Chapter 8

REDOX REACTIONS
 Oxidation and Reduction (Redox)

• Early chemists saw “oxidation”

reactions only as the combination of
a material with oxygen to produce
an oxide.
• For example, when carbon burns
in air, it is oxidised and forms
oxides of carbon
Oxidation and Reduction (Redox)
• A process called “reduction” is the opposite
of oxidation, and originally meant the loss of
oxygen from a compound
• Oxidation and reduction always occur
simultaneously and hence called REDOX
REACTION
• The substance gaining oxygen is oxidized,
while the substance losing oxygen is
reduced.
 Oxidation and Reduction (Redox)
• Today, many of these reactions may
not even involve oxygen
• Redox currently says that electrons are
transferred between reactants
• Mg + S→ Mg2+ + S2- (MgS)

•The magnesium atom (which has zero charge) changes to a

magnesium ion by losing 2 electrons, and is oxidized to Mg2+
•The sulfur atom (which has no charge) is changed to a sulfide
ion by gaining 2 electrons, and is reduced to S2-
Oxidation and Reduction (Redox)

Each sodium atom loses one electron:

Each chlorine atom gains one electron:

LEO says GER :

Lose Electrons = Oxidation

Sodium is oxidized

Gain Electrons = Reduction

Chlorine is reduced
“Oxidation-Reduction Reactions”

LEO says GER

LEO says GER :
- Losing electrons is oxidation, and the
substance that loses the electrons is
called the reducing agent.
- Gaining electrons is reduction, and the
substance that gains the electrons is
called the oxidizing agent.
Mg is the Mg is oxidized: loses e-, becomes a Mg2+ ion
reducing
agent
Mg(s) + S(s) → MgS(s)
S is the oxidizing agent S is reduced: gains e- = S2- ion
 Assigning Oxidation Numbers
• An “oxidation number” is a positive or
negative number assigned to an atom
to indicate its degree of oxidation or
reduction.
• Generally, a bonded atom’s oxidation
number is the charge it would have if
the electrons in the bond were
assigned to the atom of the more
electronegative element
 Rules for Assigning Oxidation Numbers
1) The oxidation number of any
uncombined element is zero.

2) The oxidation number of a

monatomic ion equals its charge.
 Rules for Assigning Oxidation Numbers
3) The oxidation number of oxygen in
compounds is -2, except in peroxides,
such as H2O2 where it is -1.
4) The oxidation number of hydrogen and
alkalimetals in compounds is +1, except in
metal hydrides, like NaH, where it is -1.
In all its compounds, fluorine has an oxidation
number of –1. Other halogens (Cl, Br, and I)
also have an oxidation number of –1 in most
of the compounds
 Rules for Assigning Oxidation Numbers

5) The sum of the oxidation numbers of the

atoms in the compound must equal 0.

2(+1) + (-2) = 0 (+2) + 2(-2) + 2(+1) = 0

H O Ca O H
 Rules for Assigning Oxidation Numbers
6) The sum of the oxidation numbers in
the formula of a polyatomic ion is equal
to its ionic charge.

X + 3(-2) = -1 X + 4(-2) = -2
N O S O

thus X = +5 thus X = +6
 Reducing Agents and Oxidizing Agents
•An increase in oxidation number = oxidation
• A reduction in oxidation number = reduction

Sodium is oxidized – it is the reducing agent

Chlorine is reduced – it is the oxidizing agent

 Types of
Redox Reactions
 Combination reactions
⚫ A combination reaction may be denoted as
⚫A+B→C
⚫ C+O2 → CO2
⚫ Oxidation : C (ON 0 to +4) Reducing Agent
⚫ Reduction : O2 (ON 0 to -2) Oxidising agent
⚫ 3Mg+N2 → Mg3N2
⚫ Oxidation : Mg (ON 0 to +2) Reducing Agent
⚫ Reduction : N2 (ON 0 to -3) Oxidising agent
 Decomposition reactions
⚫ A decomposition reaction leads to the
breakdown of a compound into two or more
components.
⚫ 2H2O →2H2 + O2
⚫ Oxidation : O2 (ON -2 to 0) Reducing Agent
⚫ Reduction : H2 (ON +1 to 0) Oxidising agent
⚫ 2NaH →2Na+ H2
⚫ Oxidation : H2 (ON -1 to 0) Reducing Agent
⚫ Reduction : Na (ON +1 to 0) Oxidising agent
 Displacement reactions
⚫ CuSO4 + Zn → Cu + ZnSO4
⚫ Oxidation : Zn (ON 0 to +2) Reducing Agent
⚫ Reduction : Cu (ON +2 to 0) Oxidising agent
⚫ S and O no oxidation and reduction.
⚫ Cr2O3 + 2 Al → Al2O3 + 2Cr
⚫ Oxidation : Al (ON 0 to +3) Reducing Agent
⚫ Reduction : Cr (ON +3 to 0) Oxidising agent
⚫ O - no oxidation and reduction.
⚫ 2Na + 2H2O → 2NaOH + H2
⚫ Oxidation : Na (ON 0 to +1) Reducing Agent
⚫ Reduction : H (ON +1 to 0) Oxidising agent
⚫ O (one H) - no oxidation and reduction.
⚫ 2Fe + 3H2O → Fe2O3+ 3H2
⚫ Oxidation : Fe (ON 0 to +3) Reducing Agent
⚫ Reduction : H (ON +1 to 0) Oxidising agent
⚫ O - no oxidation and reduction.
⚫ Fe + 2HCl → FeCl2+ H2
⚫ Oxidation : Fe (ON 0 to +2) Reducing Agent
⚫ Reduction : H (ON +1 to 0) Oxidising agent
⚫ Cl- no oxidation and reduction.
⚫ Br2 + 2I – → 2Br– + I2
⚫ Oxidation : I (ON -1 to 0) Reducing Agent
⚫ Reduction : Br (ON 0 to -1) Oxidising agent
 Disproportionation reactions
⚫ In a disproportionation reaction an element in
one oxidation state is simultaneously oxidised
and reduced.
⚫ 2H2O2 → 2H2O+ O2
⚫ Oxidation : O (ON -1 to 0) Reducing Agent
⚫ Reduction : O (ON -1 to -2) Oxidising agent
⚫ H- no oxidation and reduction.
Balancing of Redox Reactions
Two methods are used to balance chemical
equations for redox processes. They are
⚫ Oxidation Number Method
⚫ Half Reaction Method
 Oxidation Number Method
⚫ Step 1: Write the correct formula for each
reactant and product.
⚫ Step 2: Identify atoms which undergo change
in oxidation number in the reaction by
assigning the oxidation number to all elements
in the reaction.
⚫ Step 3: Calculate the increase or decrease in
the oxidation number per atom and for the
entire molecule/ion in which it occurs. If these
are not equal then multiply by suitable
coefficients so that these become equal.
⚫ Step 4: Ascertain the involvement of ions if the
reaction is taking place in water, add H+ or OH–
ions to the expression on the appropriate side
so that the total ionic charges of reactants and
products are equal.
⚫ Step 5 : Make the numbers of hydrogen atoms
in the expression on the two sides equal by
adding water (H2O) molecules to the reactants
or products. Now, also check the number of
oxygen atoms. If there are the same number of
oxygen atoms in the reactants and products, the
equation then represents the balanced redox
reaction.
Example
⚫ Write the net ionic equation for the reaction of
potassium dichromate(VI), K2Cr2O7 with
sodium sulphite, Na2SO3, in an acid solution to
give chromium(III) ion and the sulphate ion.
⚫ Step 1: chemical equation
⚫ Cr2O7 2–(aq) + SO32–(aq) → Cr3+(aq)+ SO42–(aq)
⚫ Step 2: assign oxidation numbers
⚫ +6 -2 +4 -2 +3 +6 -2
⚫ Cr2O7 2–(aq) + SO32–(aq) → Cr3+(aq)+ SO42–(aq)
⚫ Step 3: Calculate the increase and decrease of
oxidation number, and make them equal
⚫ +6 -2 +4 -2 +3 +6 -2
⚫ Cr2O7 2–(aq) +3 SO32–(aq) → 2Cr3+(aq)+ 3SO42–(aq)
Step 4: As the reaction occurs in the acidic
medium, and further the ionic charges are not
equal on both the sides, add 8H+ on the left to
make ionic charges equal.
Cr2O7 2–(aq)+3SO32–(aq) +8H+→2Cr3+(aq)+ 3SO42–(aq)
Step 5:Finally, count the hydrogen atoms, and add
appropriate number of water molecules (4H2O)
on the right to achieve balanced redox change.
Cr2O7 2–(aq)+3SO32–(aq) +8H+→
2Cr3+(aq)+ 3SO42–(aq) +4H2O
 Half Reaction Method
⚫ Step 1: Produce unbalanced equation for the
reaction in ionic form :
⚫ Fe2+(aq) +Cr2O7 2–(aq) → Cr3+(aq)+ Fe3+(aq)
⚫ Step 2: Separate the equation into half reactions:
⚫ Oxidation half Fe2+(aq) → Fe3+(aq)
⚫ Reduction half
⚫ +6 +3
⚫ Cr2O7 (aq) → Cr3+(aq)
2–
⚫ Step 3: Balance the atoms other than O and H
in each half reaction individually.
⚫ Fe2+(aq) → Fe3+(aq)
⚫ Cr2O7 2–(aq) → 2 Cr3+(aq)
⚫ Step 4: For reactions occurring in acidic
medium, add H2O to balance O atoms and H+
to balance H atoms.
⚫ Cr2O7 2–(aq) +14H+(aq)→ 2 Cr3+(aq) + 7 H2O(l)
⚫ Step 5: Add electrons to one side of the half
reaction to balance the charges.
⚫ Fe2+(aq) → Fe3+(aq)
⚫ Fe2+(aq) → Fe3+(aq) + e-
⚫ Cr2O7 2–(aq) +14H+(aq) → 2 Cr3+(aq) + 7H2O(l)
⚫ Cr2O7 2–(aq) +14H+(aq) +6e- → 2 Cr3+(aq) + 7H2O(l)
⚫ To equalise the number of electrons in both the
half reactions, we multiply the oxidation half
reaction by 6
⚫ 6Fe2+(aq) → 6Fe3+(aq) + 6e-
⚫ Step 6: We add the two half reactions to
achieve the overall reaction and cancel the
electrons on each side.
⚫ 6Fe2+(aq) + Cr2O7 2–(aq) +14H+(aq) →
6Fe3+(aq) +2 Cr3+(aq) + 7H2O(l)

⚫ Step 7: Verify that the equation contains the

same type and number of atoms and the same
charges on both sides of the equation.
 Redox Reactions as the Basis
for Titrations
⚫ In redox titrations, 3 types of indicators are used.
⚫ Type1: self-indicators: Here the reagent itself
acts as indicator. (e.g. KMnO4)
⚫ Type 2: Second type is not a self-indicator, but
oxidises the indicator substance diphenylamine
just after the equivalence point to produce an
intense blue colour, thus signalling the end point.
(Cr2O72–)
⚫ Type 3: On addition of starch after the
liberation of iodine from the reaction of Cu2+
ions on iodide ions, an intense blue colour
appears. This colour disappears as soon as the
iodine is consumed by the thiosulphate ions.
Limitations of Concept of
Oxidation Number
⚫ Oxidation process is now visualised as
decrease in electron density and reduction
process as an increase in electron density
around the atom(s) involved in the reaction.
REDOX REACTIONS AND
ELECTRODE PROCESSES
 Galvanic Cells
anode cathode
oxidatio reductio
n n

spontaneous
redox reaction
Galvanic cells
Cu 2+ + 2e– → Cu (s) (reduction half reaction)
Zn (s) → Zn 2+ + 2e– (oxidation half reaction)

Zn (s) + Cu 2+ (aq) → Zn 2+ (aq) + Cu (s)

cell reaction
⚫ The potential associated with each electrode is
known as electrode potential. If the
concentration of each species taking part in the
electrode reaction is unity (if any gas appears in
the electrode reaction, it is confined to 1
atmospheric pressure) and further the reaction
is carried out at 298K, then the potential of
each electrode is said to be the Standard
Electrode Potential.