Redox Reaction

PHYSICAL
CHEMISTRY

1.

 Introduction
y Chemical reactions in which reduction and oxidation takes place are known
as redox reactions.
y In order to define oxidation and reduction, there were many concepts which
are as following:

1. Classical concept

OXIDATION REDUCTION

Addition of oxygen Addition of hydrogen

or or
Removal of hydrogen Removal of oxygen

Reduction of Cl2
Oxidation of Mg

e.g.

2HCl 
→ H2 + Cl 2
Oxidation of HCl
Reduction of H2O, Oxidation of H2O

Note: Above definitions failed to define oxidation and reduction in all

reactions. Hence, its concept was modified later as following:

OXIDATION REDUCTION

Addition of electronegative element Addition of electropositive element

Or or
Removal of electropositive element Removal of electronegative element

2.

 OXIDATION REDUCTION

Addition of electronegative atom

e.g.

2Mg + O2 MgO

Addition of electropositive
Oxidation of Na
Oxidation of magnesium
and
and
Reduction of Cl2
also Reduction of O2

Removal of electro negative element

e.g.

HCl 
→ H2 + Cl 2

Oxidation and reduction of HCl

2. Modern Concept

y It is an electronic concept.

y This concept is based upon transfer of electrons.

OXIDATION REDUCTION

The process in which substance The process in which substance

looses some electrons. gains some electrons.

3.

 e–
Oxidaon of compound A2–
A e– (Loses electrons) A

Reducing agent Oxidized

B Reducon of compound B
e– B
(Gains electrons)
e–
Oxidizing agent Reduced

Oxidation of Zn and reduction of Cu2+.

Oxidation of H2 and reduction of Ag+.

Note: Modern concept can be used to identify oxidation and reduction

only in ionic reactions.

4.

 Oxidation Number

y The average charge per atom possessed by an element in a specie is called

“oxidation number” of that element in that species (atom, molecule, ion).
y In a specie, the charge is developed on atoms due to difference in
electronegativity between bonded atoms or due to transfer of electrons.

e.g. H2

Total charg e on H atoms

(Oxidation number )H = Total number of H − atoms
O
=
2
=O
Oxidation number of hydrogen in H2 = zero

e.g. i) HCl

(O.N)H =
( +1) = +1
1 H Cl  More electronegative

 −1 
(O.N)Cl =   = −1
 1

ii) HCN
+1
(O.N)H = = +1
1 H C N
−1 + 3
(O.N)C = = +2
1
−3 Order of electronegativity
(O.N)N = = −3 H<C<N
1

5.

 Note: Oxidation number may be positive, negative, integer, fractional or
even zero.

e.g.
i) C3O2 (carbon suboxide)

Now,
−2 − 2
(O.N)O =
2
= −2 ( )

+2 + O + 2  +4 
=
(O.N)C =  
3  3 

ii) Na2S4O6

O O

Na O S S S S O Na

O O

+1 + 1
(O.N)Na = = ( +1)
2
−12
(O.N)O = = ( −2)
6
+5 + 0 + 0 + 5
(O.N)S =
4
= (+2.5)

6.

 Note: An element can show different oxidation number in different
species.

e.g.

+4 −4
i) C O2 and C H4

O = C = O and H C H

Oxidation number of carbon in CO2 is +4 and in CH4 is −4.

0 +1 +1
ii) H2 , H Cl and NaOH

Oxidation number of hydrogen in H2, HCl and NaOH is 0, +1 and +1

respectively

Determination of oxidation number

For a specie, the sum of oxidation number of each atom present is equal to

the charge possessed by that specie.

Let AXByCz

y x(p) + y(q) + z(r) = 0

(AxByCz)φ

y x(p) + y(q) + z(r) = φ.

7.

 e.g.
i) H2O
• 2(+1) + 1 (−2) = 0
ii) CF4
• 1(+4) + 4(−1) = 0
iii) CO2
• 1(+4) + 2 (−2) = 0

Oxidation Number of Some Common Elements

y For elements present in their free state (Natural form at room temperature
and pressure), the oxidation number is zero.
e.g.
H2 , He, C, N2 , O2 , F2 

Na, Mg, S8 , P4 , Cl2  Oxidation number = 0
Fe, Zn, Ag, etc. 

y All IA group elements show (+1) oxidation number in their compounds.
i.e.
Li 
Na 

K  In compounds, Oxidation number = ( +1) always
Rb 

Cs 

y All IIA group elements show (+2) oxidation numbers in their compounds
i.e.
Be 
Mg 

Ca  In compounds, Oxidation number = ( +2) always
Sr 

Ba 

Note: Fluorine is most electronegative element hence always show (−1)

oxidation number in its compounds.

8.

y For hydrogen
General oxidation number = (+1)
But , In metal hydrides, (oxidation number)H = (−1)
(Electronegativity)Metal < (Electronegativity)H

e.g.
LiH ⇒ 1(+1) + 1 (x) = 0
⇒ x=−1
CaH2 ⇒ 1(+2) + 2(x) = 0
⇒ x = −1

y For oxygen
General oxidation number = (−2) in oxides.
But, In peroxides, oxidation number = (−1)
 1
In superoxides, oxidation number =  − 
 2

Na2O Na2O2 NaO2

2(+1)+ 1(x) = 0 2(+1) + 2(x)=0 1(+1) + 2x = 0

x = (−2) x = (−1)  1
x = − 
 2

Oxide Peroxide Superoxide

y Compounds of oxygen with fluorine

OF2 O2F2

1(x) + 2(−1) = 0 2(x) + 2(−1) = 0

x= (+2) x = +1

y p−block Elements
Generally have a range of oxidation number of following:
(n - 8 ) to (+ n )

9.

 Where, ‘n’ is number of valence electrons.

y For halogens (except F)

Oxidation Number Range =

(−1) to (+7)

 −1– 0 +1 +3 +5 +7 
Cl , Cl2 , Cl O− , Cl O2− Cl O3− , Cl O4− 
 

y Oxidation number of Chlorine

Case − I Chlorine in chlorides Cl −

1(x) = −1
x = −1

Case − II Chlorine molecule Cl 2

2(x) = 0
x=0

Case − III Chlorine with more electronegative ClO-1

atom 1(x) + 1(–2) = –1
x = +1

y For chalcogens except oxygen

Oxidation number range = (–2) to (+6)
−2 −1 0 −4 +6
e.g. S 2− , S 22− , S8 , SO2 , SO3
y For Nitrogen family
Oxidation number =(-3) to (+5)
−3 −2 0 +1 +2 +3 +4 +5
e.g. N H3 , N2 H4 , N2 N2 O NO N2 O3 N O2 , N2 O5

y d−block elements show multiple but fixed oxidation number in their

compounds.
e.g. Fe = (+2), (+3)
Ti = (+2), (+4)
Cu = (+2), (+1)
Mn = (+2), (+4), (+5), (+6), (+7)
Cr = (+6), (+3)
In = (+2)
Ag = (+1) etc.

10.

Note: Maximum possible oxidation number of an element in species is
+8 which is for Osmium and Xenon in their particular compounds.

e.g. O
CrO5
Oxidation of Cr O O
1(x) + 5(−2) = 0
x= (+10) Cr
Not possible
i.e.
O O

i.e. (O.N)Cr = (+6)

Note: In calculations , if O.N of p−block elements comes beyond the

range then it is incorrect.

e.g. O
+1 x −2
H2 SO5
Oxidation no of S
S
2( +1) + (x) + 5( −2) =0 O O H
X = +8 O
OH
i.e. (O.N)S = (+6)

11.

 Practice Questions and Illustrations

PRACTICE QUESTIONS
1. Calculate the oxidation number of underlined elements in the following
compounds:
i) Fe3O4
3x + 4(−2) = 0
3x = 8
8
x=
3
Oxidation number of Fe is +8/3.
ii)
FeO
x + ( −2) =0

x = +2
Oxidation number of Fe is +2.
iii) Na2S4O6
Oxidation number of S in Na2S4O6
⇒ 2(+1) + 4x + 6(−2) = 0
2 + 4x −12 = 0
4 x = 10
10
x =
4
x = +2.5
iv) C2H5OH
2(x) + 5(1) + (−2) + (1) = 0
2x + 5 −2 + 1 = 0
2x = − 4
x =−2
Oxidation number of C in C2H5OH is −2.
v) FeSO4(NH4)2SO4. 6H2O
FeSO4 ⇒ x+(−2) = 0 ⇒ x = +2

NH4+ ⇒ x + 4(1) = +1 ⇒ x = −3
Oxidation number of Fe in FeSO4.(NH4)2SO4.6H2O = +2
Oxidation number of N in FeSO4.(NH4)2SO4.6H2O = − 3
vi) CO2
x + 2(−2) = 0
x = +4
Oxidation number of C in CO2 is + 4.

12.

 vii) FeS2

(+2) + 2 (x) = 0
2x = −2
x = −1
O.N. of S in FeS2 is (−1).
viii) PbS
x + (−2) =0

x = +2
Oxidation number of Pb in PbS is +2.
ix) CS2
x + 2( −2) =
0
x − 4 = 0
x = +4
O
Oxidation number of C in CS2 is +4.
x) CrO5
x+(−2) + 4 (−1) = 0 O O
x−2 −4 = 0 Cr
O.N. of Cr in CrO5 is +6

Note: 4 oxygen atoms in peroxide linkages. O O

xi) (N2H5)2SO4
2(2x + 5(1)) + (−2) = 0
4x + 8 = 0
4x = − 8
x = -8/4 = −2
Oxidation number of N in (N2H5)2SO4 is (−2).
xii) N2O5
2(x) + 5(−2) = 0
2x − 10 = 0
⇒ 2x = 10
⇒ x = 10/2
⇒ x = +5
Oxidation number of N in N2O5 is + 5.
xiii) HCN
Oxidation number of C:
(1) + x + (−3) = 0
x = +2

13.

 Oxidation number of N:
1 + (+2) + x = 0
x = −3
Oxidation number of C in HCN is (+2).
Oxidation number of N in HCN is (−3).
xiv) Ba[H2PO2]2
Oxidation number of Ba is +2
Oxidation number of P is:
(+2)+ 2 [2(+1) + x+2(−2)] = 0
2 + 2 (2+x − 4) = 0
2 + 4 + 2x−8 = 0
2x − 2 = 0
2x = 2
x = +1 ∴ O.N of P in Ba[H2PO2]2 is (+1)
xv) OsO4

x+4(−2) = 0
x=8
Oxidation number of Os in OsO4 is (+8).
xvi) H2S2O3
2(+1) + 2(x) + 3(−2) = 0
2 + 2x − 6 = 0
2x − 4 = 0
2x = 4
x=2
Oxiation number of S in H2S2O3 = (+2)
xvii) CH3SO3H
Oxidation number of C is (−2)
Oxidation number of S is (+4)
xix) Ba2XeO6
Oxidation number of Xe is +8.
2(+2) + x + 6(−2) = 0
x = +8
xx) Ba(SCN)2
Oxidation number of S is (−2).
Oxidation number of C is (+4).
Oxidation number of N is(−3).

14.

Q1 Select the compound in which chlorine shows oxidation state +7:
(A) HClO4 (B) HClO3 (C) HClO2 (D) HClO

A1 (A)
a) HClO4
1+x+4(−2) =0
x= + 7
O.N of Cl in HClO4 is (+7).
b) HClO3
(+1) + x +3(−2) = 0
x=+5
O.N of Cl in HClO3 is (+5).
c) HClO2
(+1) +x +2(−2) = 0
x= + 3
O.N of Cl in HClO2 is (+3).
d) HClO
(+1) + x + (−2) = 0
x= + 1
O.N of Cl in HClO is (+1).

Q2 The oxidation number of C in CH4, CH3Cl, CH2Cl2, CHCl3 and CCl4 are respec-
tively.
(A) +4, +2, 0, −2, −4 (B) +2, +4, 0, −4, −2
(C) −4, −2, 0, +2, +4 (D) −2, −4, 0, +4,+2

A2 (C)
Oxidation number of C in:
(i) CH4 (ii) CH3Cl
x + 4(1) =
0 x + 3(1) + (−1) =0
x = −4 x+3−1= 0
x = −2
(iii) CH2Cl2 (iv) CHCl 3 (v) CCl 4
x+2−2 =0 x + 1 + 3(−1) =0 x + 4(−1) =0
x=0 x = +2
x = +4

15.

 Q3 The correct order of the increasing oxidation states of nitrogen in NO, N2O,
NO2 and N2O3 is:
(A) N2O < NO < N2O3 < NO2
(B) N2O < N2O3 < NO < NO2
(C) NO2 < NO < N2O3 < N2O
(D) NO2 < N2O3 < NO < N2O

A3 (A)
Oxidation states of N in NO, N2O, NO2 and N2O3 are:

NO NO2
x + ( −2) =0 x + 2(−2) =
0
x − 4 = 0
x = +2
x = +4

N2O N2O3
2x + (−2) =0 2x + 3(−2) =
0
2x = +2
2x − 6 =0
x = +1 x = +3

Q4 Oxidation number of oxygen in K2O, K2O2 and KO2, respectively, is:

(A) +1, +2 and +4

(B) +1, +4 and +2

–1
(C) –2, –1 and
2
+1
(D) −2, −1 and
2

A4 (C)
K2O → Oxide
K2O2 → Peroxide
KO2 → Superoxide

16.

Oxidation:
The process in which oxidation number of element increases is known as
oxidation.
e.g.
0 +2 +2 +3
→ Zn2+
(i) Zn  (ii) Fe2+ 
→ Fe3+
−1 0 +4 +7
(iii) Cl − 
→ Cl2 → MnO−4
(iv) MnO2 

Reduction:
The process in which oxidation number of element decreases is known as
reduction.
e.g.
0 −1 +5 −1

→ Br −
(i) Br2  (ii) Cl O3− 
→ Cl −
+2 +1 +6 +3

(iii) Cu2+ 

→ Cu+ (iv) Cr2 O27 − 
→ Cr3+
Note: Alone oxidation or alone reduction never takes place means both
process are carried out simultaneously and hence the reaction is collectively
known as Redox reaction.
e.g. (i)
Oxidation

Mg is oxidized.
0 0 +2 −2 O2 is reduced.
2Mg + O2 
→ 2Mg O
Reduction

(ii)
Oxidation

H2 is oxidized.
0 0 +1 −1 Cl2 is reduced.
H2 + Cl 2 → 2HCl
Reduction

(iii) Oxidation

O is oxidised.
+1 −2 0 0 H is reduced.
H2 O  → H2 + O2
Reduction

17.

 (iv) Oxidation

Zn is oxidized.
0 0 Cu+2 is reduced.
Zn + Cu+2 → Zn+2 + Cu
Reduction

(v) Oxidation
MnO4− is reduced.

+7 +3 +2 +4 C2O4−2 is oxidized.
− 2− 2+
MnO +4
C2 O 
4
→ Mn + C O2
Reduction

 No change in oxidation No.

⇒ Non − redox reaction

 No change in oxidation No.

⇒ Non − redox reaction

Oxidizing agent / Oxidant

Substance which oxidizes other substance by getting reduced itself.

18.

Reducing agent / Reductant
Substance which reduces other substances by getting oxidized itself.

e.g.

0 +1 +2 0
(i) Fe + H+ → Fe2+
 + H2
i.e. Fe = R.A (Reducing agent)
H+ = O.A (Oxidizing agent)

(ii) Oxidation

Cr2 O7−2 + 14H+ + 6I−  2Cr 3+ + 3I2 + yH2O


Reduction

Cr2O72− is reducing agent.

I− is oxidizing agent.

ILLUSTRATION:

Q1 Which of the following is not a redox change?

(A) 2H2S + SO2 → 2H2O + 3S (B) 2BaO + O2 → 2BaO2
(C) BaO2 + H2SO4 → BaSO4 + H2O2 (D) 2KClO3 → 2KCl + 3O2

A1 (C)
Non redox reaction means no change in oxidation number.

Q2 In the following reaction

3Br2 + 6C O32 − + 3H2 O → 5Br − + BrO3− + 6HCO3−
(A) Bromine is oxidized, carbonate is reduced
(B) Bromine is reduced, carbonate is oxidized
(C) Bromine is neither reduced nor oxidizes
(D) Bromine is reduced as well as oxidized

19.

 A2 (D)
−2 −1
0 +4 +5 −2 +4 −2
3Br2 + 6C O23− + 3H2O 
→ 5Br − + Br O−3 + 6H CO3−

Q3 In the reaction
2Na2S2O3 + I2 → Na2S4O6+2NaI,
I2 act as:
(A) Reducing agent (B) Oxidizing agent
(C) Oxidizing as well as reducing agent (D) None of above

A3 (B)
I2 get reduced from (0) oxidation state in I2 to −1 oxidation state in NaI.

Classification of redox reactions

1. Intermolecular reactions 2. Intramolecular reactions

Oxidation Oxidation

A + B → Products A + B → Products

Reduction Reduction

Reaction in which two different elements Reaction in which two different elements
in different molecules undergo oxidation & in same molecule undergo oxidation &
reduction. reduction.

20.

 (e.g) (e.g)

Reduction Reduction

0 0 +2 −2 −3 +1 0 0
2Mg + O2 → 2Mg O 2 NH3  → N + 3H2
Oxidation Oxidation 2

e.g.

(i)

(ii)

Reduction

0 –3 +1
P4 + 3NaOH + 3H2O P H3 + 3NaH2PO2
Intramolecular reaction

Oxidation

21.

 (3) Combination reactions (4) Decomposition reactions

(i) At reactant side, atleast one element in (i) At reactant side, no element in free
free state is present but no element in state but in product side, there is
free state at product side. atleast one element in free state
Re actants Pr oducts i.e.
→
(At least one element (No element  No element   At least 
   
in free state) in free state)  in free state  →  one element 
 at reactant side   in state 
   

E.g.
−4 0 +4 −2
(i) CH4 + 2O2 → CO2 + 2H2O Combination Reaction (Intermolecular)
Element in free state
 
Noelement in free state

0 +1 +3
(ii) → 3NaH2P O2 + P H3
P4 + 3NaOH  Combination Reaction (Intramolecular)

(iii) 4NH4NO 

→ 4N
2 + 3O2 + 2H2O Decomposition Reaction (Intramolecular)
 2
No element Element in
in free state free state

(5) Metal Displacement reactions (6) Non – metal displacement reactions

(i) A metal ion present in a compound is (i) A non-metal present in a

displaced by a more electropositive
metal present in free state.
e.g.
0 +2 +2
Zn+ Cu SO4 → Zn SO4 + Cu
i.e. Cu is displaced by Zn
compound is displaced by a more
electronegative non-metal present
in free state.
0 e.g.
−1 0 −1 0
2HBr + Cl 2 → 2HCl + Br2
i.e. Br is displaced by Cl

7. Disproportion Reaction

y Redox reactions in which an element present in one single oxidation number at reactant
side converts into two different oxidation number at product side showing both oxidation
and reduction.
y Means only one element is involved in redox reaction.

22.

(e.g)
(i) Self decomposition of H2O2
Re duction

–1 –2 0
2H 2O2 2H 2O + O2
Oxidation

i.e. disproportion reaction

(ii) Disproportion of KClO3

Re duction

+5 +1 +7
2KClO 3 KClO + KClO 4
Oxidation

Note: Whenever a non metal present in free state reacts with base, the
reaction is always disproportion reaction.

(iii) Disproportion of P4
Reduction

0 –3 +1
P 4 + 2NaOH + 3H 2 PH3 + NaH 2 PO2

Oxidation
(iv) Disproportion of Halogens
–1 +1
Room Temperature
NaX  NaXO

0
X2  NaOH
ExceptF2 

1 5
High Temperature Na X  NaXO3

23.

 Note: Reverse of disproportionation reaction is known as comproportionation
reaction.
−2 +4 0
(i) 2H2S + S O2 → 3 S + 2H2O
−3 +3 0
(ii) N H4 N O2 → N2 + 2H2O

ILLUSTRATION:

Q1 White phosphorus reacts with NaOH as:

P4 + 3NaOH + 3H2 O → PH3 + 3NaH2PO2 is an example of:

(A) Dimerization reaction (B) Disproportionation reaction
(C) Condensation reaction (D) Precipitation reaction

A1 B
0 –3 +1
P4 + 3NaOH + 3H2O → P H3 + 3NaH2 S O2

Q2 Which of the following chemical reactions does not depicts the oxidizing
behaviour of H2 SO4 ?
+6 +1
(A) Ca OH ( ) 2
+ H2 SO4 → Ca S O4 + 2H2 O
+1 +4
(B) NaCl + H2 SO4 → Na H SO3 + HCl
+6 −2 −1
(C) 2PCl 5 + H2 SO4 → 2POCl 3 + 2HCl + S O2 Cl 2
+6 +4
(D) 2HI + H2SO4 → I2 + SO2 + 2H2O

A2 A
Oxidising behaviour of H2SO4 means tendency to oxidise or reduction of self.
+6 +4
2HI + H2 SO4 → I2 + SO2 + 2H2O

In 1st half : 2HI → I2

Oxidation number of I is increases by one thus, oxidation reaction.
+6 +4
In 2nd half : H2SO4 
→ SO2

O.N of S decreases by 2, thus reduction reaction & H2SO4 act as oxidising

agent.

24.

Balancing of Redox Reactions:
There are two methods discussed as follows

1. Ion electron method:

This method is applicable for ionic reactions only means it is based upon
modern concept.
Step−I: Split the given redox reaction into two half reactions as oxidation
and reduction.
Step−II: In both reactions, balance elements other than H and O by hit and
trial.
Step−III: Balance O by adding suitable number of H2O.
Step− IV: To balance hydrogen and oxygen.

In acidic medium → by adding H+

To balance O → add H2O to side deficit of O and double number of H+
ions on the opposite side. The number of H2O molecules is equal to the
number of O atoms deficit.
In basic medium → by adding OH−
To balance O → add H2O to side excess of O and same number of OH−
ions on the opposite side. The number of H2O molecules is equal to the
number of O atoms deficit.
To balance H → add H2O to side deficit of H and same number of
OH− ions on the opposite side. The number of H2O molecules is equal to
the number of O atoms deficit.

Step−V: Balance charge by adding suitable number of electrons at suitable

side.
Step−VI: Multiply both reactions by suitable number separately to make
same number of electrons in both.
Step−VII: Add both half reactions due to which electrons will be cancelled
out and balanced redox reaction is obtained.

Examples:
i) MnO4− + C2O42− → Mn2+ + CO2
Step−I:
MnO4− → Mn2+
C2O42− → CO2
Step − II
MnO4− → Mn2+
2 4
C O 2− → 2CO2

25.

 Step−III
MnO4− → Mn+ + 4H2O
C2O42− → 2CO2
Step−IV
8H+ + MnO4− → Mn2+ + 4H2O
C2O42− → 2CO2
Step − V
5e− + MnO4− + 8H+ → Mn2+ + 4H2O
C2O42− → 2CO2 + 2e−
Step−VI
(MnO4− + 8H+ + 5e− → Mn2+ +4H2O) × 2
(C2O42− → 2CO2 + 2e−) × 5
Step − VII
After adding above two reactions we get:
2MnO4− + 5C2O42− + 16H+ → 2Mn2+ + 10CO2 + 8H2O
+
H
ii) NO3− + Br− → NO + Br2
3e− + 4H+ + NO3− → NO + 2H2O)×2
2Br− → Br2 + 2e−)× 3
After adding above two reactions we get
2NO3− + 6Br− + 8H+ → 2NO + 3Br2 + 4H2O
−
OH
iii) Zn + NO3−  → ZnO22− + NH3

1×(4OH + 2H2O + Zn → ZnO22− + 4H2O + 2e−
−

8e− + 9H2O + NO3− → NH3 + 3H2O + 9OH−

After adding above two reactions we get
4Zn + NO3− + 7OH− → 4ZnO22− + NH3 + 2H2O

−
OH
iv) AsO33− + NO3−  → AsO43− + NO2

2OH− + H2O + AsO33− → AsO43− + 2H2O + 2e−
2×(e− + 2H2O + NO3− → NO2 + H2O + 2OH−
After adding above two reactions we get
AsO33− + 2NO3− + H2O → AsO43− + 2NO2 + 2OH−

H+
v) BrO 4− + Br -  → BrO -3
3x ( 2e− + 2H+ + BrO4− → BrO3− + H2O
1 x ( 3H2O + Br− → BrO3− + 6H+ + 6e−
After adding above two reactions we get
3BrO4− + Br− → 4BrO3−

26.

 −
(vi) Cl 2 
OH
→ Cl − + ClO3−

2e− + Cl2 → 2Cl−

12OH− + 6H2O + Cl 2 

→ 2ClO3− + 12H2O + 10e−
After adding above two reactions we get

6Cl2 + 12OH- 

→ 10Cl- + 2ClO-3 + 6H2O

Note: If reaction is not given in ionic form then convert it (if possible) by
removing all spectator

Ions. KCl = K+ + Cl−

=
H2SO4 2H+ + SO4− 

= H+ + HSO4− 
+
=
KMnO4 K + MnO4−

Example:
i) KMnO4 + KI + HCl → MnCl2 + I2 + KCl + H2O
If all spectator ions are removed, we get
+
MnO4− + I- 
H
→ Mn2+ + I2
Balancing the equation
2MnO4− + 10I− + 16H+ → 2Mn2+ + 5I2 + 8H2O
Final equation:

2KMnO4 + 10KI + 16HCl 

→ 2MnCl 2 + 5I2 + 8H2O + 12KCl

ii) K2Cr2O7 + K2C2O4 + H2SO4 → Cr2(SO4)3 + CO2 + K2SO4

If all spectator ions are removed, we get

Cr2O72− + C2O42− + H+ → Cr3+ + CO2 + H2O

Balancing,

2Cr2O72− + 6C2O42− + 28H+ → 4Cr3+ + 12CO2 + 14H2O

Final equation:

2K2Cr2O7 + 6K2C2O4 + 14H2SO4 → 2Cr2(SO4)3 + 12CO2 + 14H2O +

8K2SO4

27.

 Balancing of Redox Reaction Continued

2. Oxidation number method:

This method is applicable for every redox reaction.
i) Select two species showing oxidation and reduction at reactant side
by observing change in oxidation number.

ii) Calculate “Net increase or decrease in oxidation number for these two
species”.

iii) Make Total increase = Total decrease by multiplying species with

suitable numbers.

iv) Now balance others by hit and trial.

v) Balance remaining O by H2O.

vi) Balance remaining H by H+ or OH− and H2O (discussed in ion electron

method).

Examples:
+1 +5 −2 +4 −2 +4 −2 +1 +6 −2
i) H N O3 + S O2 
→ N O2 + H2 S H4

+5 +4 +4 +6
Step: H N O3 + S O2 
→ N O2 + H2 S O4

There is 1 decrease in N and 2 increase in S.

2HNO3 + 1SO2 → 2NO2 + 1H2 SO4

ii)

There is 3 increase in N and 2 decrease in Br2.

So,
2NO + 3Br2 + 4H2 O → 2HNO3 + 6HBr
+2 0 +2.5 −1
iii) Na2S2O3 + I2 
→ Na2 S4 O6 + Na I

2Na2S2O3 + 1I2 

→ 1Na2S4O6 + 2NaI

+6 +3 +3 +4
iv) Cr2 O27− + C2 O24− 
→ Cr3+ + CO2
There is 6 decrease in Cr and 2 increase in C.
1Cr2 O2-
7
+ 3C 2 O42- + 14H+ → 2Cr 3 + + 6CO2 + 7H2 O

28.

Practice Question on Balancing of Redox Reactions

Practice questions

+6 −1 +3 0
+
v) Cr O24− + I− 
H
→ Cr3+ + I2

1CrO42− + 3I− + 8H+ → 1Cr3+ + 3/2 I2 + 4H2O

+3 +5 − +5 +4
vi) As O33− + NO3− OH
 → AsO34− + NO2


1AsO33− + 2NO3− + H2O → 1AsO43− + 2NO2 + 2OH−

+2 −1 0 +3 −2 +4 −2
vii) Fe S2 + O2 
→ Fe 2O3 + SO2

2FeS2 + 11/2 O2 → Fe2O3+ 4SO2

+3 −2 +5 +5 +6 +2
viii) As2 S3 + HNO3 
→ H3 AsO4 + H2 SO4 + NO

3As2S3 + 28HNO3 + 4H2O → 6H3AsO4+ 9H2SO4 + 28NO

0 ( −1) +5
−
ix) OH
Cl2  → Cl − + ClO3−


3Cl2 + 6OH– → 5Cl– + ClO3– + 3H2O

+7 +3 +2 +4
x) KMnO4 + H2C2O4 + H2SO4 
→ Mn SO4 + CO2 + K2SO4

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

+6 +2 +3 +3
xi) K2CrO7 + Fe(NO3 )2 + HNO3 
→ Cr (NO3 )3 + Fe(NO3 )3 + KNO3 + H2O

1K2Cr2O7 + 6Fe(NO3)2 + 14HNO3 → 2Cr(NO3)3 + 6Fe(NO3)3 + 2KNO3 +

7H2O

xii) KMnO4 + HCl → MnCl2 + H2O + Cl2 + KCl oxidation no. is not
All HCl is not converting into Cl2.
KMnO4 + 8HCl → 1MnCl2 + 5/2 Cl2 + KCl + 4H2O

0 +5 +2 +5 +4
xiii) Cu + HNO3 
→ Cu(N O3 )2 + NO2 + H2O

Cu + 4HNO3 → Cu(NO3)2 + 2NO2 + 2H2O

29.

 Q1 Consider the following reaction

z
xMnO4− + yC2O42− + z H+ → xMnO2+ + 2yCO2 + HO
2 2
The value of x, y and z in the reaction are, respectively
(A) 2,5 and 8 (B) 2,5 and 16 (C) 5,2 and 8 (D) 5, 2 and 16

A1 (B)
Balanced chemical reaction:
2MnO4− + 5C2O42− + 16H+ → 2Mn2+ + 10CO2 + 8H2O

The values of x, y and z are 2,5 and 16 respectively.

Q2 For the reaction:

I− + ClO3− + H2SO4 → Cl− + HSO4− + I2

The true statement(s) in the balanced equation is/are:

(A) Stoichiometric coefficient of HSO4− is 6
(B) Iodide is oxidized
(C) Sulphur is reduced
(D) H2O is one of the products

A2 Ans.: (A), (B) & (D)

The balanced equation is:
ClO3− + 6I− + 6H2SO4 → 3I2 + Cl− + 6HSO4− + 3H2O

So, stoichiometric coefficient of HSO4− is 6.

30.

 Equivalent Concept
Equivalent Concept (Gram equivalent concept)
Gram equivalent mass

It is the mass of one gram − equivalent of the substance in grams.

For a substance
Molar mass
Equivalent mass =
n - factor

Number of gm − equivalent

y Equivalents is similar property as moles but its value of not fixed.

i.e. 1 mole = NA particles
NA particles 
 
2NA particle 
But, 1 equivalent =   All are possible
or 
N / 3particles etc.
 A 
y For a substance, equivalent mass and in grams is equal to the mass of one
equivalent.
So for a substance:
Mass of subs tance(g) Mass
=
Number of equivalent = × n − Factor
Equivalent mass Molar Mass

= Moles × n−factor

Normality(N)
y It is a concentration terms means is defined for solutions
y It is defined as the number of equivalent of solute present in 1 litre of
solution.
Equivalent of solute
Normality =
Volume of solution(L)
Unit → equivalent/L or Normal
 Moles of solute 
N   × n − Factor
 Vsol. 

= Molarity × n − factor 
Normality
 Aslo
N× V =(Equivalent)Solute 

31.

 Calculation of n−factor
y n−factor is the property of a substance which have a positive value only.

n − Factor ≠ 0

≠ negative
Case −I: When no reaction is provided

i) For atom
n − factor =
General valency

e.g.

Atom n−factor

Na 1

Al 3

Fe 2

B 3

C 4 etc.

y For ions:
[n−factor = |magnitude of charge on ion]
e.g. H+ = 1
Ba2+ = 2
OH− = 1
CO32− = 2
PO43− = 3 etc.

y For acids:
n − factor =
Maximum basicity

Basicity = number of replacable H+ per molecule of acid.

HCl, HBr, HI, HNO3 , HCN,
e.g. HCOOH, CH3COOH,H3PO2 ,  n − factor =
1
H3BO3 etc. 

H2SO4, H2C2O4, H2CO3, H3PO3 etc. } n−factor = 2
H3PO4, H3AsO4 etc.} n−factor = 3

32.

y For bases:

n − factor =
Maximum acidity

No. of replacable OH− 

Acidity =  per molecule of base
No. of acceptable H+ 

e.g. NaOH, KOH, RbOH, CsOH, NH3, RNH2 etc.} = 1

Ba(OH)2, Zn(OH)2= NH2−CH2−CH2−NH2 etc.} = 2

y For salt:
n − factor =
Total charg e on cation or Total charg e on anions

Salt Ions n-factor

NaCl 1 Na+ and 1 Cl− 1

K2SO4 2 K+ and 1 SO42− 2

MgBr2 1 Mg2+ and 2 Br− 2

3 Ba2+ and
Ba3(PO4)2 6
2 PO43−

ILLUSTRATION:

Q1 Determine n−factor of K2SO4.Al2(SO4)3.24H2O

A1 From cation : 2K + + 2Al +3 From anion : 1 SO24− + 3SO24−

n − factor = 2 × 1 + 2 × 3 = 8 n − factor = 4 × 2 = 8

33.

 Q2 Calculate no. of gram equivalents in following:
i) 54 gm Al3+ ii) 98 gm H3PO4
iii) 2 mole CO32− iv) 1.5 g molecule Ba(OH)2
v) 12.04×10 ions of SO4
22 2−

A2 Using No. of equivalent =

Mass
× n − factor
Molar mass
i) 54 gm Al
54
Equivalent = ×3 =6
27
98
ii) 98 gm H3PO4 = ×3 =3
98
iii) 2 mole CO32− = 2×2 = 4
iv) 1.5 g molecule Ba(OH)2 = 1.5×2 = 3
 12.04 × 1022 
v) 12.04×1022 ions
= of SO42−  =  × 2 0.4
 NA 
 

Q3 Calculate normality of solution prepared by mixing 24.5 gm H2SO4 in its 500

ml solution.

A3 Given 24.5 gm of H2SO4

24.5
Molarity, M = 98 = 0.5
500
1000
Normality = Molarity × n−factor = 0.5 × 2 = 1 N
Mass 24.5
or, No. of equivalents = × n − factor
= ×=
2 0.5
Molar mass 98

Equivalent of solute 0.5

Normality = = = 1N
Volume of soution(L) 500 / 1000

34.

n-factor (Valency Factor)

n−factor in non−redox reaction

n − factor =
Charge Exchanged per molecule

Or
It is the magnitude of charge per molecule

       
Ag NO3   Ag Cl 
Na Cl   Na NO3

n-factor (1) (1) (1) (2)

2 
Ag NO3  Ba Cl 2 
 Ag Cl  Ba(NO3 )2

n-factor (1) (2) (1) (2)

Na 2CO3  HCl 

 H2CO3  NaCl
n-factor (2) (1) (2) (1)

Na 2CO3  HCl 

 NaHCO3  NaCl
n-factor (1) (1) (1) (1)

     
H Cl  Na OH 
 Na Cl  H2O

n-factor (1) (1) (1) (1)

H2SO4  NaOH 
 Na 2SO4  H2O
n-factor (2) (1) (2) (1)

H2SO4  NaOH 

 NaHSO4  H2O
n-factor (1) (1) (1) (1)

Note:
Acid + Base → Salt + H2O
↓ ↓ ↓ ↓
n-factor Basicity Acidity |Charge| (1)

35.

 H3PO4  NaOH 
 Na 3PO4  H2O
n-factor (3) (1) (3) (1)

H3PO4  NaOH 

 Na 2HPO4  H2O
n-factor (2) (1) (2) (1)

H3PO4  NaOH 

 NaH2PO4  H2O
n-factor (1) (1) (2) (1)

n−factor in redox reaction

For a substance present in a redox reaction, the “net increase or decrease
in oxidation number per molecule” is known as n−factor of that substance
in that reaction.
So, in a balanced redox reaction:
Total increase or decrease in the reaction
(n - factor)Subs tance =
Stoichiometric coefficient of substan ce

e.g.

n-factor

36.



2KMnO4  5H2C2O4  3H2SO4 

 2MnSO4  10CO2  K2SO4  8H2O
      
 10   10   10   10   10   10   10 
n-factor              
 2  5  3  2  10   1  8
5 1 +3 0
1H3As O4  2KI  2HCl 
 1H3 AsO3  I2  2KCl  H2O
      
2 2 2 2 2 2 2
n-factor              
 1 2 2  1  1 2  1

Lesson − n-factor (Valency Factor) Continued

Example
5
KMnO4  8HCl 
 MnCl 2  H2O  Cl 2  4KCl
   2  
5 5 5  5  5  5
n-factor           
 1 8  1 5 / 2  1 4

Cu  4HNO3 
 Cu(NO3 )2  2NO2  2H2O
    
2 2 2 2 2

n-factor          
 1 4  1 2 2
n−factor for disproportionation
xy
(n - factor )disproportion =
x+y

where x → n−factor for alone oxidation

y → n−factor for alone reduction

37.



KMnO4 + MnSO4 

→ MnO2
Re duction Oxidation Disproportion

3×2 6
(n − factor)MnO2 = =
3+2 5

Note: AxBy → Product

n−Factor ≠ 0
≠ (–ve)

e.g. NH3 → N2 + H2

(n − Factor )NH 3
≠0
=3
∴ 2NH3 
→ N2 + 3H2
6 6 6
     
2  1 3

H2 + O2 
→ H2O
(2) (4) (2)

P4 → PH3 + H2PO2−

12 × 4 48
N−factor − = = (3)
12 + 4 16

38.

Some commonly used agents
i) Permanganate ion MnO4− ( )
Since (+7) is maximum oxidation numbers for Mn so in redox reactions,
MnO4− always acts as an oxidizing agent.
The product depends upon the medium of reaction as following:
+2

acidic
→ Mn2+ (5)

+7 +4
MnO4− + R.A 
basic/neutral
→ MnO2 (3)

+6
strong basic
→ MnO24− (1)


ii) Dichromate ion (Cr2O72−)

It also acts as an oxidizing agent but only in acidic medium.
+6
+ 6 6
C r2O27 − 
H
→ 2Cr 3+ n − factor
= Cr2O7−2 = and Cr 3+
1 2

Other medium
Non − redox

iii) Oxalate ion (C2O42−)

In redox reactions, it always acts as reducing agent.
+3 +4
C 2 O24− redox

any medium
→ CO2

⇒ (n − factor)C O2 − =
2
2 4

iv) H2O2
With other reagent, will act as oxidizing and reducing agent
→ H2O
H2O2 + R.A 

(O.A) 
 (n-factor)H2O2 = 2
H2O2 + O.A 
→ O2 
(R.A) 


v) Mohr’s salt(Ferrous Ammonium sulphate

Redox
FeSO4.(NH4)2SO4.6H2O  → Fe3+ only
⇒ (n-factor)Mohr’s salt = 1

39.

 Law of equivalence
In a chemical reaction, all reactants react in equal number of equivalents
and produce same number of equivalents of each product.

i.e. A:B:C:D by moles = a:b:c:d

But
If ' x ' Equivalent

' x 'Equivalent
required
' x 'Equivalent ' x 'Equivalent
produces

⇒ A:B:C:D by equivalent = 1:1:1:1

e.g.
H2SO4 + 2NaOH 
→ Na2SO4 + 2H2O
1 mole 2 mole 1 mole 2 mole
n − factor (2) (1) (2) (1)
equivalent 2 2 2 2

Note: So, for a particular reaction,

(Equivalent )given = (Equivalent)required

where,
 Mass
Equivalent mass

 Mass
Molar mass × n − factor

Equivalent = 

Mole × n − factor

M × V × n − factor
N × V

40.

ILLUSTRATION:

Q1 To neutralize completely 20 mL of 0.1 M aqueous solution of phosphorous

acid (H3PO3), the volume of 0.1 M aqueous KOH solution required as:

(A) 10 ml (B) 20 ml (C) 40 ml (D) 60 ml

A1 (C)
Given:

H3PO3 + 2KOH → K2HPO3 + 2H2O

Volume of 0.1 M aqueous solution of phosphoric acid = 20 ml

We know from law of equivalence:

(Equivalent )H PO
3 3
= (Equivalent)KOH

M1×V1× n-factor = M2×V2×n-factor

0.1× 20×2 = 0.1 ×(V)KOH×1

⇒ 4 = (V)KOH × 0.1

⇒ VKOH = 40 ml

Q2 The number of moles of KMnO4 that will be needed to react with one mole of
sulphite ions in acidic solution is:
(A) 2/5 (B) 3/5 (C) 4/5 (D) 1

A2 A

2MnO4− + 5SO32− + 6H+ → 2Mn2+ + 5SO42− + 3H2O

We know from law of equivalence:

(Equivalent )KMnO 4
= (Equivalent)SO−2
3

(Mole × n − factor)KMnO
= (Mole × n-factor)SO−2
4 3

n × 5 =1 × 2
n = 2/5 moles

41.

 Q3 The mass of potassium dichromate crystals required to oxides 750 cm3 of
0.6 M Mohr’s salt solution is:
(Given molar mass: potassium dichromate = 294 g/mol, Mohr’s salt = 392 g/
mol)
(A) 22.05 g (B) 2.2 g (C) 0.49 g (D) 0.45 g

A3 (A)
K2Cr2O7 + 6FeSO4 + 7H2SO4 → K2SO4 + Cr2(SO4)3 + 3Fe2(SO4)3+7H2O
We know from law of equivalance:
(Equivalent )K Cr O
2 2 7
= (Equivalent)Mohr ' s salt

 Mole 
 × n − factor  = (M × V × n − factor )Mohr ' s salt
 Molar mass 

w 750
× 6 = 0.6 × ×1
294 1000
75 294
w = 0.6 × × = 22.05 gm
100 6

Q4 What weight of HNO3 is needed to convert 62 gm of P4 to H3PO4 in the reac-

tion?
P4 + HNO3 → H3PO4 + NO2 + H2O
(A) 63 gm (B) 630 gm (C) 315 gm (D) 126 gm

A4 (B)
The balance chemical reaction:
P4 + 20HNO3 → 4H3PO4 + 20NO2 + 4H2O
Molar mass of P4 = 9/mol
Molar mass of HNO3 = 63 9/mol
We know from law of equivalence:
(Equivalent )P = (Equivalent)HNO3
4

 Mass   Mass 
 × n −=
Factor   × n − Factor 
 Molar mass P4  Molar mass HNO3

62 w
⇒ × 20 = ×1
124 63
62
⇒ w= × 20 × 63 = 630 gm
124

42.

Titration (A(aq) vs B(aq))
Aim: Determination of the concentration of solution present in conical flask
by titration with standard solution from burette.

1
0
2
0 B (aq). known : Standard Solution
3
0
4
0
5 At equivalence point
0
(Eq.)A  (Eq.)B

A(aq)
Unknown

ILLUSTRATION:

Q1 It requires 40 ml of 1 M Ce4+ to titrate 20 ml of 1 M Sn2+ to Sn4+. What is the

oxidation state of the Cerium in the product?

A1 Ce4+ + Sn2+ → Sn4+ + Cen+

(Milli Equivalent )Ce = (Milli Equivalent)Sn

4+ 2+

(M × V × n − factor )Ce = (M × V × n − factor)Sn

4+ 2+

1 × 40 × (4 − n) =1 × 20 × 2
40 × (4 − n) =
40
4−n = 1
n = 4−1
n=3

43.

 Q2 6.7 gm sample of Na2C2O4 is titrated with 40 ml, 0.02 M KMnO4 solution in
acidic medium. Calculate % purity of original sample.

A2 +3 +7
H
Na2 C 2 O4 + K MnO4 → Mn2+ + CO2
+ +2 +4

(Equivalent )Na C O
2 2 4
= (Equivalent)KMnO
4

x  40 
×
= 2  0.02 × × 5
134  1000 
x 4
= 0.1 ×
67 100
4
x = 0.1 × × 67
100
26.8
x =
100
x = 0.268
0.268
=
Now, % purity × 100
6.7
= 0.04 × 100
% purity
% purity = 4 %

Q3 An aqueous solution of H2O2 is diluted 20 times. If 100 ml of this diluted

solution requires 200 ml, 0.1N K2Cr2O7 solution for complete titration in acid-
ic medium, then calculate volume strength of the original H2O2 solution.

A3 Molarity of original H2O2 solution is “x” M

x
Molarity of diluted H2O2 solution = M
20
K2Cr2O7 + H2O2 → Cr3+ + O2

∴ Milli (Equivalent )K Cr O =
(Milli Equivalent)H2O2
2 2 7

x
0.1 × 200 = × 100 × 2
20
x=2M

∴ Volume strength = 2×11.2 = 22.4 V

44.

Different Types of Titration
ILLUSTRATION:

Q1 0.84 g iron ore containing ‘x’ percent of iron was taken in a solution contain-
ing all the iron in ferrous condition. The solution required ‘x’ ml of a dichro-
matic solution for oxidizing the iron content to ferric state. Calculate the
normality of dichromatic solution.

A1 Fe2+ + Cr2O72− → Fe3+ + Cr3+

(Equivalent )Fe = (Equivalent)K2Cr2O7 from law of equivalance
x
0.84 ×
100 × 1 =x × N
56 1000
0.84 × 100
=
⇒N = 0.15 eq / L
56 × 100

Q2 An equimolar mixture of Na2C2O4 and H2C2O4 required V1 litre of 0.1 M KMnO4

in acidic medium for complete oxidation. The same amount of the mixture re-
quired V2 litre of 0.2 M NaOH for neutralization. The ratio of V1 to V2 (V1/V2) is:
(A) 2:5 (B) 1:2 (C) 4:5 (D) None of these

A2 (A)
Case−I: Equimolar mixture of Na2C2O4 and H2C2O4 required V1 L of 0.1M KMnO4
in acidic medium.
As the mixture is equimolar, 1 mole of each are present.
∴ Eq. of Na2C2O4 + Eq. of H2C2O4 = Eq. of KMnO4
1×2 + 1×2 = 0.1×V1×5
(∴ equivalent = mole × valence factor)
4
V1 =
0.5
V1 = 8L
Case − II: Equimolar mixture of Na2C2O4 and H2C2O4 required V2L of 0.2 M
NaOH for neutralization.

(Equivalent )Na C O
2 2 4
+ (Equivalent )H C O
2 2 4
=
(Equivalent)NaOH
1 × 2 + 1 × 2 = V2 × 0.2 × 1
2 + 2 = V2 × 0.2
V2 = 20L
V1 8
∴ = = 2:5
V2 20

45.

 Iodimetric Titration:
y It is used to determine strength of a reducing agent by direct titration of it
with standard solution of I2
i.e.

Iodometric Titration:
y It is used to determine strength of an oxidizing agent
y It is a two−step process as following:
Step−I:

Oxidising agent + I− (aq.) 

→ Product + I2
(excess)

Step−II:

I2 + 2Na2S2O3 
→ Na2S4O6 + 2NaI
(evolved) Sodium thiosulphate
(Hypo)

(Equivalent )  = (Equivalent)I  ...(1)

 O.A   2 1

(Equivalent )  = (Equivalent)
 Hypo 
 ...(2)
 I2  2

∴ Moles of I2 in both reactions are same.

(n − factor ) I2
1
=
2

Also (n − factor ) I2
2
=
2
⇒ (EqI )1 =
(EqI )2
2 2

So,
(Eq) O.A = (Eq.) hypo

46.

ILLUSTRATION:

Q1 50 ml KMnO4 solution is mixed with excess of KI solution in acidic medium.

The liberated I2 requires 200 ml of 0.25 M Na2S2O3 solution for complete ti-
tration. Calculate molarity of KMnO4 solution.

A1 Given
KMnO4 + I− → Mn2+ + I2
I2 + Na2S2O3 → Na2S4O6 + NaI
Volume of KMnO4 solution = 50 ml
Volume of Na2S2O3 solution = 200 ml
∴ (Mill Equivalent )KMnO =
(Mill Equivalent)Na2S2O3
4

M × 50 × 5
= 0.25 × 200 × 1
0.25 × 200 × 1
M=
50 × 5
Molarity of [KMnO4 ] = 0.2M

Q2 25 ml of household bleach solution was mixed with 30 ml of 0.50 M KI and

10 ml of 4 N acetic acid. In the titration of the liberated iodine, 48 ml of 0.25
N Na2S2O3 was used to reach the end point. The molarity of the household
bleach solution is:
(A) 0.48 M (B) 0.96 M (C) 0.24 M (D) 0.024 M

A2 C
Cl2 + I− → I2 + Cl−
I2 + Na2S2O3 → Na2S4O6 + NaI
(n − factor )I
2
is same in both steps

(Mill Equivalent )Cl =(Mill Equivalent)Hypo ∴ eq. =N × V(m) 

x=
×2 (0.25) × 48

0.25 × 48
x=
2
x=6
x 6
(Molarity)Bleach= = = 0.24 M
Volume 25

47.

 Note:

A 
→B
All B  →C
If n − Factor of B in both are same
(Eq.)A = (Eq. )C
If n − Factor of B are different
(Eq.B )1 ≠ (Eq.B )2 ,
then apply mole method for solving

Q3 10 ml of K2C2O4 solution is mixed with excess of KIO3 solution. The evolved I2

requires 20 ml, 0.5 M hypo solution for complete titration.
Determine the molarity of K2C2O4 solution.

A3 K2C2O4 + KIO3 → I2 + CO2

I2+ 2Na2S2O3 → Na2S4O6 + 2NaI

(Milli Equivalent )I = (Milli Equivalent)Na2S2O3 (Muilli Equivalent )K C O = (Milli Equivalent)I2

2 2 2 4

n × 2= 0.5 × 20 × 1 M × 10 × 2 =5 × 10
10.0 × 1 50
n= M=
2 20
n = 5 m.mole M = 2.5 M

Q4 To measure the quantity of MnCl2 dissolved in an aqueous solution, it was

completely converted to KMnO4 using reaction,
MnCl2 + K2S2O8 + H2O → KMnO4 + H2SO4 + HCl (Equation not balanced)
Few drops of concentration HCl were added to this solution and gently
warmed. Further oxalic acid (225 mg) was added in portions till the colour of
the permanganate ion disappeared. The quantity of MnCl2 (in mg) present in
the initial solution is ____________.
(Atomic weight in g mol−1; Mn=55, Cl=35.5)

48.

 A4 MnCl2 → MnO4−
+
H
MnO4− + H2C2O4 → Mn2+ + CO2

(n − Factor )MnO−
4

→ same in both reaction

(Equivalent )C O 2−
2 4
= (Equivalent)MnO−
4

0.225
2× =moles × 5
90
⇒ molesM O– =0.001
n 4

(Equivalent )MnCl 2
= (Equivalent)MnO−
4

WMnCl2
Now, ×=
5 0.001 × 5
(55 + 71)

WMnCl2= 0.001 × (55 + 71) gm

WMnCl2 = 126 mg

Given quantity of MnCl2 dissolved in an aqueous solution was completely

converted to KMnO4.
∴ Quantity of MnCl2 present in the initial solution = 126 mg

Lesson − Back Titration, Double Indicator Titration

Back Titration:
y A multistep process which can be used for both redox as well as non−redox
reactions.

Step−I:

A + B 
→ product
(L.R)

(Eq)A = (EqB )1
Step−II:
B + C → product
(remaining)
(EqB )2 = (Eq)C
(nB )1 + (nB )2 =
Initial moles of B (Given)

49.

 y If n-factor of B in both are same:
(Eq.B=
)Total (Eq.)A + (Eq.)C

y If n-factor of B in both are different:

First solve reaction in steps (2) and find (nB)2.
Now, (nB)1 = (nB)given − (nB)2
Now solve reaction in step (1) and find A.

ILLUSTRATION:

Q1 50 gm of a sample of Ca(OH)2 is dissolved in 50 ml of 0.5 N HCl solution. The

excess of HCl was titrated with 0.3 N NaOH. The volume of NaOH used was
20 cc. Calculate % purity of Ca(OH)2 sample.

A1 Ca(OH)2 + 2HCl → CaCl2 + 2H2O

HCl + NaOH 

→ NaCl + H2O
(Remaining)

Let ‘x’ gm of Ca(OH)2 present in sample

n-factor of HCl is same in both.

So,

(Eq.)HCl
= (Eq.)Ca(OH)
2
+ (Eq.)NaOH
50  x   20 
0.5 × =  × 2  +  0.3 × 
1000  74   1000 
25 x 6
= +
1000 37 1000
25 6 x
⇒ − =
1000 1000 37
19 x
=
1000 37
19
⇒ x = × 37
1000
703
= x = 0.703 g
1000
Now,

Mass of Ca(OH)2 0.703

% purity= × 100= × 100= 1.406%
Mass of sample 50

50.

Q2 9.0 g of an ammonia solution is treated with 50 ml 0.5 N H2SO4 solution, 20
ml of 0.1 N NaOH is required for back titration. What is the percentage of
ammonia in the solution?

A2 Let mass of pure NH3 = x gm

(Eq.)H SO = (Eq.)NH
2 4 3
+ (Eq.)NaOH
50  x   20 
0.5 × =  × 1  +  0.1 × 
1000  17   1000 
25 x 2
= +
1000 17 1000
25 2 x
⇒ − =
1000 1000 17
23
⇒ × 17 =x
1000
391
⇒ x = = 0.391gm
1000
0.391
∴ % NH3 = × 100= 4.34%
9

Q3 40 ml solution of Na2C2O4 is treated with 100 ml, 0.1 M KMnO4 in acidic me-
dium, the excess of MnO4− solution requires 10 ml of 0.05 M H2O2 solution in
basic medium for complete titration.
Calculate molarity of Na2C2O4.

A3
+
H
C2O42− + MnO4− → Mn2+ + CO2 …(1)
−
OH
MnO4− + H2O2  → MnO2 + O2 …(2)

(Remaining)
n-factor of MnO4− is differed in both
For reaction 2,
(m. eq.)MnO −
4
= (m. eq. )H O
2 2

m. moles × =
3 0.05 × 10 × 2
5 × 10 × 2
m. molesMnO1 =
4 100 × 3
1
m. molesMnO1 =
4 3

51.

 (
m.moles of MnO4− ) Total
=0.1 × 100 =10m.mole
1 29
m.moles of MnO4− used in 1 reaction = 10 − = m.mole
3 3
For reaction (1):
(m. eq.)Na2C2O4 = (m. eq.)MnO−
4

29
M × 40 × 2 = ×5
3
29 5 145 29
M = × = = mol / L
3 80 240 48

Double Indicator Titration:

The titration consisting two equivalence points which are detected by two
different indicators.

y Na2CO3(aq.) vs (HCl(aq.)

i) When all Na2CO3 consume to give NaHCO3,

⇒ 1st equivalence point is reached
Suitable indicator = Phenolphthalein

52.

 ii) Now on further addition of HCl
NaHCO3 + HCl → H2CO3 + NaCl (Neutral)
When all NaHCO3 consumed to give H2CO3

⇒ 2nd equivalence point is reached
Suitable indicator = Methyl orange
y If alone phenolphthalein is used then only 1st equivalence point in detected.
y If alone methyl orange is used then only 2nd equivalence point is detected.
y To detect both equivalence point, initially phenolphthalein is mixed and after
1st equivalence point, Methyl orange should be mixed.

ILLUSTRATION:

Q1 In the mixture of (NaHCO3 + Na2CO3), volume of HCl required in ‘x’ ml with

phenolphthalein indicator and y ml with methyl orange later in the same
titration. Hence volume of HCl for complete reaction of Na2CO3 is:
(A) 2x (B) y (C) x/2 (D) (y−x)

A1 A

Now, methyl orange is added to detect 2nd equivalence point

NaHCO3 + HCl → H2CO3 + NaCl

(m.eq)HCl = (m.eq)NaHCO
3

N × y = (a + b) × 1
HCl
Na2CO3 → H2CO3

(Eq)Na CO
2 3
( )HCl
= Eq

b×2 = N× V
(Nx) × 2 = N× V
2Nx
V =
N
V = 2x
∴ volume of HCl for complete reaction is 2x ml

53.

 Q2 0.1 g of a solution containing Na2CO3 and NaHCO3 requires 10 ml of 0.01 N HCl
for neutralization using phenolphthalein as an indicator. Weight percent of
Na2CO3 in solution is
(A) 25 (B) 32 (C) 50 (D) None of these

A2 D
(m.eq.)Na CO
2 3
= (Eq)HCl
x 10
× 1= 0.01 ×
106 1000
0.1
⇒ x = × 106
1000
⇒ x =106 × 10−4 gm
106 × 10−4
∴ Wt. % of Na2=
CO3 ×=
100 10.6%
0.1

Q3 A mixture of NaOH and Na2CO3 required 25 ml of 0.1 M HCl using phenol-

phthalein as the indicator. However, the same amount of the mixture re-
quired 30 ml of 0.1 M HCl when methyl orange was used as the indicator. The
molar ratio of NaOH and Na2CO3 in the mixture was:

A3 4:1
Let m.moles of NaOH = ‘x’ m.mole
and m.moles of Na2CO3 = ‘y’ m. mole
Phenolphthalein is added to detect 1st equivalence point (NaHCO3)
HCl HCl
First: All NaOH → NaCl ; Then Na2CO3 → NaHCO3
(m.eq.)HCl
= (m.eq.)NaOH + (m.eq.)Na CO
2 3

0.1 × 25 × 1 × =
1 x(1) + y(1)
⇒ x+y = 2.5 m.mole ...(1)

Titration with methyl orange is added to detect 2nd equivalence point direct
HCl
NaOH → NaCl
HCl
NaCO3 → H2CO3
(m.eq.)HCl
= (m.eq.)NaOH + (m.eq)Na CO 2 3

0.1 × 30 × 1= x(1) + y(2)

⇒ x + 2y = 3 m.mole ...(2)
⇒ x = 2 m mole and y = 0.5 m. mole, on solving (1) & (2).
2
Ratio of mole of NaOH & Na2CO3 = =4:1
0.5
54.

Hardness of Water

ILLUSTRATION:

Q1 100 ml solution of NaOH and Na2CO3 was first titrated with N/10 HCl in pres-
ence of HPh, 17.5 ml is required to end point. After this MeOH was added and
2.5 ml of same HCl is required. The amount of NaOH in mixture is

(A) 0.06 g per 100 ml

(B) 0.06 g per 200 ml

(C) 0.05 g per 100 ml

(D) 0.012 g per 200 ml

A1 A
Let ‘x’ m mole of NaOH in 100 ml solution and ‘y’ m.ole of Na2CO3 in 100 ml
solution.

HPh ⇒ 1st equivalence point (NaHCO3)

⇒ (m.eq.)HCl =
(m.eq.)NaOH + (m.eq.)Na CO
2 3

1
⇒ × 17.5 =x(1) + y(1)
10
⇒ x+y = 1.75 ...(1)
MeOH ⇒ 2nd equivalence point.

⇒ (m.eq.)HCl =
(m.eq.)NaHCO
3

1
⇒ × 2.5 =
y(1)
10
⇒ y =
0.25 m.mole

⇒ x = 1.5 m.mole

\ Weight of NaOH = 1.5×40×10−3 = 60 gm

55.

 Q2 1 g of sample CaCO3 was strongly heated and the CO2 liberated was absorbed
in 100 ml of 0.5 N NaOH solution. Assuming 90% purity for the sample. How
many mL of 0.5 M HCl would be required to react with the resulting solution
to reach the end point in presence of phenolphthalein?
(A) 73 ml (B) 41 ml (C) 82 ml (D) 100 ml

A2 C
90
Weight of CaCO3 = 1 × =
0.9 gm
100
0.9
Mole of CaCO3= mole
100
0.9
∴ mole of CO2 liberated = mole = 9 m.mole
100
CaCO3 → CaO + CO2
9 m.mole 9 m.mole

CO2 + 2NaOH 

→ Na2CO3 + CO2
CO2 + 2NaOH 
→ Na2CO3 + H2
9 m.mole 50 m.mole 9 m.mole
L.R (50-18)
=32m.mole(Remaining)

HCl

NaOH + HCl 

→ NaCl + H2O
Na 2CO3 + HCl 
→ NaHCO3 + NaCl

N aH CO 3
+
N a 2 CO 3 Phenolphthalein

1st equivalence point

(m.eq.)HCl
= (m.eq.)NaOH + (m.eq.)Na CO
2 3

0.5 × V × 1= 32(1) + 9(1)

41
VHCl =
0.5
41
= × 10
5
VHCl = 82 ml

56.

 Hardness of water

Soft water: Water which produces lathers (foam) upon mixing of soap into
it easily.

Hard water: Water which does not produce foam with soap due to presence
of Ca2+(aq.) or Mg2+(aq.) in water.

Sodium stearate : C17H35COONa (soap)

C17H35COO− (aq.) + Ca2+ (aq.) or Mg2+ (aq.) 

→(C17H35COO)2 Ca or Mg(C17H35COO)2
ppt.
y These Ca2+ or Mg2+ ions are furnished by their water soluble salts

(bicarbonates, chlorides or sulphates only)

i.e. Ca(HCO3 )2 

Mg(HCO3 )2 

CaCl 2  Hardness causing salt
MgCl 2 

CaSO4 

Degree of Hardness

y It is the measure of total hardness causing salt present in water.

y Measured in ppm as following:

* CaCO3 is hardness causing.

For a water sample:

∑ (m.eq.) salts = (m.eq.)CaCO3

∴n − factor of all =2
⇒ ∑ (n) salts =
(n)CaCO3

57.

 ILLUSTRATION:

Q1 One litre of a sample of hard water contains 1 mg of CaCl2 and 1 mg of MgCl2.

Then the total hardness in terms of parts of CaCO3 per 106 parts of water by
mass is:
(A) 1.954 (B) 1.260 (C) 0.946 (D) None of these

A1 (A)
1 litre water means 1000 gm
Given: Mass of CaCl2= 1 mg
10−3
Moles of CaCl2= mole
111
Mass of MgCl2= 1 mg
10−3
Moles of MgCl2= mole
95
 10−3 10−3 
 + 
 111 95 
=
Hardness × 100gm × 106
1000 g
Hargness = 1.954 ppm

Q2 A given sample of water containing the following impurities:

Mg(HCO3)2 = 73 mg/L, Ca(HCO3)2 = 162 mg/L
CaSO4 = 136 mg/L, MgCl2 = 95 mg/L
CaCl2 = 111 mg/L and NaCl = 100 mg / L
Then the total hardness (temporary and permanent) of above water sample
is:
(A) 300 ppm (B) 350 ppm (C) 450 ppm (D) 500 ppm

A2 C
Let volume of water =1 L = 1000 ml
Mass of water = 1000 gm
 73 162 136 95 111  6
 + + + +  × 100 × 10
−3  146 162 136 95 111 
Hardness =
10 450 ppm
1000

58.

 Removal of Hardness:

Ca2+ (aq.) or Mg2+ (aq.) 

every method
→ Water insoluble salt of Ca or Mg
(Water soluble salts) (Precipitate)

y Temporary hardness:
It is easily removed by following process:
a) By boiling of water
M(HCO3)2(aq.) → MCO3(s) + H2O(l) + CO2(g)

b) By the addition of Na2CO3

M(HCO3)2(aq.) + Na2CO3(aq.) → MCO3(s) + 2NaHCO3(aq.)

c) Clarke’s process:
By the addition of exact amount of Ca(OH)2, because excess will also
impart hardness in water.
Ca(HCO3)2(aq.) + Ca(OH)2(aq.) → 2CaCO3(s) + 2H2O(l)
Mg(HCO3)2(aq.) + Ca(OH)2 → MgCO3(s) + CaCO3(s) + 2H2O(l)

y Permanent hardness
i) By adding Na2CO3 or Na3PO4.
CaSO4 + Na2CO3 → CaCO3↓ + Na2SO4
3CaCl2 + 2Na3PO4 → Ca3(PO4)2↓ + 6NaCl

ii) Ion exchange resins process.

2RnH
cation
+ Ca2+  ( )2
→ Rn Ca + 2H+
exchanger

iii) Permutit process

Ca2+ Na2Z → CaZ + 2Na+ → Ca2+ Na2Z → CaZ + 2Na+
Mg2+ + Na2Z → MgZ + 2Na+
[Na2Z is the sodium zeolite (Na2Al2Si2O8H2O)]

iv) Calgon (Calcium gone) process

Na6(PO3)6 is called Calgon which is written as Na2[Na4(PO3)6]
Na4(PO3)6]2− + M2+ → Na2M(PO3)6]2− + 2Na+
where M = Ca2+/Mg2+

59.

 ILLUSTRATION:

Q1 A sample of hard water contains 20 mg of Ca2+ ions per litre. How many milli
equivalent of Na2CO3 would be required to soften 1 litre of the sample?
(A) 0.5 (B) 0.1 (C) 0.2 (D) 1

A1 (D)
Given mass of Ca2+ ions = 20 mg
(m.eq.)Na CO
2 3
= (m.eq.)Ca2 +

 20 
=  ×2
 40 
= 1 milliequivalent

Q2 Consider the temporary hardness of water is due to the presence of Ca(HCO3)2

and specific gravity of hardwater is 1. Then the weight of CaO required for
106 litre of water to remove the temporary hardness of 1000 ppm is:
(A) 3.6×104 gm (B) 6.5×104 gm (C) 5.6×105 gm (D) 8.5×105 gm

A2 C
Given Volume of water = 106L
= 109 ml
Mass of water = 109 gm
mass of CaCO3
=
Using, (in ppm) hardness × 106
mass of water

WCaCO3 × 106
1000 =
109
WCaCO3 = 106 gm

= 104 mole
i.e. ∴ mole of moeCaCO3 = 104 mole
(Eq.)Salt = (Eq.)CaO
w
104 × 2 = ×2
56
104 × 2 × 56
w =
2
= 56 × 104
w
w 5.6 × 105 gm
=

60.