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 Redox Reaction - Definition
Reduction
An oxidation-reduction (redox) reaction
is one in which Oxidation and Reduction REDOX REACTIONS
reactions take place simultaneously. Oxidation

Classical definition of Oxidation and Reduction is in

terms of Addition or Removal Byofarvind
HydrogenArora
or Oxygen
Interpretation – Case A
Oxidation Addition of Oxygen or any electronegative element
2 Mg + O2 2 MgO
S + O2 SO2
Mg + F2 MgF2
Fe + S FeS
Byorarvind
Reduction Removal of Oxygen Arora
any electronegative element
2 HgO 2 Hg + O2
C + H 2O H2 + CO
H2 + 2 FeCl3 2 FeCl2 + 2 HCl
SnCl2 + 2 HgCl2 Hg2Cl2 + SnCl4
Interpretation – Case B
Oxidation Removal of Hydrogen or any electropositive element
2 H2S + Cl2 2 S + 2 HCl
4 HI + O2 2 I 2 + 2 H 2O
2 KI + Cl2 I2 + 2 KCl
2 KI + H 2 O2 I2 + 2 KOH
By arvind
Reduction Addition of Hydrogen Arora
or any electropositive element
Cl2 + H2 2 HCl
C2 H 4 + H 2 C2 H 6
HgCl2 + Hg Hg2Cl2
CuCl2 + Cu Cu2Cl2
Applying the Classical Definition ! Applying the Classical
Example 1 2 Na + H2 2 NaH Definition can be tricky !
There is addition of H2 on Na.
Is Na undergoing Reduction ? NO !
The reaction represents OXIDATION of Na
Reason : H is more electronegative than Na
Example 2 O2 + 2 F2 By2 arvind
OF2 Arora
There is addition of O2 on F2.
Is F2 undergoing Oxidation ? NO !
The reaction represents REDUCTION of F2
Reason : O is less electronegative than F
 Modern Definition of Redox Reactions Electronic Concept
OXIDATION – Loss of electrons (De-electronation)
REDUCTION – Gain of electrons (Electronation)

Example of Oxidation Reactions

+
Na Na + e
Zn 2+ + 2 −
Zn
By
Example of Reduction Reactions
arvind
e
− Arora

Cl2 + 2 2
− −
S + 2
e ClS2−
−
e
Redox Reaction – Important Points
One cannot take place
All oxidation and reduction reactions
without the other
are complementary to one another
The simultaneous oxidation and reduction
reactions are termed as Redox Reactions

In a Redox Reaction:
By arvind Arora
Number of Electrons Gained= Number of Electrons Lost
Example – Exchange of Electrons Balance the electrons
2 Mg + O2 2 MgO lost and gained

Oxidation Half Reaction

Mg +
Mg2 + 2 1 × 2
−
e
Reduction Half Reaction
O2 + 4 2 By 2
arvind Arora
− − Add up the two half reactions
+ eO2 O2 2 + 2−
2 Mg 2 Mg + 2 O
2 MgO
General Representation of Oxidation and Reduction
Loss of Electrons
OXIDATION
− 2 − 1 − 0 − 1+ − 2+ −
− M − M − M − M e− M e−
+e − +e − +e +e + +
− − − − − −
e
REDUCTION e e e e e
Gain of Electrons
OIL RIG
By arvind Arora
Oxidation Is Loss Reduction Is Gain
Take CHARGE as a NUMBER.
Increase in this NUMBER is Oxidation
Decrease in this NUMBER is Reduction
Oxidizing Agents (OA) and Reducing Agents (RA)

Oxidizing Agent
The species which oxidizes a substance and gets
reduced is called as Oxidizing Agent.
It gains electrons.

Reducing Agent By arvind Arora

The species which reduces a substance and gets
oxidized is called as Reducing Agent.
It loses electrons.
Example – Recognizing OA and RA OA – It Gains Electrons
RA – It Loses Electrons
2 Mg + O2 2 MgO

Oxidation Half Reaction

+
Mg Mg2 + 2
− Mg – Reducing Agent
e By arvind Arora

Reduction Half Reaction

O2 – Oxidizing Agent
O2 + 4 2
− −
e O2
 Oxidation Number
The Oxidation Number or Oxidation State is defined as the charge,
real or imaginary which an atom appears to have when it is in
chemical combination.

Ionic Compounds
Real Charges Covalent Compounds
By arvind Arora
Imaginary Charges

Interpretation of Ionic And Covalent Compounds ?

Interpretation of Ionic Compounds
O.N. of Na = +1
O.N. of Cl = –1
NaCl Na+ Cl–
Interpretation of Covalent Compounds

HCl H ■ Cl H ■ Cl
· + · –
H Cl
H has lost 1 electron By arvind
O.N. Arora
of H = +1
Cl has gained 1 electron O.N. of Cl = –1

Shared electrons are assigned to

the more electronegative atom
Rules for assigning Oxidation Number
Rule 1
The O.N. of an atom in free or uncombined
elemental state is zero.

O.N. of O in O3 = 0
O.N. of F in F2 = 0
By arvind
O.N. Arora
of O in O 2
=0
O.N. of Br in Br2 = 0

O.N. of P in P4 = 0 O.N. of Cl in Cl2 = 0

O.N. of S in S8 = 0
Rules for assigning Oxidation Number
Rule 2
The O.N. of Fluorine is always –1 in all its O.N. of F = −1
compounds.

Rule 3
The O.N. of Oxygen is –2 in all its compounds O.N. of O = −2
By arvind
expect in Peroxides, Superoxides, OxidesArora
of
Fluorine.
Rules for assigning Oxidation Number
PEROXIDES
Example: H2O2, Na2O2 O.N. of O = −1

SUPEROXIDES
Example: KO2, RbO2 O.N. of O = −1/2
By arvind Arora
OXIDES OF FLUORINE
Example: O2F2 O.N. of O = +1

Example: OF2 O.N. of O = +2

 Rules for assigning Oxidation Number
Rule 4
The O.N. of Hydrogen is +1 in all its compounds
except Metallic Hydrides (S-Block Hydrides)
where the O.N. is −1. O.N. of H in NaH = −1

Rule 5 By arvind Arora O.N. of H in HCl = +1

The O.N. of Alkali Metals is always +1.
The O.N. of Alkaline Earth Metals is always +2.
Rules for assigning Oxidation Number
Rule 6
The sum of oxidation numbers of all atoms in a
species is equal to the net charge on the specie.

Example: KMnO4 (Neutral Molecule)

O.N. of K + O.N. of Mn + 4 × O.N. of O = 0
By arvind Arora
−
Example: Cr2O72 (Polyatomic Ion)
2 × O.N. of Cr + 7 × O.N. of O = –2
Rules for assigning Oxidation Number
INTERPRETAION OF COVALENT BONDS

Assumption : EN > EN Shared electrons are assigned to

B A
the more electronegative atom
Cases O.N. of A O.N. of B

A B +1 −1
By arvind Arora
A B +2 −2
A B +3 −3
A B +2 −2
A B 0 0
Calculation of O.N. – Covalent Bonds Interpretation

O.N. of N in HCN
O.N. of N in HNC

H C N
H N C
H +1 −1 C +3 −3 N By arvind Arora
H+1 −1N −2 +2
C
O.N. of N = −3
O.N. of N = −3
Paradox of Fractional Oxidation Number Can the exchange of electrons
be in fractions ?
O.N. of Fe in Fe3O4
Let the O.N. of Fe be x Standard Approach
3(O.N. of Fe) + 4(O.N. of O) = 0 Algebraic Method
3x + 4 (–2) = 0
x = +8/3
FeO : O.N. of Fe = +2
Fe3O4 exists as FeO•Fe2O3 By arvind Arora
Fe2O3 : O.N. of Fe = +3
Sum of O.N. of all atoms of the Element
Average O.N. =
Total number of atoms of the Element
1 (+2) + 2 (+3) 8
Average O.N. = =+
3 3
Important Structures – Caro’s Acid (H2SO5)

O.N. of S in H2SO5

H O S OBy arvind H
O Arora

O
Important Structures – Caro’s Acid (H2SO5)

O.N. of S in H2SO5
O.N. of S = +6
O
−2
+2
H+1 −1O S
−1 +1 +1 −1 0 O 0 +1H
O−1 Arora
+2 By arvind
−2
O
Important Structures – Marshall’s Acid (H2S2O8) O.N. of S in H2S2O8

O O

H O S O O S O H
By arvind Arora
O O
Important Structures – Marshall’s Acid (H2S2O8) O.N. of S in H2S2O8

O
−2
O
−2
+2 +2
H+1 −1O S
−1 +1 +1 −1 O0 0 O−1 +1+2S+1 −1O−1 +1H
+2
−2 −2
By arvind Arora
O O
O.N. of S = +6
Important Structures – Chromium Oxide Peroxide (CrO5)

O.N. of Cr in CrO5

O
O O
Cr By arvind Arora
O O
Important Structures – Chromium Oxide Peroxide (CrO5)

O.N. of Cr in CrO5

O O.N. of Cr = +6
−2
O0 −1 +2
O0
−1
+1 +1
0
Cr+1
+1 0By arvind Arora
−1
O O
−1
Important Structures – Bleaching Powder (CaOCl2)

O.N. of Cl in CaOCl2

−
C
2+
Ca l
− Cl By arvind Arora
O
Hypochlorite Ion
(OCl−)
Important Structures – Bleaching Powder (CaOCl2)

O.N. of Cl in CaOCl2

−
C
2+
Ca l
− −1 +1Cl By arvind Arora
O
Hypochlorite Ion
(OCl−)
Balancing of Redox Reactions
Balancing a Redox Reaction involves:
• Balancing of Atoms
• Balancing of Charge
• Balancing of Electrons – lost and gained
Methods:
Oxidation Number Method
By arvind Arora
Half-Reaction Method

Balancing a Reaction also involves MEDIUM

Acidic or Basic or Neutral
 O.N. Change
Oxidation Number Method – Steps
Loss/Gain of Electrons
Step 1
Calculate the O.N. of all elements and balance
the atoms of elements whose O.N. changes.
Step 2
Find out the total O.N. change of all elements
and balance the electrons lost with electrons
gained. By arvind Arora
Step 3 Balance the charge using the
+
medium given. Acidic Medium : H
–
Alkaline/Basic Medium: OH
Balancing of H and O Atoms In general, balancing the CHARGE
Alternative to Step 3 balances H and O atoms

Acidic Medium
Do check H and O
H Atom : Add H+ to the side lesser in H.
O Atom : Add H2O to the side lesser in O
+
and 2 H to the other side.
Basic Medium By arvind Arora
H Atom : Add H2O to the side lesser in H
−
and OH to the other side.
O Atom : Add 2 OH− to the side lesser in
O and H2O to the other side.
 Applying Oxidation Number Method
The RAW equation is called
Ex-1 SKELETAL EQUATION

+2 +7 +3 +2
+ − + +
Fe2 (aq) + MnO4 (aq) Fe3 (aq) + Mn2 (aq) Acidic Medium

By arvind Arora
 Applying Oxidation Number Method
The RAW equation is called
SKELETAL EQUATION

+2 +7 +3 +2
+ − + +
Fe2 (aq) + MnO4 (aq) Fe3 (aq) + Mn2 (aq) Acidic Medium

Fe is balanced. O.N. Calculation

Mn is balanced. By arvind
Algebraic MethodArora

Step 1 In general, O.N. of O = –2 and H = +1

Calculate the O.N. of all elements and balance
the atoms of elements whose O.N. changes.
Applying Oxidation Number Method

+2 +7 +3 +2
+ − + +
Fe2 (aq) + MnO4 (aq) Fe3 (aq) + Mn2 (aq) Acidic Medium

For Fe : (+2) – (+3) = –1e (Oxidation)

For Mn : (+7) – (+2) = +5e (Reduction)
By arvind Arora

Step 2 O.N. Change = Initial O.N. – Final O.N.

Find out the total O.N. change of all elements
and balance the electrons lost with electrons
gained.
Applying Oxidation Number Method

+2 +7 +3 +2
+ − + +
Fe2 (aq) + MnO4 (aq) Fe3 (aq) + Mn2 (aq) Acidic Medium
+5e–
Reduction Half Reaction
–1e– ×5
Oxidation Half Reaction By arvind Arora

Step 2
Find out the total O.N. change of all elements
and balance the electrons lost with electrons
gained.
Applying Oxidation Number Method

+2 +7 +3 +2
5 Fe2+(aq) + − 5 Fe3+(aq) + +
MnO4 (aq) Mn2 (aq) Acidic Medium

By arvind Arora

Step 2
Find out the total O.N. change of all elements
and balance the electrons lost with electrons
gained.
 Applying Oxidation Number Method

+2 +7 +3 +2
5 Fe2+(aq) + − 5 Fe3+(aq) + +
MnO4 (aq) Mn2 (aq) Acidic Medium
Reactant Side : 5 × (2+) + 1 × (1–) = 9+
Product Side : 5 × (3+) + 1 × (2+) = 17+
+
Add 8 H on reactant side to balance the charge.
By arvind Arora
Add 4 H2O on product side to balance H atoms.
Step 3
Balance the charge using the medium given.
+
Acidic Medium : H
–
Alkaline/Basic Medium: OH
Applying Oxidation Number Method

+ − + + +
5 Fe2 (aq) + MnO4 (aq) + 8 H (aq) 5 Fe3 (aq) + Mn2 (aq) + 4 H2O (l)

The reaction is balanced in terms of:

• Atoms
• Charge
• Electrons Exchanged By arvind Arora
 Half-Reaction Method – Steps
Ion-Electron Method
Step 1
Separate half-reactions and balance the
atoms. Balance H and O atoms using H2O
+ –
and H /OH depending upon medium.
Step 2
Balance the charges by marking loss/gain of
electrons. By arvind Arora
Step 3
Combine the half-reactions by balancing
electrons lost with electrons gained.
Balancing of H and O Atoms

Acidic Medium
H Atom : Add H+ to the side lesser in H.
O Atom : Add H2O to the side lesser in O
+
and 2 H to the other side.
Basic Medium
H Atom : Add H2O to theBy sidearvind
lesser in H
Arora
−
and OH to the other side.
O Atom : Add 2 OH− to the side lesser in
O and H2O to the other side.
Applying Half-Reaction Method

Ex-1
S 2 O3 2 + I2 S 4 O6 2 + I
− − −

By arvind Arora
Applying Half-Reaction Method Separate the Half-Reactions
S 2 O3 2 + I2 S 4 O6 2 + I
− − −
2 2
S 2 O3 S 4 O6
− −
I2 I
−

By arvind Arora

Step 1
Separate half-reactions and balance the
atoms. Balance H and O atoms using H2O
+ –
and H /OH depending upon medium.
Applying Half-Reaction Method
S 2 O3 2 + I2 S 4 O6 2 + I
− − −
2 S 2 O3 2 S 4 O6 2
− −
I2 I
−
Balance S and O atoms.
By arvind Arora

Step 1
Separate half-reactions and balance the
atoms. Balance H and O atoms using H2O
+ –
and H /OH depending upon medium.
Applying Half-Reaction Method
S 2 O3 2 + I2 S 4 O6 2 + I
− − −
2 S 2 O3 2− S 4 O6 2
−
I2 2I
−
Balance I atoms.
By arvind Arora

Step 1
Separate half-reactions and balance the
atoms. Balance H and O atoms using H2O
+ –
and H /OH depending upon medium.
Applying Half-Reaction Method
S 2 O3 2 + I2 S 4 O6 2 + I
− − −
2 S 2 O3 2− S 4 O6 2 + 2 O.H.
− −
I2 2I e
−
Reactant Side : 2 × (2−) = 4−
Product Side : 1 × (2−) By
= 2−arvind Arora
−
Add 2e to the product side. This is Oxidation Half (O.H.)
Step 2
Balance the charges by marking loss/gain of
electrons.
Applying Half-Reaction Method
S 2 O3 2 + I2 S 4 O6 2 + I
− − −
2 S 2 O3 2− S 4 O6 2 + 2 O.H.
− −
2 + I2 2I e R.H.
− −
e
Reactant Side : 1 × (0) = 0
Product Side : 2 × (1−) =By
2−arvind Arora
−
Add 2e to the reactant side. This is Reduction Half (R.H.)
Step 2
Balance the charges by marking loss/gain of
electrons.
Applying Half-Reaction Method
S 2 O3 2 + I2 S 4 O6 2 + I
− − −
2 S 2 O3 2− S 4 O6 2 + 2 O.H.
− −
2 + I2 2I e R.H.
− −
e

By are
Since electrons lost and gained arvind
equal,Arora
add O.H. and R.H.
Step 3
Combine the half-reactions by balancing
electrons lost with electrons gained.
Applying Half-Reaction Method

2 S 2 O3 2− + I2 S 4 O6 2 + 2
− −
I
The reaction is balanced in terms of:
• Atoms
• Charge
• Electrons Exchanged By arvind Arora
Balancing – Disproportionation Reactions – Example

Cl2 + Cl2 ClO + Cl Alkaline Medium

− −

By arvind Arora
 Determining EW in a Redox Reaction
Equivalent Weight is determined by using z factor. It is defined
as the number of electrons lost/gained per molecule of RA/OA.

Molecular Weight
Equivalent Weight =
Valency Factor
MW
EW = z By arvind Arora
Half-Reactions will be analyzed for determining EW

Method used : Half-Reaction Method

• EW of Important OA and RA
• KMnO4, K2Cr2O7, H2C2O4, H2O2, Na2S2O3

By arvind Arora
KMnO4 MnO4– changes to Mn2
+
EW depends on Medium
MW
Acidic Medium EW =
5

5 + 8H
+ + MnO4– Mn2
+ + 4H O
2
−
e 4 H O on product side.
Add 2
Add 8 H on reactant side. By arvind Arora
+
Reactant Side : 8 × (1+) + 1 × (1−) = 7+
Product Side : 1 × (2+) + 4 × (0) = 2+
−
Add 5e to the reactant side.
KMnO4 MnO4– changes to MnO2
MW
Neutral or Weakly Alkaline Medium EW =
3

3 + 2 H 2O + MnO4– MnO2 + 4
− −
e − OH
Add 4 OH on product side.
Add 2 H2O on reactant side.By arvind Arora
Reactant Side : 2 × (0) + 1 × (1−) = 1−
Product Side : 1 × (0) + 4 × (1−) = 4−
−
Add 3e to the reactant side.
KMnO4 MnO4– changes to MnO42–
MW
Strongly Alkaline Medium EW =
1

1 + MnO4– MnO42–
−
e
Reactant Side : 1 × (1−) = 1−
Product Side : 1 × (2−) = 2−By arvind Arora
−
Add 1e to the reactant side.
KMnO4 B A N
1 5 3
How’s My Balancing
By arvind Arora
?
K2Cr2O7 Cr2O72– changes to Cr3
+

MW
Acidic Medium EW =
6

+ 2– 2 Cr3+
6 +14 H + Cr2O7 + 7 H 2O
−
Creneeds to be balanced.
Add 7 H2O on product side. By arvind Arora
+
Add 14 H on reactant side.
Reactant Side : 14 × (1+) + 1 × (2−) = 12+
Product Side : 2 × (3+) + 7 × (0) = 6+
−
Add 6e to the reactant side.
H 2 C2 O4 H2C2O4 changes to CO2

MW
Acidic Medium EW =
2

H 2 C 2 O4 2 CO2 + 2 H+ + 2
−
C needs to be balanced. e
+
Add 2 H on product side. By arvind Arora
Reactant Side : 1 × (0) = 0
Product Side : 2 × (0) + 2 × (1+) = 2+
−
Add 2e to the product side.
H 2 C2 O4 −
C2O42 changes to CO2
MW
Basic Medium EW =
2

− 2 CO2 + 2
C 2 O4 2
−
C needs to be balanced. e
Reactant Side : 2 × (1−) = 2−By arvind Arora
Product Side : 2 × (0) = 0
−
Add 2e to the product side.
H 2 O2 H2O2 changes to O2 H2O2 as Reducing Agent

MW
Acidic Medium EW =
2

H 2 O2 O2 + 2 H+ + 2
−
+ e
Add 2 H on product side.
By arvind Arora
Reactant Side : 1 × (0) = 0
Product Side : 1 × (0) + 2 × (1+) = 2+
−
Add 2e to the product side.
H 2 O2 H2O2 changes to O2 H2O2 as Reducing Agent

MW
Basic Medium EW =
2

2 + H 2 O2 O2 + 2 H 2O + 2
− −
OH e
Add 2 H2O on product side.
Add 2 OH on reactant side.By arvind Arora
−
Reactant Side : 2 × (1−) + 1× (0) = 2−
Product Side : 1 × (0) + 2 × (0) = 0
−
Add 2e to the product side.
 − − N2S2O3 – HYPO Solution
Na2S2O3 S2O32 changes to S4O62

MW −
EW = 2e are exchanged for 2 molecules of Na2S2O3.
1 Number of electrons exchanged per molecule of Na2S2O3 = 1
2 S O 2− S 4 O6 2
− + 2
2 3
−
S and O needs to be balanced. e
By arvind Arora
Reactant Side : 2 × (2−) = 4−
Product Side : 1 × (2−) = 2−
−
Add 2e to the product side.
 VALENCY FACTOR
Valency Factor can be expressed in terms of:
a) Number of electrons exchanged per molecule of OA or RA
b) Total O.N. change per molecule of OA or RA

KMnO4 – Acidic Medium

By arvind Arora
MnO4– + 8 H+ + 5 2+ + 4 H O
Mn 2
−
+7 e +2
O.N. Change = Initial O.N. – Final O.N.
O.N. Change = (+7) – (+2) = +5
 Arvind Arora

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