Electrochemistry

Chapter 18

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 Oxidation-Reduction
Reactions
…are electron transfer reactions

Examples:

• Combustion
• Bleaching
• Extracting metals
• Batteries
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 Electrochemical Processes
Electrochemical processes are oxidation-reduction reactions
in which:
• the energy released by a spontaneous reaction is
converted to electricity or
• electrical energy is used to cause a nonspontaneous
reaction to occur

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 Electrochemical Processes: Example

0 0 2+¿ 2 −
2 Mg ( 𝑠 )+ O 2 ( 𝑔 ) → 2 MgO ( 𝑆 )

−
2+¿+ 4 e ¿ Oxidation half-reaction (lose )
2 Mg → 2 Mg
O 2 + 4 e − → 2O 2 − Reduction half-reaction (gain )
2Mg + O2 2MgO OVERALL REACTION

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 Oxidation Numbers
• oxidation numbers are a
way keep track of what loses
electrons and what gains
electrons.
• If oxidation number
increases: that element is
oxidized.
• If the oxidation number
decreases: that element is
reduced.

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 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 , H 2 ,O 2 , P4 =0
2. In monatomic ions, the oxidation number is equal to
the charge on the ion.
2 −
3+ ¿ , Fe = +3 ; O , O= − 2¿
+ ¿ , Li=+1 ; Fe ¿
Li
3. The oxidation number of oxygen is usually . In and it is
.
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 Oxidation Number (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.

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 Practice

Assign oxidation numbers to all the elements in the following

compounds and ion:

Li2O

HNO3

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 Types of Oxidation-Reduction Reactions

Combination Reaction
A+B C
0 0 +3 -1
2Al + 3Br2 2AlBr3

Decomposition Reaction
C A+B

+1 +5 -2 +1 -1 0
2KClO3 2KCl + 3O2
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 Types of Oxidation-Reduction Reactions

Displacement Reaction
A + BC AC + B
0 +1 +2 0
Sr + 2H2O Sr(OH)2 + H2 Hydrogen Displacement
+4 0 0 +2
TiCl4 + 2Mg Ti + 2MgCl2 Metal Displacement
0 -1 -1 0
Cl2 + 2KBr 2KCl + Br2 Halogen Displacement

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 Zn(s) + CuSO4(aq) ZnSO4(aq) + Cu(s)

Zn Zn2+ + 2e- Zn is oxidized

Zn is the reducing agent

Cu2+ + 2e- Cu Cu2+ is reduced

Cu2+ is the oxidizing agent

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 Types of Oxidation-Reduction Reactions
Disproportionation Reaction
The same element is simultaneously oxidized and
reduced.

Example: reduced

0 +1 -1
Cl2 + 2OH- ClO- + Cl- + H2O

oxidized

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Half-Reactions
The oxidation and reduction are written and balanced separately.
We will use half-reactions to balance a redox reaction.

For example, when Sn 2 and Fe 3 react,

Oxidation : Sn 2 aq   Sn 4 aq   2e 

Reduction : 2 Fe 3 aq   2e   2 Fe 2 aq 

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 Balancing Redox Equations
2+ ¿ ¿
+ ¿ + Zn → Ag+ Zn ¿
Ag
This equation is balanced in terms of mass,
but NOT in terms of CHARGE

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 Balancing Redox Equations
Balance this reaction in acid solution:

1. Write the unbalanced equation for the reaction in ionic form.

3 +¿ ¿
2 − 3+ ¿ +Cr ¿
2 +¿ +Cr 2 O7 → Fe ¿
F e

2. Separate the equation into two half-reactions.

+2 +3
3 +¿ ¿
¿
Oxidation: Fe 2+¿ → Fe

+6 +3
2− 3 +¿ ¿
Reduction: Cr 2 O 7 →Cr

3. Balance the atoms other than O and H in each half-reaction.

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 Balancing Redox Equations (1)
4. Add to balance O atoms and to balance H atoms (if the
reaction happens in basic solution, we’ll fix this later).

5. Add electrons to one side of each half-reaction to balance the

charges on the half-reaction.

6. If necessary, equalize the number of electrons in the two half-

reactions by multiplying the half-reactions by appropriate
coefficients.

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 Balancing Redox Equations (2)
7. Add the two half-reactions together and balance the final
equation by inspection. The number of electrons on both
sides must cancel.

8. Verify that the number of atoms and the charges are balanced.

14 × 1− 2+6 × 2=24=6 ×3 +2 ×3
9. For reactions in basic solutions, add to both sides of the
equation for every that appears in the final equation.
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Example 18.1
Write a balanced ionic equation to represent the oxidation of
iodide ion by permanganate ion in basic solution to yield
molecular iodine and manganese(IV) oxide .

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