PROBLEMS
In these problems, temperature is 25 °C unless otherwise stated.
1. Calculate the value for 2.303 RT/F at 50 °C.
2. Calculate the exact half-cell potential for the Ag–AgCl electrode in 1 M
NaCl.
3. Calculate the exact half-cell potential of zinc in 0.01 M ZnCl2.
4. Calculate the half-cell potential of the hydrogen electrode in a solution of
pH = 7 and partial pressure of H2 = 0.5 atm at 40 °C.
5. The emf of a cell made up of zinc (anode) and hydrogen electrode (cathode)
immersed in 0.5 M ZnCl2 is +0.590 V. What is the pH of the solution?
6. Calculate the theoretical tendency of zinc to corrode (in volts) with evolution
of hydrogen when immersed in 0.01 M ZnCl2 acidified to pH = 2.
7. Calculate the theoretical tendency for nickel to corrode (in volts) in deaer-
ated water of pH = 7. Assume that the corrosion products are H2 and Ni(OH)2,
the solubility product of which is 1.6 × 10−16.
8. (a) What is the emf of a cell made up of a copper electrode and a hydrogen
electrode ( pH2 = 2 atm) in copper sulfate (activity Cu2+ = 1) of pH = 1?
(b) What is the polarity of the cell and which electrode is anode?
9. (a) Calculate whether copper will corrode in deaerated CuSO4, pH = 0, to
form Cu2+ (activity = 0.1) and H2 (1 atm). What is the corrosion tendency
in volts?
(b) Similarly, calculate whether copper will corrode in deaerated KCN
(activity CN− = 0.5) of pH = 10, assuming that Cu(CN)−2 is formed, the
activity of which is 10−4.
Cu(CN)−2 + e − → 2CN − + Cu φ = −0.446 V
10. (a) Calculate the emf of the following cell:
Pt; Fe3+ (activity = 0.1), Fe2 + (activity = 0.001), Ag + (activity = 0.01);
0 Ag
(b) Write the spontaneous reaction for the cell. What is the polarity and
which electrode is anode?
11. (a) Calculate the emf of a concentration cell made up of copper electrodes in
0.1 M CuSO4 and 0.5 M CuSO4, neglecting the liquid-junction potential.
(b) Write the spontaneous reaction of the cell and indicate which electrode
is anode.
12. (a) Calculate the emf of the following cell at 40 °C:
O2 (1 atm), Pt; H 2 O; O2 (0.1 atm), Pt
(b) What is the polarity and which electrode is anode?
13. a) Calculate the emf of a cell made up of a hydrogen electrode ( pH2 = 1atm )
(
and an oxygen electrode ( pO2 = 0.5 atm ) in 0.5 M NaOH.
(b) What is the polarity and which electrode is anode? (Assume that the
oxygen electrode is reversible.)
14. Calculate whether silver will corrode if immersed in 0.1M CuCl2 to form solid
AgCl. What is the corrosion tendency in volts?
15. Calculate whether silver will corrode with hydrogen evolution in deaerated
KCN solution, pH = 9, when CN− activity = 1.0 and Ag(CN)−2 activity is
0.001.
16. Zinc is immersed in a solution of CuCl2. What is the reaction and at what
activity ratio Zn2+/Cu2+ will the reaction stop?
17. Calculate the emf of a cell made up of iron and lead electrodes in a solution
of Fe2+ and Pb2+ of equal activity. Which electrode tends to corrode when the
cell is short-circuited?
18. Calculate the emf as in Problem 17 in an air-saturated alkaline solution of
pH = 10. Which electrode corrodes on short-circuiting the cell? (Assume that
HPbO−2 forms as corrosion product and that its activity is 0.1; also assume
that iron is passive and that its potential approximates the oxygen
electrode.)
HPbO−2 + H 2 O + 2e − → Pb + 3OH − φ = −0.54 V
19. Given Fe2+ + 2e− → Fe, φ° = −0.440 V, and Fe3+ + e− → Fe2+, φ° = 0.771 V, cal-
culate φ° for Fe3+ + 3e− → Fe.
20. Given O2 + 2H2O + 4e− → 4OH−, φ° = 0.401 V, calculate φ° for O2 + 4H+ + 4e−
→ 2H2O.
21. Calculate the pressure (fugacity) of hydrogen required to stop corrosion of
iron immersed in 0.1 M FeCl2, pH = 3.
22. Calculate the pressure of hydrogen, as in Problem 21, in deaerated water with
Fe(OH)2 as the corrosion product. [Solubility product Fe(OH)2 = 1.8 ×
10−15.]
23. Calculate the pressure of hydrogen required to stop corrosion of cadmium
at 25 °C in deaerated water, with Cd(OH)2 as the corrosion product. [Solubil-
ity product Cd(OH)2 = 2.0 × 10−14.]
24. A copper storage tank containing dilute H2SO4 at pH = 0.1 is blanketed with
hydrogen at 1 atm. Calculate the maximum Cu2+ contamination of the acid
in moles Cu2+ per liter. What is the corresponding contamination if the hydro-
gen partial pressure is reduced to 10−4 atm?
Answers to Problems
1. 0.0641 V.
2. 0.233 V.
3. −0.827 V.
4. −0.426 V.
5. 3.28.
6. 0.709 V.
7. −0.111 V.
8. −0.405 V; H2 electrode is negative and is the anode.
9. (a) No; −0.307 V.
(b) Yes; 0.056 V.
10. (a) 0.208 V.
(b) Ag is negative and is the anode.
11. (a) 0.0096 V.
(b) 0.1M CuSO4 electrode is anode.
12. (a) 0.0155 V.
(b) 0.1 atm O2 electrode is negative and is the anode.
13. 1.225 V; H2 electrode is negative and is the anode.
14. Yes; 0.019 V.
15. No; emf = −0.045 V.
16. 1.45 × 1037.
17. 0.314 V; Fe.
18. −0.84 V; Pb.
19. −0.036 V.
20. 1.23 V.
21. 1.26 × 1010 atm.
22. 42 atm.
23. 0.42 atm.
24. 2.6 × 10−12; 2.6 × 10−8 mole/liter.
PROBLEMS 41
