SCHOOL OF CHEMISTRY AND PHYSICS, Westville Campus, 2021

CHEM 11O

REDOX REACTIONS

AND

BALANCING REDOX REACTIONS

IN ACIDIC AND BASIC MEDIUM

USING THE ION-ELECTRON METHOD

BY A.BISSESSUR

1|Page
 SCHOOL OF CHEMISTRY AND PHYSICS, Westville Campus, 2021

A. RULES FOR ASSIGNING OXIDATION NUMBERS

1. In free elements (that is, in the uncombined state), each atom has an
oxidation number of zero (o). Thus each atom in H2, Br2, Na, Be, K, O2 and P4
has the same oxidation number: zero

2. For ions composed of only one atom (that is monoatomic ions) the oxidation
number is equal to the charge on the ion. Thus the Li+ ion has an oxidation
number of +1, Ba2+ ion = +2, Fe3+ = +3, I- = -1, O2- = -2 and so on.

All alkali metals have an oxidation number of +1 and all alkaline earth metals
have an oxidation number of +2 in their compounds. Aluminium has an
oxidation number of +3 in all its compounds.

3. The oxidation number of oxygen in most compounds (for example MgO and
H2O) is -2 (oxide), but in hydrogen peroxide (H2O2) and in the peroxide ion (O22-),
it is -1.

4. The oxidation number of hydrogen is +1, except when it is bonded to metals in

binary compounds. In these cases (for example, LiH, NaH, CaH2 – hydrides), its
oxidation number is -1.

5. Fluorine has an oxidation number of -1 in all its compounds. Other halogens (Cl,
Br, I) have negative oxidation numbers when they occur as halide ions in their
compounds. When combined with oxygen – for example in oxoacids and
oxoanions-they have positive oxidation numbers for example OCl-, OBr-.

6. In neutral molecules, the sum of the oxidation numbers of all the atoms must
be zero. In a polyatomic ion, the sum of oxidation numbers of all the elements in
the ion must be equal to the net charge of the ion. For example, in the ammonium
ion NH4+, the oxidation number of N=-3 and that of H = +1. Thus the sum of the
oxidation numbers is -3 + 4(+1) = +1, which is equal to the net charge of the
ion.

7. Oxidation numbers do not have to be integers. For example, the oxidation

number of O in superoxide, O = -½ .
2-

2|Page
 SCHOOL OF CHEMISTRY AND PHYSICS, Westville Campus, 2021

8. PRACTICE EXERCISE

Give the oxidation states of the underlined atoms in the following compounds:

a) BaCrO4 b) Hg2I2 c) NaOCl d) NaBH4 e) Cu2S f) Ca(HSO3)2

g) Na2O2 h) Ag2(CrO4) i) NO3- j) SO32- k) N2O5 l) Na2C2O4

3|Page
 SCHOOL OF CHEMISTRY AND PHYSICS, Westville Campus, 2021

2. STEPS IN BALANCING EQUATIONS IN REDOX REACTIONS

Step 1 Write unbalanced equations for the reaction in ionic

form

Step 2 Write two ½ cell reactions

Oxidation and reduction half reactions

Step 3 Carry out mass balance, that is, balance all atoms
other than O and H in each ½ reaction
Step 4 Balance O and H atoms in each ½ reaction

(follow rules in acidic and basic medium)

Step 5 Carry out charge balance by adding electrons

Step 6 Normalise the number of electrons in both ½

reactions

Step 7 Add the two ½ reactions

Cancel electrons on opposite sides of each ½ reaction
Cancel H2O and O on opposite sides
Add H2O and O on the same side of ½ reactions

Step 8 Write the overall balanced equation

4|Page
 SCHOOL OF CHEMISTRY AND PHYSICS, Westville Campus, 2021

3. Rules applied to balancing Redox Equations

(a) In Acidic medium

For deficient O atoms,

Add 1H2O to the side deficient in O

Add 2H+ to the opposite side

For example: C2O42- → CO2

(2H+ → H2O) – acidic medium rule

4H+ + C2O42- → CO2 + 2H2O

(b) In Basic medium

Add 2 OH- to the side deficient in O

Add 1 H2O to the opposite side

For example: MnO4- → MnO2

(1H2O → 2OH-) – basic medium rule

2H2O + MnO4- → MnO2 + 4OH-

5|Page
 SCHOOL OF CHEMISTRY AND PHYSICS, Westville Campus, 2021

4. Balancing a Redox Reaction in Acidic Medium by the Ion-Electron

Method

Example 1.

Step 1. Write the overall unbalanced equation

Fe2+(aq) + Cr2O72-(aq) → Fe3+(aq) + Cr3+(aq)

Step2. Write equations for the two ½ reactions

Oxidation ½ rxn: Fe2+(aq) → Fe3+(aq)

Reduction ½ rxn: Cr2O72-(aq) + e- → Cr3+(aq)

Step 3. Mass balance other than O and H

Fe2+(aq) → Fe3+(aq)

Cr2O72-(aq) → 2Cr3+(aq)

Step 4. Balance O and H atoms

Fe2+(aq) → Fe3+(aq)

14H+ + Cr2O72-(aq) → 2Cr3+(aq) + 7H2O

Step 5. Charge Balance

Fe2+(aq) → Fe3+(aq) + e-

14H+ + Cr2O72-(aq) + 6e- → 2Cr3+(aq) + 7H2O

6|Page
 SCHOOL OF CHEMISTRY AND PHYSICS, Westville Campus, 2021

Step 6. Normalise number of electrons

6Fe2+(aq) → 6Fe3+(aq) + 6e-

14H+ + Cr2O72-(aq) + 6e- → 2Cr3+(aq) + 7H2O

Step 7. Normalising O, H and H2O

6Fe2+(aq) → 6Fe3+(aq)+ 6e-

14H+ + Cr2O72-(aq) + 6e- → 2Cr3+(aq) + 7H2O

Step 8. Overall Balanced Equation

14H+ + Cr2O72-(aq) + 6Fe2+(aq) → 2Cr3+(aq) + 6Fe3+(aq)+ 7H2O

NOTE:

1. Cancel H2O’s; H’s and OH-‘s on both sides of the ½ rxns

For example:

3H2O + Fe2+(aq) → Fe3+(aq)+ 6e- + 6H+

14H+ + Cr2O72-(aq) + 6e- → 2Cr3+(aq) + 7H2O

8 4

2. Writing ½ rxns from a single reactant

KClO3(s) → KCl(s) + O2(g)

KClO3(s) → KCl(s) – reduction ½ rxn

KClO3(s) → O2(g) - oxidation ½ rxn

5. Practice Exercise

7|Page
 SCHOOL OF CHEMISTRY AND PHYSICS, Westville Campus, 2021

Balancing the following redox reactions in Acidic Medium by the Ion-Electron

Method

1. MnO4- + Br- → Mn2+ + Br2

2. Cr2O72- + 6S2O32- + 14H+ → 2Cr3+ + 3S4O62- + 7H2O

3. Fe2+(aq) + MnO4-(aq) → Fe3+(aq) + Mn2+(aq)

4. H2O2(aq) + Fe2+(aq) →Fe3+(aq) + H2O(ℓ)

5. Cu(s) + HNO3(aq) →Cu2+(aq) + NO(g) + H2O(ℓ)

6. ClO3-(aq) + Cl-(aq) → Cl2(g) + ClO2(g)

8|Page
 SCHOOL OF CHEMISTRY AND PHYSICS, Westville Campus, 2021

6. Balancing a Redox Reaction in Basic Medium by the Ion-Electron Method

Example 1.

Step 1. Write the overall unbalanced equation

MnO4- (aq) + I-(aq) → MnO2(s) + I2(s)

Step2. Write equations for the two ½ reactions

Oxidation ½ rxn: I-(aq) → I2(s)

Reduction ½ rxn: MnO4- (aq) → MnO2(s)

Step 3. Mass balance other than O and H

Oxidation ½ rxn: 2I-(aq) → I2(s)

Reduction ½ rxn: MnO4- (aq) → MnO2(s)

Step 4. Balance O and H atoms

Oxidation ½ rxn: 2I-(aq) → I2(s)

Reduction ½ rxn: 2H2O(ℓ) + MnO4- (aq) → MnO2(s) + 4OH-

Step 5. Charge balance

Oxidation ½ rxn: 2I-(aq) → I2(s) + 2e-

Reduction ½ rxn: 2H2O(ℓ) + MnO4- (aq) + 3e- → MnO2(s) + 4OH-

9|Page
 SCHOOL OF CHEMISTRY AND PHYSICS, Westville Campus, 2021

Step 6. Normalise number of electrons

Oxidation ½ rxn: 2I-(aq) → I2(s) + 2e- ( x 3)

Reduction ½ rxn: 2H2O(ℓ) + MnO4- (aq) + 3e- → MnO2(s) + 4OH- ( x 2)

Step 7. Normalising O, H and H2O

Oxidation ½ rxn: 6I-(aq) → 3I2(s) + 6e-

Reduction ½ rxn: 4H2O(ℓ) + 2MnO4- (aq) + 6e- → 4MnO2(s) + 8OH-

Step 8. Overall Balanced Equation in basic medium

6I-(aq) + 4H2O(ℓ) + 2MnO4- (aq) → 4MnO2(s) + 8OH- + 3I2(s)

10 | P a g e
 SCHOOL OF CHEMISTRY AND PHYSICS, Westville Campus, 2021

Example 2.

Balance the following reaction in basic medium by the ion-electron method, show all relevant
steps.

(5)

MnO4-(aq) + Br-(aq) → MnO2(s) + BrO3-(aq)

Redox ½ rxns:

Oxidn ½ rxn: Br-(aq) → BrO3-(aq)

Reduction ½ rxn: MnO4-(aq)) → MnO2(s)

Balancing atoms other than H and O

Br-(aq) → BrO3-(aq)

MnO4-(aq)) → MnO2(s)

Balancing H and O atoms

6OH-(aq) + Br-(aq) → BrO3-(aq) + 3H2O(ℓ) + 6e-

2H2O(ℓ) + MnO4-(aq) + 3e- → MnO2(s) + 4OH-(aq) x2

Charge balance

6OH-(aq) + Br-(aq) → BrO3-(aq) + 3H2O(ℓ) + 6e-

4 1H2O(ℓ) + 2MnO4-(aq) + 6e- → 2MnO2(s) + 8 2OH-(aq)

Overall balanced equation

Br-(aq) + H2O(ℓ) + 2MnO4-(aq) → 2MnO2(s) + 2OH-(aq) + BrO3-(aq)

11 | P a g e
 SCHOOL OF CHEMISTRY AND PHYSICS, Westville Campus, 2021

7. Practice Exercise

Balancing the following Redox Rxns in Basic Medium by the Ion-Electron Method

1. CN- + Fe3+ → CNO- + Fe2+

2. Mn2+(aq) + H2O2(aq) → MnO2(s) + H2O(ℓ)

3. CN-(aq) + MnO4-(aq) → CNO-(aq) + MnO2(s)

4. Br2(ℓ) → BrO3-(aq) + Br-(aq)

12 | P a g e