CHAPTER 7

OXIDATION AND REDUCTION REACTIONS

REDOX REACTIONS

Redox reactions: - oxidation and reduction reactions that occurs simultaneously. Oxidation: 1) addition of oxygen 2) loss of hydrogen 3) loss of electron 4) increase in the oxidation state / oxidation number

Reduction: 1) loss of oxygen 2) addition of hydrogen 3) gain of electrons 4) decrease in the oxidation state / oxidation number

Electron Transfer Reactions

Oxidation reactions: half-reaction that involves loss of electrons
Reduction reactions: half-reaction that involves gain of electrons Oxidizing agents: substance that accepts electrons (substances that are reduced)

Reducing agents: substances that donates electrons (substances that are oxidized)

Electron Transfer Reactions

2Mg O2 + 4e2Mg2+ + 4e- Oxidation half-reaction (lose e-) 2O2-

Reduction half-reaction (gain e-)

2Mg2+ + 2O2- + 4e-

2Mg + O2 + 4e-

2Mg + O2

2MgO

Examples:
1)

Zn (s) + CuSO4 (aq)

Zn2+ + 2e- Zn is oxidized
Cu Cu2+ is reduced

ZnSO4 (aq) + Cu (s)

Zn is the reducing agent Cu2+ is the oxidizing agent

Zn

Cu2+ + 2e-

2) Copper wire reacts with silver nitrate to form silver metal. What is the oxidizing agent in the reaction?

Cu (s) + 2AgNO3 (aq)

Cu Cu2+ + 2eAg Ag+ + 1e-

Cu(NO3)2 (aq) + 2Ag (s)

Ag+ is reduced Ag+ is the oxidizing agent

Oxidation number
The charge the atom would have in a molecule (or an ionic compound) if electrons were completely transferred. 1. Free elements (uncombined state) have an oxidation number of zero. Na, Be, K, Pb, H2, O2, P4 = 0 2. In monatomic ions, the oxidation number is equal to the charge on the ion. Li+, Li = +1; Fe3+, Fe = +3; O2-, O = -2 3. The oxidation number of oxygen is usually 2. In H2O2 and 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, its oxidation number is 1. 5. Group IA metals are +1, IIA metals are +2 and fluorine is always 1. 6. The sum of the oxidation numbers of all the atoms in a molecule or ion is equal to the charge on the molecule or ion. 7. Oxidation numbers do not have to be integers. Oxidation number of oxygen in the superoxide ion, O2-, is .

The Oxidation Numbers of Elements in their Compounds

Examples: What are the oxidation numbers of all the elements in this folowing compounds or ion? i) HCO3-

O = 2

H = +1
3x(2) + 1 + ? = 1

C = +4

ii) NaIO3 Na = +1

O = -2 3x(-2) + 1 + ? = 0
I = +5 iii) IF7 iv) K2Cr2O7 v) Li2O vi) HNO3

Titrations in Redox Reactions

5Fe2+ + MnO4- + 8H+ Mn2+ + 5Fe3+ + 4H2O

Dark purple (MnO4-) to light pink (Mn2+)

16.42 mL of 0.1327 M KMnO4 solution is needed to oxidize 25.00 mL of an acidic FeSO4 solution. What is the molarity of the iron solution?

5Fe2+ + MnO4- + 8H+

Mn2+ + 5Fe3+ + 4H2O

volume red

M
red

moles red

rxn coef.

moles oxid

V
oxid

M oxid

16.42 mL = 0.01642 L
0.01642 L x 0.1327 mol KMnO4 1L

25.00 mL = 0.02500 L
5 mol Fe2+ 1 mol KMnO4

1 0.02500 L Fe2+

= 0.4358 M

Balancing Redox Equations

Ion electron method

Balancing Redox Equations for Reaction Takes Place in Acidic Solution

Following is the guideline for balancing an oxidation-reduction equation in acidic solution by the ion-electron method. Step 1: - Write the two half-reactions that contain the elements being oxidised and reduced using the entire formula of the ion or molecule.

Step 2: - Balance all the elements except oxygen and hydrogen. Step 3: - Balance oxygen using H2O and hydrogen using H+. Step 4: - Balance the charge using electrons. If

necessary, multiplying one or both balanced halfreaction by integers to equalize the number of electrons transferred in the two half reactions.

Step 5: - Add the half-reactions and cancel identical species. - Verifying check to be sure that the elements and charges are balanced.

Example 1: Balance the following equation by the ionelectron method. Cr2O72- + ClCr3+ + Cl2 Solution: Determine the oxidation number of the species involved. 2Oxn(Cr) + 7Oxn(O) = -2 2Oxn(Cr) + 7(-2) = -2 Oxn(Cr) = +6

The oxidation number of Cr is +6 The oxidation number of Cl- is -1 whereas the oxidation number of Cl2 is zero.
Step 1:The ionic equation is divided in 2 distinct half-reactions. One representing oxidation and the other representing reduction. Cr2O72- (aq) Cr3+ (aq) ..(1)(reduction) Cl- (aq) Cl2 ..(2)(oxidation)

Step 2 : Balance the atoms in each halfequation separately (except H and O) Cr2O72- (aq) 2Cl- (aq) 2Cr3+ (aq) (3) Cl2 (4)

Step 3 : For reaction in acid medium, add H2O to balance the O atoms and H+ to balance the H atoms.
14H+ + Cr2O72- (aq) 2Cl- (aq) 2Cr3+ (aq) + 7H2O Cl2 (5) (6)

Step 4: Balance the charges of each halfreaction by adding electron(s) to either the left or right side of the equation. If the electron(s) appears on the right, the process is an oxidation process. If electron(s) appears on the left, it is a reduction process.

The net charge on the left is +12. The net charge of Cr on the right is +6. Therefore, we add 6 electrons (-6) to the left so that the net charges on both sides are equal +6
6 e- + 14H+ + Cr2O72- (aq) 2Cr3+ (aq) + 7H2O (7)

For the 2nd half-equation, the net charges on the left is -2 while the net charge on the right is 0. Therefore, we add 2 electrons to the right so that the net charges on both sides are equal -2. 2Cl- (aq) Cl2 + 2 e(8)

Equalise the number of electrons in both half-equations by multiplying one or two half-equations with appropriate coefficients. By looking at the 2 half equations, the 2nd half-equation is multiplied by 3 to balance the electrons on both half-reaction.
2Cr3+ (aq) + 7H2O Cl2 + 2 e3Cl2 + 6 e(7) (8) (9)

Cr2O72- (aq) + 14H+ + 6 e2Cl- (aq) (equation (8) 3) 6Cl- (aq)

Step 5: Then, add the 2 half-reaction equations together and balance the final equation by inspection. The electrons on both sides should be cancelled.
Cr2O72- (aq) + 14H+ + 6 e6Cl- (aq)
(7) + (9) Cr2O72-

2Cr3+ (aq) + 7H2O (7) 3Cl2 + 6 e(9) 2Cr3+ (aq) + 7H2O

(aq) + 14H+ + 6Cl- (aq)

+ 3Cl2