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.

3
 Oxidation and Reduction

• A species is oxidized when it loses electrons

hence it is called Reducing Agent.
– Here, zinc loses two electrons to go from neutral zinc
metal to the Zn2+ ion.

4
 Oxidation and Reduction

• A species is reduced when it gains electrons

hence it is called Oxidizing Agent.
– Here, each of the H+ gains an electron, and they
combine to form H2.

5
 Oxidation and Reduction

• 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.

6
 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 H2 O2
and O2 2− it is – 1.
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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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 Galvanic Cells
Copyright © McGraw-Hill Education. Permission required for reproduction or display.

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

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 Galvanic Cells (1)
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 10
 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

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Standard hydrogen electrode (SHE)
 Standard Reduction Potentials (2)
°
𝐸cell = 0.76 V
Copyright © McGraw-Hill Education. Permission required for reproduction or display.

∘
Standard emf 𝑬𝒄𝒆𝒍𝒍
∘ ∘ ∘
𝐸cell = 𝐸cathode − 𝐸anode

Zn 𝑠 ȁZn2+ 1 𝑀 ȁȁH + 1 𝑀 ȁH2 1 atm ȁPt 𝑠

°
𝐸cell = 𝐸𝐻° +Τ𝐻2 − 𝐸Zn
°
2+ ΤZn
°
0.76 V = 0 − 𝐸Zn 2+ ΤZn
°
𝐸Zn 2+ ΤZn = −0.76 V

Zn2+ 1 𝑀 + 2𝑒 − → Zn 𝐸 ° = −0.76 V 12
 Standard Reduction Potentials (3)

°
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

°
𝐸Cu2+ 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 13
  = −0.76 V
For the oxidation in this cell Ered
For the reduction Ered = +0.34 V

 = Ered
Ecell  (cathode) − Ered
 (anode)
= +0.34 V − (−0.76 V)
= +1.10 V

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Standard Reduction
°
Potentials E

15
 Oxidizing and Reducing Agents
• The strongest oxidizers
have the most positive
reduction potentials.
• The strongest reducers
have the most negative
reduction potentials.

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Oxidizing and Reducing Agents
The greater the
difference between the
two, the greater the
voltage of the cell.

17
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

Practice Exercise What is the standard emf of a galvanic

cell made of a Cd electrode in a 1.0 M Cd(NO ) solution and a
3 2

Cr electrode in a 1.0 M Cr(NO ) solution at 25°C?

3 3

Cd2+ (aq) + 2e- Cd (s) E0 = − 0.40 V

Cr3+ (aq) + 3e- Cr (s) E0 = − 0.74 V

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 The Effect of Concentration on Cell Emf
DG = DG0 + RT ln Q DG = -nFE DG0 = -nFE 0

-nFE = -nFE0 + RT ln Q

Nernst equation

RT
E = E0 - ln Q
nF
(8.314 J/K•mol)(298 K)
E= E0 - ln Q
n (96,500 J/V•mol)
0.0257 V 0.0592 V
E = E0 - ln Q E = E0 - log Q
n n

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Will the following reaction occur spontaneously at 250C if
[Fe2+] = 0.60 M and [Cd2+] = 0.010 M?
Fe2+ (aq) + Cd (s) Fe (s) + Cd2+ (aq)

Oxidation: Cd Cd2+ + 2e-

n=2
Reduction: 2e- + Fe2+ 2Fe
2+/Fe – ECd2+/Cd
0
E0 = EFe 0

E0 = -0.44 – (-0.40) 0.0257 V

E = E0 - ln Q
n
E0 = -0.04 V
0.0257 V 0.010
E = -0.04 V - ln
2 0.60
E = 0.013 volt Spontaneous

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Example 18.6 ample 18.6
Predict whether the following reaction would proceed
spontaneously as written at 298 K:
Co(s) + Fe2+(aq) →Co2+(aq) + Fe(s)
given that [Co2+] = 0.15 M and [Fe2+] = 0.68 M.
Anode (oxidation): Co2+(aq) + 2e- → Co(s) Eo oxi= −0.28 volt
Cathode (reduction): Fe2+(aq) + 2e- →Fe(s) Eo red= −0.44 volt

Practice Exercise Will the following reaction occur

spontaneously at 25°C, given that [Fe2+] = 0.60 M and
[Cd2+] = 0.010 M ?
Cd(s) + Fe2+(aq) → Cd2+(aq) + Fe(s)
Cathode (reduction): Fe2+(aq) + 2e- →Fe(s) Eo red= −0.44 volt
Anode (oxidation): Cd2+(aq) + 2e- → Cd(s) Eo oxi= −0.40 volt
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