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UNIT 8
REDOX REACTIONS
1.CLASSICAL IDEA OF REDOX REACTIONS –OXIDATION AND REDUCTION
REACTIONS

“Oxidation”
It is the addition of oxygen/electronegative element to a substance .
It is the removal of hydrogen/electropositive element from a substance.

2 Mg + O2 → 2 MgO
Mg + F2 → MgF2
2 H2S + O2 → 2 S + 2 H2O

Reduction
It is the removal of oxygen/electronegative element from a substance
It is the addition of hydrogen/electropositive element to a substance.

2 HgO →2 Hg + O2
CH2 = CH2 + H2 → CH3 – CH3
2 FeCl3 + H2 →2 FeCl2 + 2 HCl

Redox reactions
Those reactions in which both oxidation and reduction occur simultaneously are
called redox reactions.

2.REDOX REACTIONS IN TERMS OF ELECTRON TRANSFER REACTIONS

Oxidation –It is the process that involve loss of electrons.[LEO]

2 Na→ 2 Na+ + 2e–

Reduction - It is the process that involve gain of electrons.[GER]

Cl2 + 2e– → 2 Cl–

3.MODERN CONCEPT

Oxidation: It is the process which involves an increase in the oxidation number

of the element in the given substance.
2 Na→ 2 Na+ + 2e–

Reduction: It is the process which involves a decrease in the oxidation number

of the element in the given substance.
Cl2 + 2e– → 2 Cl–

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OXIDATION NUMBER
Charge an atom appears to have when all other atoms are removed as ions in a
molecule.

Rules for the calculation of oxidation number

Rule 1: The oxidation number of an element in its free (uncombined) state is zero.
Eg- Al(s) or Zn(s).
This is also true for elements found in nature as diatomic (two-atom) elements.
.
Rule 2: The oxidation number of a monatomic (one-atom) ion is the same as the
charge on the ion, for example:
Na+ = +1 S2— = -2

Rule 3:The oxidation number of oxygen in a compound is usually –2.

Exceptions-
In peroxides (H2O2 ), oxygen has an ON of –1.
In superoxides (NaO2 )(KO2), oxygen has an ON of –1/2
If the oxygen is bonded to fluorine, O2F2 and OF2 oxygen has an ON of +1,+2 resp.

Rule 4: The oxidation state of hydrogen in a compound is usually +1.

Exceptions-
In metal hydrides then the oxidation state of hydrogen is –1.

Rule 5: The oxidation number of fluorine is always

–1. Chlorine, bromine, and iodine usually have an
oxidation number of –1, unless they’re in
combination with an oxygen or fluorine.

Rule 6: The algebraic sum of the oxidation number of all the atoms in a
compound must be zero.
The sum of all oxidation numbers in a polyatomic ion is equal to the charge on the
ion.

Rule 7: The oxidation number of a Group1[alkali metal] in a compound is +1; the

oxidation number of a Group 2 element in a compound is +2.

QUES: Calculate the oxidation number of the species which is highlighted.

1.H2SO4

2.HNO3

3.CaCO3

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4.KMnO4

5. K2CrO4

6.SO42-

Oxidising agent: The substance which can cause oxidation. The substance whose
oxidation number decreases. These reagents are called as oxidants also.

Reducing agent: The substance which can cause reduction. The substance whose
oxidation number increases. These reagents are also called as reductants.

QUES:Identify the substance oxidised, reduced, oxidising agent and reducing

agent for each of the following reactions:

CuO + H2 → Cu + H2O

4 NH3 + 5 O2 → 4NO + 6H2O

QUES:Identify the substance oxidised, reduced, oxidising agent and reducing

agent for each of the following reactions:

(a) N2 + O2 → 2 NO

(b) 2Pb(NO3)2→ 2PbO+ 2 NO2+ ½ O2

(c) 2AgBr + C6H6O2→ 2Ag + 2HBr + C6H4O2

(d) CH2O +2 Cu2+ +5OH– → Cu2O + H2CO2 + 3H2O

Stock notation.
The oxidation number state of a metal in a compound is sometimes presented
according to the notation given by German chemist, Alfred Stock.
According to this, the oxidation number is expressed by putting a Roman numeral
representing the oxidation number in parenthesis after the symbol of the metal in
the molecular formula.

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Thus aurous chloride and auric chloride are written as Au(I)Cl and Au(III)Cl3.

QUES :Using Stock notation, represent the following compounds :

1.HAuCl4

2. Tl2O

3. FeO

4. Fe2O3

5. CuI

6. CuO

7. MnO

8. MnO2.

Types of Redox Reactions

1.Combination reactions
A+B→C
C(s) + O2 (g) →CO2(g)
3Mg(s) + N2(g)→ Mg3N2(s)
2.Decomposition reactions
A→B+C
2H2O (l) →2H2 (g) + O2(g)
2NaH (s) →2Na (s) + H2(g)
3. Displacement reactions
X + YZ → XZ + Y
A. Metal displacement:
CuSO4(aq) + Zn (s) → Cu(s) + ZnSO4
B. NonMetal displacement:
2Na(s) + 2H2O(l) → 2NaOH(aq) + H2

4. Disproportionation reactions
In a disproportionation reaction an element is simultaneously oxidised and
reduced.
2H2O2 (aq) → 2H2O(l) + O2(g)
Cl2 + 2 OH– → ClO– + Cl– + H2O

QUES :Suggest a scheme of classification of the following redox reactions

1.N2 (g) + O2 (g) → 2 NO (g)

2. 2Pb(NO3)2(s) → 2PbO(s) + 2 NO2 (g) +½ O2

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3. NaH(s) + H2O(l) → NaOH(aq) + H2 (g)

4.2NO2 + 2OH– → NO2– +NO3–+H2O

Balancing of Redox Reactions

Two methods are used to balance chemical equations for redox processes.
Oxidation Number Method
Half Reaction Method
(A) BALANCING BY OXIDATION NUMBER METHOD

Step 1: Write the Skeletal ionic equation and assign the oxidation number.

Step 2: Calculate the increase or decrease in the oxidation number per atom and
make them equal. [ Make the no. of atoms equal and write equation].Ignore
oxygen and hydrogen.

Step 3 :(a) If the reaction occurs in acidic medium, add sufficient no. of H+ ions to
LHS to make charges equal.
(b) If the reaction occurs in basic medium, add sufficient no. of OH- ions to make
charges equal.

Step 4 : Count the number of hydrogen atoms and add appropriate no. of water
(H2O) molecules on the other side.
Now it will be balanced.

BALANCE THE GIVEN EQUATION BY Oxidation Number Method

1.Cr2O72–(aq) + SO32–(aq) → Cr3+(aq + SO42– (aq)
[In acidic medium]
Step 1: Write the Skeletal ionic equation and
assign the oxidation number.

Step 2: Calculate the increase or decrease in

the oxidation number per atom and make them equal. [ Make the no. of atoms
equal and write equation.]Ignore oxygen and hydrogen.

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Step 3 :If the reaction occurs in acidic medium, add sufficient no. of H+ ions to
LHS to make charges equal.

Step 4 : Count the number of hydrogen atoms and add appropriate no. of water
(H2O) molecules on the other side.

2.Permanganate ion reacts with bromide ion in basic medium to give manganese
dioxide and bromate ion. Write the balanced ionic equation for the reaction.

Step 1: Write the Skeletal ionic equation and assign the oxidation number.
MnO4–+ Br– → MnO2 + BrO3–

Step 2: Calculate the increase or decrease in the oxidation number per atom and
make them equal. [ Make the no. of atoms equal and write equation].Ignore
oxygen and hydrogen.

Step 3: If the reaction occurs in basic medium, add sufficient no. of OH- ions to
make charges equal.

Step 4 : Count the number of hydrogen atoms and add appropriate no. of water
(H2O) molecules on the other side.

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(B) BALANCING USING HALF REACTION METHOD [ION ELECTRON METHOD]

In this method, the two half equations are balanced separately and then added
together to give balanced equation.

Step 1: Write the Skeletal ionic equation and identify the oxidation and reduction
reactions.

Step 2: Separate the equation into two half reactions:

Step 3: Balance the atoms other than O and H in each half reaction individually.

Step 4: (a)For reactions occurring in acidic medium, add H2O (usually RHS)to
balance O atoms and add H+ on the other side to balance H atoms.
(b)For reactions occurring in basic medium, after step 3(a) ,add OH- Ions on both
sides.

Step 5: Add electrons to one side of the half reaction to balance the charges.
Make the number of electrons gained equal to number of electrons lost.

Step 6: Add the two half reactions to achieve the overall reaction.

BALANCE THE GIVEN EQUATION BY ION ELECTRON METHOD

1. Fe2+ + Cr2O72– → Fe3+ +Cr3+ [Acidic medium}

Step 1: Write the Skeletal ionic equation and identify the oxidation and reduction
reactions.

Step 2: Separate the equation into two half reactions:

Step 3: Balance the atoms other than O and H in each half reaction individually.

Step 4: (a)For reactions occurring in acidic medium, add H2O (usually RHS)to
balance O atoms and add H+ on the other side to balance H atoms.

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Step 5: Add electrons to one side of the half reaction to balance the charges.
Make the number of electrons gained equal to number of electrons lost.

Step 6: Add the two half reactions to achieve the overall reaction

BALANCE THE GIVEN EQUATION BY ION ELECTRON METHOD

1. [Cr(OH)4]- + H2O2→ CrO42- +H2O [Basic medium]

Step 1: Write the Skeletal ionic equation and identify the oxidation and reduction
reactions.

Step 2: Separate the equation into two half reactions:

Step 3: Balance the atoms other than O and H in each half reaction individually.

Step 4: (a)For reactions occurring in acidic medium, add H2O (usually RHS)to
balance O atoms and add H+ on the other side to balance H atoms.
(b)For reactions occurring in basic medium, after step 3(a) ,add OH- Ions on both
sides.

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Step 5: Add electrons to one side of the half reaction to balance the charges.
Make the number of electrons gained equal to number of electrons lost.

Step 6: Add the two half reactions to achieve the overall reaction

BALANCE THE GIVEN EQUATION BY ion electron Method

1.Cu + (NO3)- → Cu2+ + NO2 [Acidic]
2.SnO2 + C → Sn + CO2 [Acidic]
3. Fe2+ + H2O2 → Fe3+ + H2O [Acidic]
4.N2H4 + ClO3- →NO + Cl- [Basic]
5.MnO4- + I- → MnO2 + I2[Basic]

Redox Reactions as the Basis for Titrations

In Redox systems the titration method is used to determine the strength of a

reductant or oxidant using a redox sensitive indicator.
• In this the reagent itself is intensely coloured.There is an auto-colour change at
the end point.
Eg: Permanganate ion MnO4– which acts as a self indicator.

• If there is no dramatic auto-colour change. There are indicators which are

oxidised immediately after the last bit of the reactant is consumed, producing
a dramatic colour change. Eg: Cr2O72– which is not a self-indicator.

• In this iodine itself gives an intense blue colour with starch and has a very
specific reaction with thiosulphate (S2O32–)ions

2Cu2+(aq) + 4I–(aq) → Cu2I2(s) + I2(aq)

I2(aq) + 2 S2O32–(aq) → 2I–(aq) + S4O62–(aq)

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Redox Reactions and Electrode Processes

Daniell cell:

• Take two beakers in which one beaker contains copper sulphate solution and
the other beaker contains zinc sulphate solution.
• The solutions in two beakers are connected by a salt bridge which provides
contact between two solutions without mixing them.
• The zinc and copper rods are connected by a metallic wire with a provision for
an ammeter and a switch.
• When switch is off then no reaction takes place and no current flows through
metallic wire.

When the switch is in the on position, the following are observed:

• The transfer of electrons takes through the metallic wire connecting the two
rods but not take place directly from Zn to Cu2+
• The electricity from solution in one beaker to solution in the other beaker
flows by the migration of ions through the salt bridge.
• The flow of current is possible only if there is a potential difference between
the copper and zinc rods (electrodes). The potential associated with each
electrode is known as electrode potential.

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Standard Electrode Potential.

If the concentration of each species taking part in the electrode reaction is unity and
the reaction is carried out at 298K, then the potential of each electrode is said to be
the Standard Electrode Potential.
Standard electrode potential of hydrogen electrode= 0 volts
• A negative Standard electrode potential means that redox couple is a stronger
reducing agent than the H+/H2 couple
• A positive Standard electrode potential means that redox couple is a weaker
reducing agent than the H+/H2 couple.

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