LESSON 9:

REDOX Reactions
OXIDATION STATES
 The concept of oxidation states (also called oxidation numbers) provides a way
to keep track of electrons in oxidation–reduction reactions, particularly redox
reactions involving covalent substances.
 The rules for assigning oxidation states are summarized in the table.
Element by itself: 0 Ex: Na(s), O2(g), Hg(l)
Gr. IA: Always +1
Gr. IIA: Always +2
Halogens: usually -1
Monoatomic ion: charge of ion Ex: Na+, Cl-
Fluorine: always -1 Ex: HF, PF3
Oxygen: usually -2 Ex: CO2. H2O, H2O2
-1 in peroxides (O2 )
2-

Hydrogen: +1 with non-metals Ex: CH4 , HCl

-1 with metals

 Application of these simple rules allows the assignment of oxidation states in

most compounds. To apply these rules, recognize that the sum of the
oxidation states must be zero for an electrically neutral compound. For an
ion, the sum of the oxidation states must equal the charge of the ion.
 Chemical reaction in which the oxidation state of one or more substances
changes are called oxidation-reduction reactions (or redox reactions)
 Oxidation is an increase in oxidation state or oxidation number (a loss of
electrons).
 Reduction is a decrease in oxidation state (a gain of electrons). Consider
the oxidation states in this reaction,
0 0 +1 -1 LE O RA: Loss of Electron, Oxidation,
2Na(s) + Cl2(g) →2NaCl(s)Reducing Agent
GE R OA: Gain of Electron, Reduction,
 The oxidation states of sodium changes from 0 to +1 (increased) and chlorine
changes from 0 to -1(decrease). Sodium is oxidized and chlorine is reduced. In
addition, Cl2 is called the oxidizing agent (electron acceptor), and Na is called
the reducing agent (electron donor).
I. ASSIGNING THE OXIDATION NUMBER
For example,
 1. Assign the oxidation number for CO2
 The oxidation state of oxygen is -2. The oxidation state of the carbon atom
can be determined by recognizing that since CO2 has no charge, the sum of
the oxidation states for oxygen and carbon must be zero. Since each oxygen
is -2 and there are two oxygen atoms, the carbon atom must be assigned an
oxidation state of +4:
 We can check the C+4O-22 assigned oxidation states by noting that when the
number of atoms is taken into account, the sum is zero as required:
(1 atom of C) (+4) + (2atoms of O) (-2) = 0
2. Assign oxidation number for SF6
 Since we have no rule for sulfur, we first assign the oxidation state of each
fluorine as -1. The sulfur must then be assigned an oxidation state of +6 to
balance the total of -6 S+6F-16 from the fluorine atoms:
Reality Check: +6 + 6(-1) = 0
3. Assign oxidation number for NO3-
 Oxygen has an oxidation state of -2. Because the sum of the oxidation
states of the three oxygens is -6 and the net charge on the NO 3- ion is 1-, the
nitrogen N+5O-23- must have an oxidation state of +5:
Reality Check: +5 + 3(-2) = -1
For oxidation–reduction reactions that occur in aqueous solution, it is useful to
separate the reaction into two half-reactions: one involving oxidation and the other
involving reduction.
II. DETERMINING WHICH REACTANT HAS OXIDIZED, REDUCED,
OXIDIZING AGENT AND REDUCING AGENT
Let’s take another example.
Cu(s) + 2NO3-(aq) + 4H3O+(aq) → Cu2+(aq) + 2NO2(g) + H2O(l)
Assign the oxidation number by applying the rules.
0 +5-2 +1 -2 +2 +4-2 +1 -2
Cu(s) + 2NO + 4H3O → Cu
-
3 (aq) + 2NO2(g) + H2O(l)
+
(aq)
2+
(aq)
Determine which atom has a change in oxidation state after the reaction. In
this case, Copper has oxidized (O.N. from 0 to +2) and Nitrogen has reduced
(O.N. from +5 to +4).

0 +5-2 +1 -2 +2 +4-2 +1 -2
Cu(s) + 2NO -
3 (aq) + 4H3O +
(aq) → Cu 2+
(aq) + 2NO2(g) + H2O(l)
Reduced Oxidized
Oxidizin Reducing
g Agent Agent
IDENTIFYING THE REDUCTION AND OXIDATION REACTION
For example, consider the unbalanced equation for the oxidation–reduction reaction
between cerium (IV) ion and tin (II) ion:
Ce4+(aq) + Sn2+(aq) → Ce3+(aq) + Sn4+(aq)
Reduction Reaction: Ce4+(aq) → Ce3+(aq)
Oxidation Reaction: Sn2+(aq) → Sn4+(aq)

REDOX REACTION CAN BE BALANCED BY HALF-REACTION

METHOD
A. Balancing Redox Reaction (Acidic Solution) By Half-Reaction Method
 Acidic condition usually implies excess H+ concentration, hence making
the solution acidic.
STEPS IN BALANCING (ACIDIC SOLUTION)
1. Write separate equations for the oxidation and reduction half-reactions.
2. For each half-reaction:
a) Balance all the elements except hydrogen and oxygen.
b) Balance oxygen using H2O.
c) Balance hydrogen using H+.
d) Balance the charge using electrons.
3. If necessary, multiply one or both balanced half-reactions by an integer to
equalize the number of electrons transferred in the two half-reactions.
4. Add the half-reactions, and cancel identical species.
5. Check that the elements and charges are balanced.
Example: MnO4-(aq) + Fe2+(aq) → Fe3+(aq) + Mn2+(aq)
Step 1: Identify and write equations for the half-reactions.
Reduction: MnO4-(aq) → Mn2+(aq)
Oxidation: Fe2+(aq) → Fe3+(aq)
Step 2: Balance each half-reaction.
For reduction, we have
MnO4-(aq) → Mn2+(aq)
a) The manganese is balanced.
b) Balance oxygen by adding H2O to the right side of the equation.
MnO4-(aq) → Mn2+(aq) + 4H2O(l)
c) Next, we balance hydrogen by adding 8H+ to the left side.
8H+(aq) + MnO4-(aq) → Mn2+(aq) + 4H2O(l)
 d) All the elements have been balanced, but we need to balance the
charge using electrons.
8H+(aq) + MnO4-(aq) → Mn2+(aq) + 4H2O(l)
8+ + 1- 2+ + 0

7+ 2+

We can equalize the charges by adding five electrons on the left side:
5e- + 8H+(aq) + MnO4-(aq) → Mn2+(aq) + 4H2O(l)
2+ 2+

This represents the balanced reduction half-reaction.

For oxidation reaction,
Fe2+(aq) → Fe3+(aq)
The elements are balanced, and we must simply balance the charge:
Fe2+(aq) → Fe3+(aq)
2+ 3+
One electron is needed on the right side to give a net 2+ charge on both
sides:
Fe2+(aq) → Fe3+(aq) + e-
2+ 2+
Step 3: Equalize the electron transfer in the two half-reactions.
(Fe2+(aq) → Fe3+(aq) + e-) x 5
5Fe2+(aq) → 5Fe3+(aq) + 5e-
Step 4: Add the half-reactions.
5e- + 5Fe2+(aq) + 8H+(aq) + MnO4-(aq) → 5Fe3+(aq) + 5e- + Mn2+(aq) + 4H2O(l)
Note that the electrons cancel (as they must) to give the final balanced
equation:
5Fe2+(aq) + 8H+(aq) + MnO4-(aq)  5Fe3+(aq) + Mn2+(aq) + 4H2O(l)
Step 5: Check that the elements and charges are balanced.
Elements: 5Fe, 1Mn, 4O, 8H → 5 Fe, 1Mn, 4O, 8H
Charges: 5(2+) + 8(1+) + (1-) = 17+ → 5(3+) + (2+) + 0 = 17+
B. Balancing Redox Reaction (Basic Solution) Using Half Cell Reaction
STEPS IN BALANCING IN BASIC CONDITION)
1. Use the half-reaction method as specified for acidic solutions to obtain the
final balanced equation as if H+ ions were present.
2. To both sides of the equation obtained above, add a number of OH - ions that is
equal to the number of H+ ions. (We want to eliminate H+ by forming H2O.)
3. Form H2O on the side containing both H+ and OH- ions, and eliminate the
number of H2O molecules that appear on both sides of the equation.
4. Check that elements and charges are balanced.
Example:
Zn + NO3- → Zn(OH)42- + NH3
Step 1: Balance the equation as if H+ ions were present.
Balance the oxidation half-reaction:
Zn → Zn(OH)42-

Balance Oxygen:
4H2O + Zn → Zn(OH)42-
Balance Hydrogen:
4H2O + Zn → Zn(OH)42- + 4H+
Balance the charge:
4H2O + Zn → Zn(OH)42- + 4H+ + 2e-
Balance the reduction half-reaction:
NO3- → NH3
Balance Oxygen:
NO3- → NH3 + 3H2O
Balance Hydrogen:
9H+ + NO3- → NH3 + 3H2O
Balance the charge:
8e- + 9H+ + NO3- → NH3 + 3H2O
Multiply the balanced oxidation half-reaction by 4:
[4H2O + Zn → Zn(OH)42- + 4H+ + 2e-] 4
16H2O +4Zn → 4Zn(OH)42- + 16H+ + 8e-
Add the half-reactions, and cancel identical species:
Oxidation Half-Reaction: 16H2O +4Zn → 4Zn(OH)42- + 16H+ + 8e-
Reduction Half-reaction: 8e- + 9H+ + NO3- → NH3 + 3H2O .
13H2O + 4Zn + NO3- → 4Zn(OH)42- + 7H+ + NH3
 Step 2: Add OH– to both sides of the balanced equation to eliminate the H+ ions.
We need to add 7 OH- to each side:
7OH- + 13H2O + 4Zn + NO3- → 4Zn(OH)42- + 7H+ + NH3 + 7OH-
Step 3: Form H2O on the side containing both H + and OH- ions, and eliminate the
number of H2O molecules that appear on both sides of the equation.
7OH- +13H2O + 4Zn + NO3- → 4Zn(OH)42- + NH3 + 7H2O
7OH- + 6H2O + 4Zn + NO3- → 4Zn(OH)42- + NH3
Step 4: Check that elements and charges are balanced.
Elements balanced: 19H, 16O, 4Zn, 1N → 4Zn, 19H, 16O, 1N
Charges balanced: 7 (1-) + 1 (1-) = -8  4 (2-) = -8