Chapter 4

Oxidation-Reduction Reactions (Redox )

Origin of the Term Oxidation

Introduction

Phlogiston

The term “phlogiston” was coined by Georg Stahl in a paper published in 1718. Stahl was expanding on a concept
originated by his teacher, Joachim Becker. The phlogiston theory held that all flammable materials contain a
substance named phlogiston in addition to the other components of the material.
When nitrogen was discovered in 1772, it was referred to as phlogisticated air because it would not support
combustion nor life and when oxygen was discovered by Priestly in 1774, it was referred to as dephlogisticated air
because it could accept more phlogiston, that is, support combustion and life.
Lavoisier and Combustion
Lavoisier suggested that combustion was the combination of the flammable material with some component of the air
– namely oxygen. This theory of combustion was quickly accepted and the phlogiston theory was relegated to the
scrap heap of theories.
Review Questions
1. What would be the experimental difference between phlogisticated air and de-phlogisticated air?
 Oxidizing and Reducing Agents

Ag+(aq) + Cu(s) → Ag(s) + Cu2+(aq)

Oxidation Numbers
We use a bookkeeping system called oxidation numbers to keep track of the electrons gained and lost
during a redox reaction.

Example 1: Example 4:
What is the oxidation number of sulfur in Na2SO4? What is the oxidation number of phosphorus in the phosphate
Solution: ion, PO4−3 ?
2(Na) + 1(S) + 4(O) = 0 Solution:
2(1+) + 1(x) + 4(2-) = 0 and x = 6+ 1(P) + 4(O) = 3-
Example 2: 1(x) + 4(2-) = 3-
What is the oxidation number of chromium in K2Cr2O7? And x = 5+
Solution: Example 5:
2(K) + 2(Cr) + 7(O) = 0 What is the oxidation number of iron in Fe2O3?
2(1+) + 2(x) + 7(2-) = 0 Solution:
And x = 6+ 2(Fe) + 3(O) = 0
Example 3: 2(x) + 3(2-) = 0
What is the oxidation number of nitrogen in the nitrate ion, NO -? And x = 3+
Solution: Example 6:
1(N) + 3(O) = -1 What is the oxidation number of iron in Fe3O4?
1(x) + 3(2-) = -1 Solution:
And x = 5+ 3(Fe) + 4(O) = 0
3(x) + 4(2-) = 0
And x = 8/3
Review Questions
1. Indicate the oxidation numbers for each of the following atoms. (Beginning)
A. Mn2+
B. Al
C. Al in Al2O3
D. Br in NaBr
E. Fe in Fe2O3
F. arsenic in AsO4
G. chlorine in ClO4
H. sulfur in H2SO3
2. In the following reaction, identify the element that is being oxidized and the element that is being reduced.
MnO2 + 4 HCl → MnCl2 + Cl2 + 2 H2O
Example 9:
Balance the following redox equation KMnO4 + HCl → KCl + MnCl2 + H2O + Cl2

2 KMnO4 + 10 HCl → KCl + 2 MnCl2 + H2O + 5 Cl2

2 KMnO4 + 10 HCl → 2 KCl + 2 MnCl2 + 8 H2O + 5 Cl2

2 KMnO4 + 16 HCl → 2 KCl + 2 MnCl2 + 8 H2O + 5 Cl2

Review Questions
1. Balance the following equation using the oxidation number method. (Challenging)
HNO3 + Br2 → HBrO3 + NO2 + H2O
2. Balance the following equation using the oxidation number method. (Challenging)
Zn + HNO3 → Zn(NO3)2 + NO2 + H2O

3. In terms of electron gain and loss, explain why chlorine undergoes both oxidation and reduction in the
following unbalanced reaction. (Challenging)
Cl2 + KOH→ KCl + KClO3 + H2O
4. Balance the equation in the previous problem. (Challenging)