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OpenCourseWare (2023)
CHEMISTRY II
Verónica San Miguel Arnanz
Teresa Pérez Prior
Berna Serrano Prieto
Department of Materials Science and Engineering and Chemical Engineering
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SOLUTIONS OF ELECTROCHEMISTRY I EXERCISES
EP 1.1. SOLUTIONS OF ELECTROCHEMISTRY I
Exercise 1. Iron (II) is oxidized by dichromate ion in acidic solution to yield Fe3+ and Cr3+. Write the balanced
ionic equation.
SOLUTION
Oxidation: Fe2+ → Fe3+ + 1e-
Reduction: Cr2O72− + 14 H+ + 6 e− → 2 Cr3++ 7 H2O
Overall Reaction: 6 Fe2+ + Cr2O72− + 14 H+ → 6 Fe3+ + 2 Cr3++ 7 H2O
Exercise 2. In the oxidation of CN− by permanganate ion in basic medium, the following products are
generated: CNO− and MnO2. Write the balanced ionic equation.
SOLUTION
Oxidation: CN− + 2 OH− → CNO− + 2 e− + H2O
Reduction: MnO4− + 2 H2O + 3 e− → MnO2 + 4 OH−
Overall Reaction: 3 CN− + 2 MnO4− + H2O → 3 CNO− + 2 MnO2 + 2 OH−
Exercise 3. A galvanic cell consists of a Mg electrode in a 1 M Mg(NO3)2 solution and a Ag electrode in a 1
M AgNO3 solution. Calculate the standard cell potential of this cell at 25 oC.
Data: E (Mg2+/Mg) = − 2.37 V; E (Ag+/Ag) = + 0.80 V.
SOLUTION
Oxidation (Anode): Mg → Mg2+ + 2e− E0 = + 2.37 V
Reduction (Cathode): Ag+ + e− → Ag E0 = + 0.80 V
Overall Reaction: Mg + 2 Ag+ → Mg2+ + 2 Ag E0 = + 3.17 V
Exercise 4. Given the following cell diagram: Pt|Fe2+, Fe3+||Ag+|Ag
a) Write the overall reaction in the cell. Indicate the oxidizing and reducing species.
b) Calculate the equilibrium constant at 25 C if the standard potential of the cell at this temperature
is 0.028 V.
Data: E (Fe3+/ Fe2+) = + 0.77 V; E0 (Ag+/ Ag) =+ 0.80 V; R = 8.314 J K-1 mol-1; F = 96500 C mol-1.
0
SOLUTION
a) Oxidation (Anode): Fe2+ → Fe3+ + 1 e− E0 = − 0.77 V
Reduction (Cathode): Ag+ + e− → Ag E0 = + 0.80 V
Overall Reaction: Fe2+ + Ag+ → Fe3+ + 2 Ag E0 = + 0.03 V
Reducing agent: Fe2+
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EP 1.1. SOLUTIONS OF ELECTROCHEMISTRY I
Oxidizing agent: Ag+
b) K = e nFE°/RT; K = 2.97
Exercise 5. A cell built with an electrode of solid MnO2 introduced in a solution of Mn2+ (0.05 M) connected
to another electrode of solid Zn in a solution of Zn2+ (0.01 M) generates a potential of 1.947 V at 25 oC and
pH = 4.
a) Write the half-reactions that take place at the anode and at the cathode and balance the global
redox process. Identify the reducing and the oxidazing agents.
b) Reason qualitatively how the cell potential varies if pH increases.
Data: E0 (Zn2+/Zn) = − 0.76 V; E0 (MnO2/Mn2+) = + 1.23 V.
SOLUTION
a) Oxidation (Anode): Zn → Zn2+ + 2 e− E0 = + 0.76 V
Reduction (Cathode): MnO2 + 4 H+ + 2 e− → Mn2+ + 2 H2O E0 = + 1.23 V
Overall Reaction: Zn + MnO2 + 4 H+ → Zn2+ + Mn2+ + 2 H2O E0 = + 1.99 V
Reducing agent: Zn
Oxidizing agent: MnO2
b) The Nernst equation: E = E0 − (RT/nF) ln [Mn2+] [Zn2+] / [H+]4
If pH increases, [H+] decreases and E decreases.
Exercise 6. Calculate the potential of the following cell at 25 C:
Mg (s)Mg2+(0.24 M)Mg2+(0.53 M)Mg (s)
Data: E0 (Mg2+/Mg) = − 2.37 V.
SOLUTION
Concentration cell.
The Nernst equation: E = E0 – (RT/nF) ln [Mg2+]diluted/[Mg2+]concentrated
E = 0 – [(0.082 atm L K-1 mol-1 × 298 K) / (2 × 96500 C mol-1)] ln [0.24 M] / [0.53 M] = 0.010 V.
Exercise 7. Given the following cell diagram in acidic medium and at 25 C:
MnO2(s)Mn2+(aq)Ce4+(aq), Ce3+(aq)
a) Write the oxidation and reduction half-reactions and the adjusted overall redox equation.
b) If the electrochemical cell works under standard conditions, would it be spontaneous? Would it be
working as a galvanic cell or an electrolytic cell? Justify your answers.
If [Ce3+] = 10-2 M, [Ce4+] = 10-1 M, and [Mn2+] = 10-1 M:
c) Calculate the pH at which the electrochemical cell is able to generate a potential of +0.65 V.
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EP 1.1. SOLUTIONS OF ELECTROCHEMISTRY I
d) Calculate the concentration of a HF solution necessary to reach the pH obtained in d).
Data: E0 (MnO2/Mn2+) = + 1.23 V; E 0(Ce4+/Ce3+) = + 1.61 V; Ka (HF) = 6.6 × 10-4, R = 8.314 J K-1 mol-1; F = 96500
C mol-1.
SOLUTION
a) Oxidation (Anode): Mn2+ + 2 H2O → MnO2 + 4 H+ + 2 e− E0 = – 1.23 V
Reduction (Cathode): Ce4+ + 1 e− → Ce3+ E0 = + 1.61 V
Overall Reaction: Mn2+ + 2 H2O + 2 Ce4+ → MnO2 + 4 H+ + 2 Ce3+ E0 = + 0.38 V
b) Under standard conditions, the potential E0 = + 0.38 V, so G0 = −nFE0 < 0 and the process is spontaneous.
This cell works as a galvanic cell.
c) The Nernst equation: E = E0 − (RT/nF) ln [H+]4 [Ce3+]2/ [Mn2+] [Ce4+]2
0.65 V = 0.38 V − [(0.082 atm L K-1 mol-1 × 298 K) / (2× 96500 C mol-1)] ln [H+]4 × [0.01 M]2 / [0.1 M] × [0.1
M]2
[H+] = 9.12 × 10-3 M; pH = 2.04.
d) Ka = [F-][H+] / [HF]; 6.6 × 10-4 = x2 / ([HF]0 – x) where x = 9.12 × 10-3 M
The initial concentration of hydrofluoric acid will be: [HF]0 = 0.14 M.
