Oxidation-Reduction Reactions

Introduction

 Oxidation-reduction reactions are also known as redox reactions

Terminology

 The key idea is the net movement of electrons from one reactant to the other
 Oxidation is the loss of electrons
 Reduction is the gain of electrons
 Oxidizing agent is the species doing the oxidizing
 Reducing agent is the species doing the reducing

Redox Illustration

• H2+F2 2HF

• Oxidation (electron loss by H2)

– H2 2H+ + 2e-

• Reduction (electron gain by F2)

– F2 + 2e- 2F

H2 F2

- Oxidized - Reduced - Reducing agent - Oxidizing agent

Oxidation Number

• Oxidation number (O.N.) is also known as oxidation state

• It is defined as the charge the atom would have if electrons were not shared but were transferred completely

• For a binary ionic compound, the O.N. is equivalent to the ionic charge

• For covalent compounds or polyatomic ions, the O.N. is less obvious and can be determined by a given set of rules

Rules for Assigning an Oxidation Number

General Rules

1. For an atom in its elemental form (Na, O2): O.N. = 0

2. For a monatomic ion: O.N. = ion charge

3. The sum of O.N. values for the atoms in a molecule or formula unit of a compound equals to zero. (equals to the
ion’s charge if it is a polyatomic ion)

Rules for Specific Atoms or Periodic Table Groups

1. For Group 1A (1): O.N. = +1 in all compounds

2. For Group 2A (2): O.N. = +2 in all compounds

3. For hydrogen: O.N. = +1 in combination with nonmetals O.N. = -1 in combination with metals and boron

4. For fluorine: O.N. = -1 in all compounds

5. For oxygen: O.N. = -1 in peroxides O.N. = -2 in all other compounds (except with F)
6. For Group 7A (17): O.N. = -1 in combination with metals, nonmetals (except O), and other halogens lower in the
group

Example 1

Determine the oxidation number (O.N.) of each element in these compounds:

a) CaO (s)

b) KNO3 (s)

c) NaHSO4 (aq)

d) CaCO3 (s)

e) N2 (g)

f) H2O (l)

Solution to Example 1

Simply apply the rules for assigning an oxidation number as described earlier

a) CaO (s)

b) KNO3 (s) N = 0-(+1)-3(-2) = +5

c) NaHSO4 (aq) S = 0-(+1) -(+1)-4(-2) = +5

d) CaCO3 (s) C = 0-(+2)-3(-2) = +4

e) N2 (g)

f) H2O (l)

Example 2

Identify the oxidizing agent and reducing agent in each of the following:

a) 2H2 (g) + O2 (g)  2H2O (g)

b) Cu (s) + 4HNO3 (aq)  Cu(NO3 )2 (aq) + 2NO2 (g) + 2H2O (l)

Solution to Example 2

Assign oxidation numbers and compare. Oxidation is represented by an increase in oxidation number Reduction is
represented by a decrease in oxidation number

a) 2H2 (g) + O2 (g)  2H2O (g)

- O2 was reduced (O.N. of O: 0 -> -2); O2 is the oxidizing agent

- H2 was oxidized (O.N. of H: 0 -> +1); H2 is the reducing agent

b) Cu + 4HNO3  Cu(NO3 )2 + 2NO2 + 2H2O

- Cu was oxidized (O.N. of Cu: 0 -> +2); Cu is the reducing agent

- HNO3 was reduced (O.N. of N: +5 -> +4); HNO3 is the oxidizing agent

Balancing Redox Equations

• When balancing redox reactions, make sure that the number of electrons lost by the reducing agent equals the
number of electrons gained by the oxidizing agent

• Two methods can be used:

2. Half-reaction method

METHOD 1: Oxidation number method

1. Assign oxidation numbers to all elements in the reaction

2. From the changes in O.N., identify the oxidized and reduced species

3. Compute the number of electrons lost in the oxidation and gained in the reduction from the O.N. changes

4. Multiply one or both of these numbers by appropriate factors to make the electrons lost equal the electrons gained,
and use the factors as balancing coefficients

5. Complete the balancing by inspection, adding states of matter

Example 3

Use the oxidation number method to balance the following equations:

a) Al(s) + H2 SO4 (aq)  Al2 (SO4 )3 (aq) + H2 (g)

b) PbS(s) + O2 (g)  PbO(s) + SO2 (g)

Part a: Solution to Example 3

• Step 1. Assign oxidation numbers to all elements

Al(s) + H2 SO4 (aq)  Al2 (SO4 )3 (aq) + H2 (g)

• Step 2. Identify oxidized and reduced species – Al was oxidized (O.N. of Al: 0 -> +3) – H2 SO4 was reduced (O.N.
of H: +1 -> 0)

• Step 3. Compute e- lost and e- gained

– In the oxidation: 3e- were lost from Al

– In the reduction: 1e- was gained by H

• Step 4. Multiply by factors to make e- lost equal to e- gained, and use the factors as coefficients

– Al lost 3e- , so the 1e- gained by H should be multiplied by 3. Put the coefficient 3 before H2 SO4 and H2.

Al(s) + 3H2 SO4 (aq)  Al2 (SO4 )3 (aq) + 3H2 (g)

• Step 5. Complete the balancing by inspection

2Al(s) + 3H2 SO4 (aq)  Al2 (SO4 )3 (aq) + 3H2 (g)

Part b: Solution to Example 3

• Step 1. Assign oxidation numbers to all elements

PbS(s) + O2 (g)  PbO(s) + SO2 (g)

• Step 2. Identify oxidized and reduced species

– PbS was oxidized (O.N. of S: -2 -> +4)

– O2 was reduced (O.N. of O: 0 -> -2)

• Step 3. Compute e- lost and e- gained

– In the oxidation: 6e- were lost from S

• Step 4. Multiply by factors to make e- lost equal to e- gained, and use the factors as coefficients

– S lost 6e-, O gained 4e- (2e- each O). Thus, put the coefficient 3/2 before O2.

PbS(s) + 3/2O2 (g)  PbO(s) + SO2 (g)

• Step 5. Complete the balancing by inspection

2PbS(s) + 3O2 (g)  2PbO(s) + 2SO2 (g)

METHOD 2: Half-reaction method

1. Divide the skeleton reaction into two half-reactions, each of which contains the oxidized and reduced forms of one
of the species

2. Balance the atoms and charges in each half-reaction

– Atoms are balanced in order: atoms other than O and H, then O, then H

– Charge is balanced by adding electrons

• To the left in reduction half-reactions

• To the right in oxidation half-reactions

3. If necessary, multiply one or both half-reactions by an integer to make the number of

e- gained equal to the number of e-lost

4. Add the balanced half-reactions, and include states of matter

5. Check that the atoms and charges are balanced

Example 4

Use the half-reaction method to balance the following equations:

a) ClO3 - (aq) + I- (aq)  I2 (s) + Cl- (aq) [acidic]

b) Fe(OH)2 (s) + Pb(OH)3 - (aq)  Fe(OH)3 (s) + Pb(s) [basic]

Part a: Solution to Example 4

• Step 1. Divide the reaction into half-reactions

ClO3 - (aq)  Cl- (aq) I - (aq)  I2 (s)

• Step 2. Balance atoms and charges in each half-reaction

– Atoms other than O and H

ClO3 - (aq) -> Cl- (aq) Cl is balanced

2I- (aq) -> I2 (s) I now balanced

– Balance O atoms by adding H2O molecules

ClO3 - (aq) -> Cl- (aq) + 3H2O(l) Add 3H2O

2I- (aq) -> I2 (s) No change

– Balance H atoms by adding H+ ions

2I- (aq) -> I2 (s) No change

– Balance charge by adding electrons

ClO3 - (aq) + 6H+ + 6e- -> Cl- (aq) + 3H2O(l) Add 6e-

2I- (aq) -> I2 (s) + 2e- Add 2e-

• Step 3. Multiply each half-reaction by an integer to equalize number of electrons

ClO3 - (aq) + 6H+ + 6e- -> Cl- (aq) + 3H2O(l) x1

3[2I- (aq) -> I2 (s) + 2e- ] x3

• Step 4. Add the half-reactions together

ClO3 - (aq) + 6H+ + 6e- -> Cl- (aq) + 3H2O(l)

6I- (aq) -> 3I2 (s) + 6e

ClO3 - (aq) + 6H+ (aq) + 6I- (aq)  Cl- (aq) + 3H2O(l) + 3I2 (s)

• Step 5. Check that atoms and charges balance

– Reactants (Cl, 3O, 6H, 6I, -1) -> products (Cl, 3O, 6H, 6I, -1)

• ClO3 - is the oxidizing agent

• I - is the reducing agent

Part b: Solution to Example 4

• The only difference in balancing a redox equation that takes place in basic solution is in Step 4.

• At this point, we add one OHion to both sides of the equation for every H+ ion present

• The H+ ions on one side are combined with the added OHions to form H2O, and OHions appear on the other side of
the equation

• Step 1. Divide the reaction into half-reactions

Pb(OH)3 - (aq) -> Pb(s) Fe(OH)2 (s) -> Fe(OH)3 (s)

• Step 2. Balance atoms and charges in each half-reaction

– Atoms other than O and H

Pb(OH)3 - (aq) -> Pb(s) Pb is balanced

Fe(OH)2 (s) -> Fe(OH)3 (s) Fe is balanced

– Balance O atoms by adding H2O molecules

Pb(OH)3 - (aq) -> Pb(s) + 3H2O Add 3H2O

Fe(OH)2 (s) + H2O -> Fe(OH)3 (s) Add H2O

– Balance H atoms by adding H+ ions

Pb(OH)3 - (aq) + 3H+ -> Pb(s) + 3H2O Add 3H+

Fe(OH)2 (s) + H2O -> Fe(OH)3 (s) + H+ Add H+

Pb(OH)3 - (aq) + 3H+ + 2e- -> Pb(s) + 3H2O Add 2e

Fe(OH)2 (s) + H2O -> Fe(OH)3 (s) + H+ + e- Add e-

• Step 3. Multiply each half-reaction by an integer to equalize number of electrons

Pb(OH)3 - (aq) + 3H+ + 2e- -> Pb(s) + 3H2O x1

2[Fe(OH)2 (s) + H2O -> Fe(OH)3 (s) + H+ + e-] x2

• Step 4. Add the half-reactions together

Pb(OH)3 - (aq) + 3H+ + 2e- -> Pb(s) + 3H2O

2Fe(OH)2 (s) + 2H2O -> 2Fe(OH)3 (s) + 2H+ + 2e

Pb(OH)3 - (aq) + H+ (aq) + 2Fe(OH)2 (s)  Pb(s) + H2O(l) + 2Fe(OH)3 (s)

Step 4(basic). Add OH-

– Here, we add 1 OH

Pb(OH)3 - (aq) + H+ (aq) + OH- + 2Fe(OH)2 (s) -> Pb(s) + H2O(l) + 2Fe(OH)3 (s) + OH

Pb(OH)3 - (aq) + 2Fe(OH)2 (s)  Pb(s) + 2Fe(OH)3 (s) + OH- (aq)

• Step 5. Check

– Reactants (Pb, 7O, 7H, 2Fe, -1) -> products (Pb, 7O, 7H, 2Fe, -1)

• Pb(OH)3 - is the oxidizing agent

• Fe(OH)2 is the reducing agent