Electrochemistry
Module-10
Chapter 18
1
Electrochemical Processes
Electrochemical processes are oxidation-reduction reactions
in which:
• the energy released by a spontaneous chemical reaction is
converted to electricity by Voltaic/Galvanic Cell
• electrical energy is used to cause a nonspontaneous
chemical reaction to occur by Electrolytic cell
0 0 2+ 2−
2Mg 𝑠 + O2 𝑔 → 2MgO 𝑆
2Mg → 2Mg 2+ + 4e− Oxidation half-reaction (lose e− )
O2 + 4e− → 2O2− Reduction half-reaction (gain e− )
2
Oxidation Numbers
In order to keep track
of what loses electrons
and what gains them,
we assign oxidation
numbers.
• What is reduced is the oxidizing agent.
– H+ oxidizes Zn by taking electrons from it.
• What is oxidized is the reducing agent.
– Zn reduces H+ by giving it electrons.
3
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 , O , P = 0
2 2 4
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. Group IA metals are +1, IIA metals are +2 and fluorine is always
–1.
4. The sum of the oxidation numbers of all the atoms in a 4
molecule or ion is equal to the charge on the molecule or ion.
Exercise
Find the oxidation number of underlined in the compounds:
1. OF2 =+2
2. HNO3 =+5
=+6
3. Cr2O72-
=+1
4. NaClO
5
Galvanic Cells
anode cathode
oxidation reduction
spontaneous
redox reaction
Net reaction
Zn 𝑠 ⟶ Zn2+ 𝑎𝑞 + 2𝑒 − Zn 𝑠 + Cu2+ 𝑎𝑞 ⟶ Zn2+ 𝑎𝑞 + Cu 𝑠 2𝑒 − + Cu2+ 𝑎𝑞 ⟶ Cu 𝑠
6
Galvanic Cells
The difference in electrical
potential between the anode
and cathode is called:
• cell voltage
• electromotive force (emf)
• cell potential
Zn 𝑠 + Cu2+ 𝑎𝑞 → Cu 𝑠 + Zn2+ 𝑎𝑞
Cu2+ = 1 𝑀 and Zn2+ = 1 𝑀
Cell Diagram
phase boundary
Zn 𝑠 ȁ Zn2+ 1 𝑀 ȁȁCu2+ 1 𝑀 ȁ Cu 𝑠
anode salt bridge cathode 7
Standard Reduction Potentials
Standard reduction potential 𝑬∘ is the voltage associated
with a reduction reaction at an electrode when all solutes
are 1 M and all gases are at 1 atm.
Copyright © McGraw-Hill Education. Permission required for reproduction or display.
Reduction Reaction
2𝑒 − + 2H + 1 𝑀 → H2 1 𝑎𝑡𝑚
𝐸∘ = 0 V
8
Standard hydrogen electrode (SHE)
Standard Reduction Potentials
°
𝐸cell = 0.34 V
° ° °
Copyright © McGraw-Hill Education. Permission required for reproduction or display. 𝐸cell = 𝐸cathode − 𝐸anode
° ° °
𝐸cell = 𝐸Cu 2+ ΤCu − 𝐸H+ ΤH
2
°
0.34 = 𝐸Cu 2+ ΤCu − 0
°
𝐸Cu 2+ ΤCu = 0.34 V
Pt 𝑠 H2 1 𝑎𝑡𝑚 H + 1 𝑀 ȁ Cu2+ 1 𝑀 Cu 𝑠
Anode (oxidation): H2 1 𝑎𝑡𝑚 → 2H+ 1 𝑀 + 2𝑒 −
Cathode (reduction): 2𝑒 − + Cu2+ 1 𝑀 → Cu s
H2 1 𝑎𝑡𝑚 + Cu2+ 1 𝑀 → Cu 𝑠 + 2H + 1 𝑀 9
Standard Reduction Potentials
For the oxidation in this cell For the
reduction
= −0.76 V Ered
Ered = +0.34 V
= Ered
Ecell (cathode) − (anode)
Ered
= +0.34 V − (−0.76 V)
= +1.10 V
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Example 18.3
A galvanic cell consists of a Mg electrode in a 1.0 M Mg NO3 2
solution and a Ag electrode in a 1.0 M AgNO3 solution. Calculate the
standard emf of this cell at 25° C.
• Ag + 1.0 𝑀 + 𝑒 − → Ag 𝑠 • 𝐸 ° = 0.80 V
• Mg 2+ 1.0 𝑀 + 2𝑒 − → Mg 𝑠 • 𝐸 ° = −2.37 V
3.17 V
Practice Exercise What is the standard emf of a galvanic cell
made of a Cd electrode in a 1.0 M Cd(NO3)2 solution and a Cr
electrode in a 1.0 M Cr(NO3)3 solution at 25°C?
Cd2+ (aq) + 2e- Cd (s) E0 = − 0.40 V
Cr3+ (aq) + 3e- Cr (s) E0 = − 0.74 V
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