PROBLEMS

In these problems, temperature is 25 C unless otherwise stated.

1. Calculate the value for 2.303 RT/F at 50 C.
2.
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 ZnCl 2 .
4. Calculate the half - cell potential of the hydrogen electrode in a solution of
pH = 7 and partial pressure of H 2 = 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 ZnCl 2 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 ZnCl 2 acidifi ed to pH = 2.
7. Calculate the theoretical tendency for nickel to corrode (in volts) in deaerated
water of pH = 7. Assume that the corrosion products are H 2 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 Cu 2+ = 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 CuSO 4 , pH = 0, to
form Cu 2+ (activity = 0.1) and H 2 (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)2e2CNCu _0.446V
10. ( a ) Calculate the emf of the following cell:
Pt; Fe3(activity0.1), Fe2(activity0.001), Ag(activity 0.01); 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 CuSO 4 and 0.5 M CuSO 4 , 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(1atm), Pt; H2O;O2(0.1atm), 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 ( pH atm 2 1 )

and an oxygen electrode ( pO atm 2 0.5 ) 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 0.1 M CuCl 2 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 CuCl 2 . What is the reaction and at what
activity ratio Zn 2+ /Cu 2+ will the reaction stop?
17. Calculate the emf of a cell made up of iron and lead electrodes in a solution
of Fe 2+ and Pb 2+ 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
HPbO2
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.)
HPbO2H2O2ePb3OH _0.54V
19. Given Fe 2+ + 2 e Fe,
= 0.440 V, and Fe
for Fe 3+ + 3 e Fe.

3+

+ e Fe

2+

, = 0.771 V, calculate

20. Given O 2 + 2H 2 O + 4 e 4OH

, = 0.401 V, calculate for O 2 + 4H

2H
2 O.

+4e

21. Calculate the pressure (fugacity) of hydrogen required to stop corrosion of

iron immersed in 0.1 M FeCl 2 , 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. [Solubility
product Cd(OH) 2 = 2.0 10 14 .]
24. A copper storage tank containing dilute H 2 SO 4 at pH = 0.1 is blanketed with
hydrogen at 1 atm. Calculate the maximum Cu 2+ contamination of the acid
in moles Cu 2+ per liter. What is the corresponding contamination if the hydrogen
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; H 2 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 ) 0.1 M CuSO 4 electrode is anode.
12. ( a ) 0.0155 V.
( b ) 0.1 atm O 2 electrode is negative and is the anode.
13. 1.225 V; H 2 electrode is negative and is the anode.
14. Yes; 0.019 V.
15. No; emf = 0.045 V.
16. 1.45 10 37 .
17. 0.314 V; Fe.
18. 0.84 V; Pb.
19. 0.036 V.
20. 1.23 V.
21. 1.26 10 10 atm.
22. 42 atm.
23. 0.42 atm.
24. 2.6 10 12 ; 2.6 10 8 mole/liter.