Balancing Simple Oxidation–Reduction (Redox) Equations

Redox reactions do not deviate from the law of conservation of matter. Just as atoms are neither created nor destroyed in a
chemical reaction, so also, charges are conserved in a redox reaction.
Sometimes, the medium (acid solution or basic solution) in which the redox reaction is taking place is not explicitly stated. If
an acid or base is one of the reactants or products, the solution or medium is the same. If ammonia is present, it is acidic. If
metals which would form insoluble hydroxides are shown in their ionic form, the solution is acidic.
Example
State whether each of the following equations should be balanced in acid or basic solution:
(a) HNO3 + Fe2+ → Fe3+ + NO2
(b) NH3 + MnO4- → MnO2 + NO2
(c) Fe3+ + H2O2 → Fe2+ + O2
(d) Cr(OH)2 + I2 → Cr(OH)3 + 2I-

Methods used in Balancing Redox Equations

There are many ways to balance redox equations systematically but the two most commonly used are:
(A) Half-cell Reaction (Ion-Electron) Method
(B) Oxidation-State Method
 (A) Balancing Redox Equations Using Half-Cell Reaction Method
1. Write down the half-equations to show the species reduced or oxidized and the products formed.
2. Balance all atoms (except oxygen) on the LHS and RHS of the half-equations.
3. For reactions taking place in an acidic medium, determine the difference in the number of oxygen atom present on the left
and right hand sides of the half-equations; represent the difference in oxygen with H2O on the side with minimum oxygen
atom and balance up with H+ on the other side.
4. For reactions taking place in an alkaline medium, represent the difference in oxygen atoms with H2O on the side with the
maximum oxygen atom and balance up with OH- on the other side.
5. Balance with respect to charges by adding an appropriate number of electrons.
6. Balance the half-equations such that the number of electrons lost equals the number of electrons gained.
7. Add the half-equations together cancelling out species that appear unchanged on both sides of the equation.
Example I
1. Balance the following redox equations/reactions in acidic solution:
(a) C2O42-(aq) + MnO4-(aq) → Mn2+(aq) + CO2(g)
(b) KMnO4(aq) + FeSO4(aq) → MnSO4(aq) + Fe2(SO4)3(aq) + K2SO4(aq)

Solution:
(a) For C2O42- + MnO4- → Mn2+ + CO2,
Oxidation: C2O42- → CO2,
Reduction: MnO4- → Mn2+
Now, C2O42- → 2CO2 + 2e- --------(1)
MnO4- + 8H+ + 5e- → Mn2+ + 4H2O --------(2)
(1) x 5: 5C2O42- → 10CO2 + 10e- -------(3)
(2) x 2: 2MnO4- + 16H+ + 10e- → 2Mn2+ + 8H2O --------(4)
(3) + (4): 5C2O42- + 2MnO4- + 16H+ → 2Mn2+ + 10CO2 + 8H2O.
(b) KMnO4 + FeSO4 → MnSO4 + Fe2(SO4)3 + K2SO4
i.e. K+ + MnO4- + Fe2+ + SO42- → Mn2+ + SO42- + 2Fe3+ + 3SO42- + 2K+ + SO42-
Thus, K+ and SO42- are spectator ions.
Hence, the equation becomes: MnO4- + Fe2+ → Mn2+ + Fe3
Oxidation: Fe2+→ Fe3+
Reduction: MnO4- → Mn2+
Now,
Fe2+ → Fe3+ + e- -------(1)
MnO4- + 8H+ + 5e- → Mn2+ + 4H2O -------(2)
(1) x 5: 5Fe2+ → 5Fe3+ + 5e- ---- (3)
(2) x 1: MnO4- + 8H+ + 5e- → Mn2+ + 4H2O ------(4)
(3) + (4): MnO4- + 5Fe2+ + 8H+ → Mn2+ + 5Fe3+ + 4H2O
Written in terms of the original equation, we have:
2MnO4- + 10Fe2+ + 16H+ → Mn2+ + 10Fe3+ + 8H2O
i.e. 2KMnO4 + 10FeSO4 + → 2MnSO4 + 5Fe2(SO4)3 + K2SO4+ 8H2O

Example II
Balance the following redox reactions in a basic medium
1. N2O4(g) + Br-(aq) → NO2- + BrO3-
2. CN- + MnO4- → CNO- + MnO2
Solution
1. N2O4 + Br- → NO2- + BrO3-
Reduction: N2O4 → NO2-
Oxidation: Br- → BrO3-
Now,
N2O4 + 2e- → 2NO2- ------- (1)
Br- + 6OH- → BrO3- + 3H2O + 6e- ------ (2)
(1) x 3: 3N2O4 + 6e- → 6NO2- -------- (3)
(2) + (3): 3N2O4 + Br- + 6OH- → 6NO2- + BrO3- + 3H2O

2. CN- + MnO4- → CNO- + MnO2

Oxidation: CN- → CNO-
Reduction: MnO4- + MnO2
Now,
CN- + 2OH- → CNO- + H2O + 2e- ------ (1)
MnO4- + 2H2O + 3e- → MnO2 + 4OH- ------- (2)
(1) x 3: 3CN- + 6OH- → 3CNO- + 3H2O + 6e- ------- (3)
(2) x 2: 2MnO4- + 4H2O + 6e- → 2MnO2 + 8OH- --- (4)
(3) + (4): 3CN- +2MnO4- + 6OH- + 4H2O → 3CNO- + 2MNO2 + 8OH- + 3H2O
:- 3CN- +2MnO4- + H2O → 3CNO- + 2MnO2 + 2OH-

Exercise
1. Balance the following redox reactions in acidic medium using the half-reaction method
(a) Cu(s) + NO3-(aq) → Cu2+(aq) + NO(g)
(b) Cr2O72-(aq) + Cl-(aq) → Cr3+(aq) + Cl2(g)
(c) Br-(aq) + MnO4-(aq) → Br2(l) + Mn2+(aq)
2. Balance the following redox reactions in basic solution using the half-reaction method
(a) Al(s) + MnO4-(aq) → MnO2(s) + Al(OH)4-(aq)
(b) Cl2(g) → Cl-(aq) + ClO-(aq)
(c) NO2-(aq) + Al(s) → NH3(g) + AlO2-(aq)