Reduction-Oxidation Reactions

- Reactions involving transfer of electrons

OXIDATION – loss of electrons

Electrochemistry REDUCTION – gain of electrons

NOTE: Electrons lost in oxidation are gained in simultaneous

reduction of other species

• LEORA = Loss of Electrons – Oxidation – Reducing Agent

• GEROA = Gain of Electrons – Reduction – Oxidizing Agent

Oxidation Numbers GENERAL RULES: they always apply

• mark the flow of electrons and are useful for balancing Rule 1: The oxidation number of an element in its free
reduction-oxidation equations. (uncombined) state is zero. This is also true for elements found in
• Either positive or negative numbers nature as diatomic (two-atom) elements: H2, O2, Cl2
Rule 2: The sum of all oxidation numbers in a neutral compound
is zero. The sum of all oxidation numbers in a polyatomic (many-
atom) ion is equal to the charge of the ion.
Rule 3: The oxidation number of an alkali metal (IA family) in a
compound is +1; the oxidation number of alkaline earth metals
(IIA family) in a compound is +2.
 GENERAL RULES: they always apply STEPS
Rule 4: The oxidation number of oxygen in a compound is 1. Write the half-reactions.
usually -2. If, however, oxygen is in a class of compounds called
peroxides (Example: Hydrogen Peroxide or H2O2), then oxygen 2. Balance the moles.
has an oxidation number of -1. If the oxygen is bonded to 3. Balance the charges by adding electrons (e-). NOTE:
fluorine, the oxidation number is +1. Electrons have a charge of -1.
Rule 5: The oxidation number of Fluorine is always -1. Chlorine, 4. Balance in a way that the two half-reactions have the same
bromine, and iodine usually have an oxidation number of -1, number of electrons.
unless they’re in combination with an oxygen or fluorine.
Rule 6: The oxidation state of hydrogen in a compound is usually 5. Combine the two half-reactions and simplify.
+1. If the hydrogen is part of a binary metal hydride (compound of
hydrogen and some metal), then the oxidation state of hydrogen
is -1.

EXAMPLE: Cu(s) + AgNO3 → Ag(s) + Cu(NO3)2

EXAMPLE: Zn(s) + AgCl(aq) → Ag(s) + ZnCl2(aq)
HALF REACTIONS HALF REACTIONS
Oxidation of Copper Reduction of Silver Oxidation of Zinc Reduction of Silver
Cu (s) → Cu2+ (aq) + 2 e- Ag+ (aq) + e- → Ag(s) Zn (s) → Zn2+ (aq) + 2 e- Ag+ (aq) + e- → Ag(s)

Balance equations to cancel e-: Balance equations to cancel e-:

Cu (s) → Cu2+ (aq) + 2 e- Zn (s) → Zn2+ (aq) + 2 e-
(Ag+ (aq) + e- → Ag(s)) * 2 (Ag+ (aq) + e- → Ag (s)) * 2
2 Ag (aq) + Cu (s) → 2 Ag (s) + Cu2+ (aq)
+ 2 Ag (aq) + Zn (s) → 2 Ag (s) + Zn2+ (aq)
+

2 AgNO3 (aq) + Cu (s) → 2 Ag (s) + Cu(NO3)2 (aq) 2 AgCl (aq) + Zn (s) → 2 Ag (s) + ZnCl2 (aq)
EXAMPLE: Cu(s) + Ni2+(aq) → Ni(s) + Cu2+(aq) EXAMPLE: Ba(s) + Fe3+ → Fe(s) + Ba2+(aq)

HALF REACTIONS HALF REACTIONS

Oxidation of Copper Reduction of Nickel Oxidation of Barium Reduction of Iron
Cu (s) → Cu2+ (aq) + 2 e- Ni2+ (aq) + 2e- → Ni(s) Ba (s) → Ba2+ (aq) + 2 e- Fe3+(aq) + 3e- → Fe(s)

Balance equations to cancel e-: Balance equations to cancel e-:

Cu (s) → Cu2+ (aq) + 2 e- (Ba (s) → Ba2+ (aq) + 2 e-)*3
Ni2+ (aq) + 2e- → Ni(s) (Fe3+ (aq) + 3e- → Fe(s))*2
Ni2+ (aq) + Cu (s) → Ni (s) + Cu2+ (aq) 3Ba(s) + 2Fe3+ → 2Fe(s) + 3Ba2+(aq)

Ni2+ (aq) + Cu (s) → Ni (s) + Cu2+ (aq) 3Ba(s) + 2Fe3+ → 2Fe(s) + 3Ba2+(aq)

Balancing Redox Reactions in Acidic EXAMPLE: Mn2+ + BiO3- → MnO4- + Bi2+

Solution
HALF REACTIONS
1. Write the half-reactions. STEPS 1 & 2: STEPS 1 & 2:
2. Balance the moles. Mn2+ → MnO4- BiO3- → Bi2+
3. Balance the oxygen by adding H2O. STEP 3: STEP 3:
4. Balance the hydrogen by adding H+. 4H2O + Mn2+ → MnO4- BiO3- → Bi2+ + 3H2O
5. Balance the charges by adding electrons (e-). NOTE: STEP 4: STEP 4:
Electrons have a charge of -1.
4H2O + Mn2+ → MnO4- + 8H+ 6H++ BiO3- → Bi2+ + 3H2O
6. Balance in a way that the two half-reactions have the same STEP 5:
number of electrons. STEP 5:
4H2O + Mn2+→ MnO4- + 8H+ + 5e- 3e- + 6H++ BiO3- → Bi2+ + 3H2O
7. Combine the two half-reactions and simplify.
 EXAMPLE: Mn2+ + BiO3- → MnO4- + Bi2+ EXAMPLE: MnO4- + Zn(s) → MnO2 + Zn(OH)42-

HALF REACTIONS HALF REACTIONS

STEP 6: STEP 6: STEPS 1 & 2: STEPS 1 & 2:
(4H2O + Mn2+→ MnO4- + 8H+ + (3e-+6H++ BiO3-→Bi2+ + 3H2O) * 5 MnO4- → MnO2 Zn(s) →Zn(OH)42-
5e-) * 3 STEP 3: STEP 3:
STEP 7: Combine half-reactions MnO4 → MnO2 + 2H2O
- 4H2O + Zn(s) →Zn(OH)42-
12H2O + 3Mn2+ → 3MnO4- + 24H+ + 15e- STEP 4: STEP 4:
15e-+ 30H+ + 5BiO3- → 5Bi2+ + 15H2O 4H + MnO4- → MnO2 + 2H2O
+ 4H2O + Zn(s) →Zn(OH)42- + 4H+
STEP 5: STEP 5:
3Mn2+ + 5BiO3- + 6H+ → 3MnO4- + 5Bi2+ + 3H2O
3e- + 4H++ MnO4- → MnO2 + 4H2O + Zn(s) →Zn(OH)42- + 4H+ +
2e-
2H2O
3Mn2+ + 5BiO3- + 6H+ → 3MnO4- + 5Bi2+ + 3H2O

EXAMPLE: MnO4- + Zn(s) → MnO2 + Zn(OH)42-

HALF REACTIONS
STEP 6: STEP 6:
(3e- + 4H++ MnO4- → MnO2 + 2H2O (4H2O + Zn(s) → Zn(OH)42- + 4H+ +
2e-) * 3
)*2

STEP 7: Combine half-reactions

6e- + 8H++ 2MnO4- → 2MnO2 + 4H2O
812H2O + 3Zn(s) → 3Zn(OH)42- + 412H+ + 6e-
8H2O + 2MnO4- + 3Zn(s) → 3Zn(OH)42- + 2MnO2 + 4H+

8H2O + 2MnO4- + 3Zn(s) → 3Zn(OH)42- + 2MnO2 + 4H+