4 & Pb3O4, which are mixed oxides.
(i) Fe3O4 is mixture of FeO & Fe2O3 in 1 : 1 ratio
so, individual oxidation number of Fe = +2 & +3
& average oxidation number =

1( 2) 2( 3)
= 8/3
3

(ii) Pb3O4 is a mixture of PbO & PbO2 in 2 : 1 molar ratio

so, individual oxidation number of Pb are +2 & +4
& average oxidation number of Pb =
3.

2( 2) 1( 4)
8/3
3

Balance the following equations :

(a)

H2O2 + MnO4 Mn+2 + O2 (acidic medium)

(b)

Zn + HNO3 (dil) Zn(NO3)2 + H2O + NH4NO3

(c)

Cr3 + KOH + Cl2 K2CrO4 + KO4 + KCl + H2O.

(d)

P2H4 PH3 + P4

(e)

Ca3 (PO4)2 + SiO2 + C CaSiO3 + P4 + CO

(a) 6H+ + 5H2O2 + 2MnO4 2Mn+2 + 5O2 + 8H2O

Ans.

(b) 4Zn + 10HNO3 (dil) 4Zn(NO3)2 + 3H2O + NH4NO3

(c) 2Cr3 + 64KOH + 27Cl2 2K2CrO4 + 6KO4 + 54KCl + 32H2O.
(d) 6P2H4 8PH3 + P4
(e) 2Ca3 (PO4)2 + 6SiO2 + 10C 6CaSiO3 + P4 + 10CO
4.
Ans.
5.
Ans.
6.

Find the valency factor for following acids

(i) CH3COOH
(ii) NaH2PO4
(iii) H3BO3
(i) 1
(ii) 2
(iii) 1
Find the valency factor for following bases :
(i) Ca (OH)2
(ii) CsOH
(iii) Al(OH)3
(i) 2
(ii) 1
(iii) 3

Ans.

Find the valence factor for following salts :

(i)
K2SO4 .Al2(SO4)3.24H2O
(ii)
CaCO3
(i) 8
(ii) 2

7.

Find the valency factor for following redox reactions :

acidic

Mn 2

(i)

neutral
KMnO 4

MnO 2
alkaline

K 2MnO 4

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CHEMISTRY

Ans.
8.
Sol.

(ii)

K2Cr2O7 acidic

Cr3+

(iii)

C2O42

CO2

(iv)
Fe2+
(i) 5, 3, 1;

(ii) 6 ;

Fe3+
(iii) 2 ; (iv) 1

Calculate the normality of a solution obtained by mixing 50 mL of 5 M solution of K2Cr2O7 and 50 mL of

2 M K2Cr2O7 in acidic medium.
v.f. of K2Cr2O7 = 6
so

Nf =
=

N1V1 N2 V2
V1 V2

5 6 50 2 6 50
= 21 N
50 50

9.

Calculate the normality of a solution containing 13.4 g of Sodium oxalate in 100 mL Sol.

Sol.

wt. in g / eq. wt
Normality = vol of solution in litre
Here, eq. wt. of Na2C2O4 = 134/2 = 67
so

10.

N=

13.4 / 67
= 2N
100 / 1000

The number of moles of ferrous oxalate oxidised by one mole of KMnO4 in acidic medium is :
2
5
(B)
5
2
Eq. of FeC2O4 = Eq. of KMnO4
moles of FeC2O4 3 = moles of KMnO4 5
so,
moles of FeC2O4 = 5/3 Ans. (D)

(A)
Sol.

11.

3
5

(D)

5
3

How many moles of KMnO4 are needed to oxidise a mixture of 1 mole of each FeSO4 & FeC2O4 in acidic
medium ?
4
5

5
3
(C)
4
4
Eq. of KMnO4 = Eq. of FeSO4 + Eq. of FeC2O4
moles of KMnO4 5 = moles of FeSO4 1 + moles of FeC2O4 3
moles of KMnO4 = 4/5
Ans. (A)
(A)

Sol.

(C)

(B)

(D)

5
3

12.

A sample of hydrazine sulphate [N2H6SO4] was dissolved in 100 mL water. 10 mL of this solution was treated
with excess of FeCl3 Sol. Ferrous ions formed were estimated and it required 20 mL of M/50 KMnO4 solution
in acidic medium.
Fe3+ + N2H4 N2 + Fe2+ + H+
MnO4 + Fe2+ + H+ Mn2+ + Fe3+ + H2O
(a) Write the balanced redox reactions.
(b) Estimate the amount of hydrazine sulphate in one litre of Sol.

Sol.

(a) Given

4Fe3+ + N2H4 N2 + 4Fe2+ + 4H+

MnO4 +5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O

(b) In 10 mL solution, eq. of N2H6SO4 = Eq. of Fe2+ = Eq. of KMnO4
= 20

1
5 103 = 2 103
50

v.f. of N2H6SO4 = 4
so,

weight of N2H6SO4 in 1 L solution =

2 10 3 1000
130 = 6.5 g.
4 10

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CHEMISTRY
13.

Write the balanced redox reaction and calculate the equivalent weight of oxidising agent and reducing agent
for titration of K2Cr2O7 Vs Ferrous ammonium sulphate.

Ans.

The reaction :

6[FeSO4(NH4)2 SO4 . 6H2O] + K2Cr2O7 + 7H2SO4

3Fe2(SO4)3 + Cr2(SO4)3 + K2SO4 + 6(NH4)2SO4 + 43H2O

M
M

Redox changes : EFeSO 4 ; EK 2Cr2O7

1
6

14.

One litre of acidified KMnO 4 solution containing 15.8 g KMnO 4 is decolorized by passing sufficient
SO2. If SO2 is produced by FeS2, what is the amount of FeS2 required to give desired SO 2 ?

Ans.
Sol.

15 g.
v.f. of KMnO4 = 5 & v.f. of SO2 = 2
Now, Eq. of KMnO4 = Eq. of SO2
15.8
= moles of SO2 2
158 / 5

15.

Sol.

so,
Now,

moles of SO2 = 1/4

applying POAC on S, we get :
2 mole of FeS2 = 1 moles of SO2

so,

moles of FeS2 =

1 1 1

4 2 8

so,

weight of FeS2 =

1
120 = 15 g.
8

An aqueous solution containing 0.1 g KIO3 (formula weight = 214) and an excess of K was acidified with
HCl. The liberated 2 consumed 45 mL of thiosulphate. The molarity of sodium thiosulphate solution is :
The reaction involved is :
O3 + + H+ 2 + H2O
(A) 0.0623 M
(B) 0.0313 M
O3 + 5 + H+ 32 + H2O
2Na2S2O3 + 2 2Na + Na2S4O6
Now,
So,

(C) 0.126 M

(D) 0.252 M

0.1
214
0.1
Moles of 2 = 3
214

Moles of KO3 =

0.1
214

Now,

Moles of Na2S2O3 = 2 3

M VL = 2 3

Now,

Molarity of hypo solution = 2 3

0.1
214

45
0.1
=23
1000
214

0.1 1000

= 0.0623 M
214
45

Ans. (A)

16.

A fresh H2O2 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 H2O2 =
Now,

vol. strength 11.2

=1
11.2
11.2

wt. of solute in g
%(w/v) = wt. of solution in mL 100
= Molarity Mol. wt. of solute
= 1 34

1
= 3.4%
10

1
10

Ans. (C)

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CHEMISTRY
17.

Sol.

100 mL each of 1 N H2O2 and 11.2 V H2O2 solution are mixed, then the final solution is equivalent to :
(A) 3 M H2O2 solution
(B) 0.5 N H2O2 solution
(C) 25.5 g/L H2O2 solution
(D) 2.55 g/L H2O2 Sol.

Nfinal

= N1V1 N2 V2
V1 V2

11.2
1 100
100
5. 6
= 3/2 = 1.5 N
100 100

Normality 1.5

= 0.75 M
v.f .
2
Strength of solution in g/L = Molarity Mol. wt. = 0.75 34 = 25.5 g/L
So,

18.

Molarity =

Ans. (C)

Ans.

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.
10 %

Sol.

CaOCl2 + H2O Ca(OH)2 + Cl2

Cl2 + 2K 2KCl + 2
2 + 2Na2S2O3 Na2S2O6 + 2Na
In 25 mL solution,
moles of Na2S2O3 =

20
0.125

= 25 104
1000
1

1
moles of Na2S2O3
2

So,

moles of 2 =

So,
So,

1
25 104 = 12.5 104
2
in 100 mL solution,
moles of Cl2 = 4 12.5 104 = 50 104
4
weight of Cl2 = 50 10 71 g
=

% of available Cl2 =

50 10 4 71
100 = 10%
3.55

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