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Exercises 511

Discussion Questions
These questions are designed to be considered by groups of solutions contain the same compound, but at different
students in class. Often these questions work well for intro- concentrations. How could this cell run spontaneously?
ducing a particular topic in class. 9. Explain why cell potentials are not multiplied by the
1. Sketch a galvanic cell, and explain how it works. Look at coefficients in the balanced equation. (Hint: Use the rela-
Figs. 11.1 and 11.2. Explain what is occurring in each tionship between G and cell potential.)
container and why the cell in Fig. 11.2 “works” but the 10. What is the difference between  and ? When is 
one in Fig. 11.1 does not. equal to zero? When is  equal to zero? (Consider “reg-
2. In making a specific galvanic cell, explain how one deter- ular” galvanic cells as well as concentration cells.)
mines which electrodes and solutions to use in the cell. 11. Consider the following galvanic cell:
3. You want to “plate out” nickel metal from a nickel nitrate
solution onto a piece of metal inserted into the solution.
Should you use copper or zinc (or can you use either)?
Explain. Zn Ag
4. A copper penny can be dissolved in nitric acid but not in
hydrochloric acid. Using reduction potentials given in the
book, show why this is so. What are the products of the
reaction? Newer pennies contain a mixture of zinc and
copper. What happens to the zinc in the penny when 1.0 M Zn2+ 1.0 M Ag+
placed in nitric acid? Hydrochloric acid? Support your
explanations with the data from the book, and include
balanced equations for all reactions.
5. Sketch a cell that forms iron metal from iron(II) while What happens to  as the concentration of Zn2 is
changing chromium metal to chromium(III). Calculate increased? as the concentration of Ag is increased?
the voltage, show the electron flow, label the anode and What happens to  in these cases?
cathode, and balance the overall cell equation. 12. Look up the reduction potential for Fe3 to Fe2. Look
6. Which of the following is the best reducing agent: F2, up the reduction potential for Fe2 to Fe. Finally, look
H, Na, Na, or F? Explain. Order as many of these up the reduction potential for Fe3 to Fe. You should
species as possible from the best to the worst oxidizing notice that adding the reduction potentials for the first
agent. Why can’t you order all of them? From Table 11.1 two does not give you the potential for the third. Why
choose the species that is the best oxidizing agent. not? Show how you can use the first two potentials to
Choose the best reducing agent. Explain. calculate the third potential.
7. You are told that metal A is a better reducing agent than 13. If the cell potential is proportional to work and the stan-
metal B. What, if anything, can be said about A com- dard reduction potential for the hydrogen ion is zero,
pared with B? Explain. does this mean that the reduction of the hydrogen ion
8. Explain the following relationships: G and w, cell poten- requires no work?
tial and w, cell potential and G, cell potential and Q. 14. Is the following statement true or false? Concentration
Using these relationships, explain how you could make a cells work because standard reduction potentials are
cell in which both electrodes are the same metal and both dependent on concentration. Explain.

Exercises
A blue exercise number indicates that the answer to that 16. When magnesium metal is added to a beaker of HCl(aq),
exercise appears at the back of this book and a solution a gas is produced. Knowing that magnesium is oxidized
appears in the Solutions Guide. and that hydrogen is reduced, write the balanced equation
for the reaction. How many electrons are transferred in the
Galvanic Cells, Cell Potentials, and Standard balanced equation? What quantity of useful work can be
Reduction Potentials obtained when Mg is added directly to the beaker of HCl?
15. What is electrochemistry? What are redox reactions? How can you harness this reaction to do useful work?
Explain the difference between a galvanic cell and an elec- 17. Sketch the galvanic cells based on the following overall
trolytic cell. reactions. Calculate , show the direction of electron
512 CHAPTER 11 Electrochemistry

flow and the direction of ion migration through the salt relative to the standard hydrogen electrode. Calculate the
bridge, identify the cathode and anode, and give the over- potential for each of the following galvanic cells contain-
all balanced reaction. Assume that all concentrations are ing a saturated calomel electrode and the given half-cell
1.0 M and that all partial pressures are 1.0 atm. Stan- components as standard conditions. In each case indicate
dard reduction potentials are found in Table 11.1. whether the SCE is the cathode or the anode. Standard
a. Cr3(aq)  Cl2(g) 34 Cr2O72(aq)  Cl(aq) reduction potentials are found in Table 11.1.
b. Cu2(aq)  Mg(s) 34 Mg2(aq)  Cu(s) a. Cu2  2e 88n Cu
c. IO3(aq)  Fe2(aq) 34 Fe3(aq)  I2(s) b. Fe3  e 88n Fe2
d. Zn(s)  Ag(aq) 34 Zn2(aq)  Ag(s) c. AgCl  e 88n Ag  Cl
18. Calculate  values for the following cells. Which reac- d. Al3  3e 88n Al
tions are spontaneous as written (under standard condi- e. Ni2  2e 88n Ni
tions)? Balance the reactions. Standard reduction poten- 23. Answer the following questions using data from Table
tials are found in Table 11.1. 11.1 (all under standard conditions).
a. MnO4(aq)  I(aq) 34 I2(aq)  Mn2(aq) a. Is H(aq) capable of oxidizing Cu(s) to Cu2(aq)?
b. MnO4(aq)  F(aq) 34 F2(g)  Mn2(aq) b. Is Fe3(aq) capable of oxidizing I(aq)?
c. H2(g) 34 H(aq)  H(aq) c. Is H2(g) capable of reducing Ag(aq)?
d. Au3(aq)  Ag(s) 34 Ag(aq)  Au(s) d. Is Fe2(aq) capable of reducing Cr3(aq) to Cr2(aq)?
19. Sketch the galvanic cells based on the following half- 24. Using data from Table 11.1, place the following in order
reactions. Calculate , show the direction of electron of increasing strength as oxidizing agents (all under stan-
flow and the direction of ion migration through the salt dard conditions).
bridge, identify the cathode and anode, and give the over-
all balanced reaction. Assume that all concentrations are Cd2, IO3, K, H2O, AuCl4, and I2
1.0 M and that all partial pressures are 1.0 atm. 25. Using data from Table 11.1, place the following in order
a. Cl2  2e 88n 2Cl   1.36 V of increasing strength as reducing agents (all under stan-
Br2  2e 88n 2Br   1.09 V dard conditions).
b. MnO4  8H  5e
88n Mn2  4H2O   1.51 V Cu, F, H, H2O, I2, and K
IO4  2H  2e

26. Consider only the species (at standard conditions)
88n IO3  H2O   1.60 V
c. H2O2  2H  2e88n 2H2O   1.78 V Na, Cl, Ag, Ag, Zn2, Zn, and Pb
O2  2H 2e 88n H2O2   0.68 V
d. Mn2  2e 88n Mn   1.18 V in answering the following questions. Give reasons for
Fe3  3e 88n Fe   0.036 V your answers. (Use data from Table 11.1.)
a. Which is the strongest oxidizing agent?
20. Consider the following galvanic cells:
b. Which is the strongest reducing agent?
c. Which species can be oxidized by SO42(aq) in acid?
d. Which species can be reduced by Al(s)?
Au Pt Cd Pt
27. Use the table of standard reduction potentials (Table
11.1) to pick a reagent that is capable of each of the fol-
lowing oxidations (under standard conditions in acidic
solution).
1.0 M Au3+ 1.0 M Cu+ 1.0 M Cd2+ 1.0 M VO2+
a. oxidizes Br to Br2 but does not oxidize Cl to Cl2
1.0 M Cu2+ 1.0 M H+
b. oxidizes Mn to Mn2 but does not oxidize Ni to Ni2
1.0 M VO2+
28. Use the table of standard reduction potentials (Table
a. b. 11.1) to pick a reagent that is capable of each of the fol-
For each galvanic cell, give the balanced cell reaction and lowing reductions (under standard conditions in acidic
determine . Standard reduction potentials are found in solution).
Table 11.1. a. reduces Cu2 to Cu but does not reduce Cu2 to Cu
b. reduces Br2 to Br but does not reduce I2 to I
21. Give the standard line notation for each cell in Exer-
cise 19. 29. Hydrazine is somewhat toxic. Use the half-reactions
shown below to explain why household bleach (a highly
22. The saturated calomel electrode, abbreviated SCE, is often alkaline solution of sodium hypochlorite) should not be
used as a reference electrode in making electrochemical mixed with household ammonia or glass cleansers that
measurements. The SCE is composed of mercury in con- contain ammonia.
tact with a saturated solution of calomel (Hg2Cl2). The
electrolyte solution is saturated KCl. SCE is 0.242 V ClO  H2O  2e 88n 2OH  Cl   0.90 V
Exercises 513

N2H4  2H2O  2e 88n 2NH3  2OH a. Calculate  and G at 298 K for the fuel-cell
  0.10 V reaction.
b. Predict the signs of H and S for the fuel-cell
30. A patent attorney has asked for your advice concerning reaction.
the merits of a patent application claiming the invention c. As temperature increases, does the maximum
of an aqueous single galvanic cell capable of producing a amount of work obtained from the fuel-cell reaction
12-V potential. Comment. increase, decrease, or remain the same? Explain.
Cell Potential, Free Energy, and Equilibrium 39. Combine the equations
31. The free energy change for a reaction G is an extensive G  nF and G  H  TS
property. What is an extensive property? Surprisingly, one
can calculate G from the cell potential  for the reac- to derive an expression for  as a function of tempera-
tion. This is surprising because  is an intensive property. ture. Describe how one can graphically determine H
How can the extensive property G be calculated from and S from measurements of  at different tempera-
the intensive property ? tures, assuming that H and S do not depend on tem-
perature. What property would you look for in designing
32. The equation G  nF also can be applied to half-
a reference half-cell that would produce a potential rela-
reactions. Use standard reduction potentials to estimate
tively stable with respect to temperature?
Gf for Fe2(aq) and Fe3(aq). (Gf for e  0.)
40. Calculate  for the reaction
33. Calculate the maximum amount of work that can be ob-
3
tained from the galvanic cells at standard conditions in CH3OH(l)  2O2(g) 88n CO2(g)  2H2O(l)
Exercise 20.
using values of Gf in Appendix 4. Will  increase or
34. Under standard conditions, what reaction occurs, if any, decrease with an increase in temperature? (See Exercise
when each of the following operations are performed? 39 for the dependence of  on temperature.)
a. Crystals of I2 are added to a solution of NaCl.
b. Cl2 gas is bubbled into a solution of NaI. 41. A disproportionation reaction involves a substance that
c. A silver wire is placed in a solution of CuCl2. acts as both an oxidizing agent and a reducing agent,
d. An acidic solution of FeSO4 is exposed to air. producing higher and lower oxidation states of the same
element in the products. Which of the following dispro-
For the reactions that occur, write a balanced equation portionation reactions are spontaneous under standard
and calculate , G, and K at 25C. conditions? Calculate G and K at 25C for those reac-
35. Calculate G and K at 25C for the galvanic cell reac- tions that are spontaneous under standard conditions.
tions in Exercise 19. a. 2Cu(aq) 88n Cu2(aq)  Cu(s)
36. Chlorine dioxide (ClO2), which is produced by the reaction b. 3Fe2(aq) 88n 2Fe3(aq)  Fe(s)
c. HClO2(aq) 88n ClO3(aq)  HClO(aq) (unbalanced)
2NaClO2(aq)  Cl2(g) 88n 2ClO2(g)  2NaCl(aq)
Use the half-reactions:
has been tested as a disinfectant for municipal water
treatment. ClO3  3H  2e 88n HClO2  H2O   1.21 V
a. Using data from Table 11.1, calculate , G, and
HClO2  2H  2e 88n HClO  H2O   1.65 V
K at 25C for the production of ClO2.
b. One of the concerns in using ClO2 as a disinfectant is 42. Calculate the value of the equilibrium constant for the re-
that the carcinogenic chlorate ion (ClO3) might be a action of zinc metal in a solution of silver nitrate at 25C.
by-product. It can be formed from the reaction 43. For the following half-reaction,   2.07 V:
ClO2(g) 34 ClO3(aq)  Cl(aq)
AlF63  3e 88n Al  6F
Balance the equation for the decomposition of ClO2.
Using data from Table 11.1, calculate the equilibrium con-
37. The amount of manganese in steel is determined by chang- stant at 25C for the reaction
ing it to permanganate ion. The steel is first dissolved in
nitric acid, producing Mn2 ions. These ions are then Al3(aq)  6F(aq) 34 AlF63(aq)
oxidized to the deeply colored MnO4 ions by periodate
44. Calculate Ksp for iron(II) sulfide given the following data:
ion (IO4) in acid solution.
a. Complete and balance an equation describing each FeS(s)  2e 88n Fe(s)  S2(aq)   1.01 V
of the above reactions.
Fe2(aq)  2e 88n Fe(s)   0.44 V
b. Calculate , G, and K at 25C for each reaction.
38. The overall reaction and equilibrium constant value for a 45. The solubility product for CuI(s) is 1.1  1012. Calcu-
hydrogen–oxygen fuel cell at 298 K is late the value of  for the half-reaction
2H2(g)  O2(g) 88n 2H2O(l) K  1.28  1083 CuI  e 88n Cu  I
514 CHAPTER 11 Electrochemistry

Galvanic Cells: Concentration Dependence 52. A chemist wishes to determine the concentration of
46. Calculate the pH of the cathode compartment for the fol- CrO42 electrochemically. A cell is constructed consisting
lowing reaction given cell  3.01 V when [Cr3]  of a saturated calomel electrode (SCE; see Exercise 22)
0.15 M, [Al3]  0.30 M, and [Cr2O72]  0.55 M. and a silver wire coated with Ag2CrO4. The  value for
the following half-reaction is 0.446 V relative to the
2Al(s)  Cr2O72(aq)  14H(aq) 88n standard hydrogen electrode:
2Al3(aq)  2Cr3(aq)  7H2O(l)
Ag2CrO4  2e 88n 2Ag  CrO42
47. Consider the galvanic cell based on the following half-
a. Calculate cell and G at 25C for the cell reaction
reactions:
when [CrO42]  1.00 mol/L.
Au3  3e 88n Au   1.50 V b. Write the Nernst equation for the cell. Assume that

Tl  e 
88n Tl   0.34 V the SCE concentrations are constant.
c. If the coated silver wire is placed in a solution (at
a. Determine the overall cell reaction and calculate cell. 25C) in which [CrO42]  1.00  105 M, what is
b. Calculate G and K for the cell reaction at 25C. the expected cell potential?
c. Calculate cell at 25C when [Au3]  1.0  102 M d. The measured cell potential at 25C is 0.504 V when
and [Tl]  1.0  104 M. the coated wire is dipped into a solution of unknown
48. Consider the following galvanic cell at 25C: [CrO42]. What is the [CrO42] for this solution?
e. Using data from this problem and from Table 11.1,
Pt⏐Cr2(0.30 M), Cr3(2.0 M)⏐⏐Co2(0.20 M)⏐Co
calculate the solubility product (Ksp) for Ag2CrO4.
The overall reaction and equilibrium constant value are 53. What are concentration cells? What is  in a concentra-
2Cr2(aq)  Co2(aq) 88n tion cell? What is the driving force for a concentration
2Cr3(aq)  Co(s) K  2.79  107 cell to produce a voltage? Is the higher or the lower ion
concentration solution present at the anode? When the
Calculate the cell potential  for this galvanic cell and G anode ion concentration is decreased and/or the cathode
for the cell reaction at these conditions. ion concentration is increased, both give rise to larger cell
49. Consider the cell described below: potentials. Why?
Al⏐Al3(1.00 M)⏐⏐Pb2 (1.00 M)⏐Pb 54. Concentration cells are commonly used to calculate the
value of equilibrium constants for various reactions. For
Calculate the cell potential after the reaction has example, the silver concentration cell illustrated in Fig.
operated long enough for the [Al3] to have changed by 11.11 can be used to determine the Ksp value for AgCl(s).
0.60 mol/L. (Assume T  25C.) To do so, NaCl is added to the anode compartment un-
50. The Nernst equation can be applied to half-reactions. til no more precipitate forms. The [Cl] in solution is then
Calculate the reduction potential at 25C of each of the determined somehow. What happens to cell when NaCl
following half-cells. is added to the anode compartment? To calculate the Ksp
a. Cu/Cu2 (0.10 M) value, [Ag] must be calculated. Given the value of cell,
(The half-reaction is Cu2  2e  Cu.) how is [Ag] determined at the anode?
b. Cu/Cu2 (2.0 M) 55. Consider the concentration cell shown below. Calculate the
c. Cu/Cu2(1.0  104 M) cell potential at 25C when the concentration of Ni2 in the
d. MnO4 (0.10 M)/Mn2 (0.010 M) at pH  3.00 compartment on the right has each of the following values.
(The half-reaction is MnO4  8H  5e 
Mn2  4H2O.)
e. MnO4 (0.10 M)/Mn2 (0.010 M) at pH  1.00 Ni Ni
51. The overall reaction in the lead storage battery is
Pb(s)  PbO2(s)  2H(aq)  2HSO4(aq)
88n 2PbSO4(s)  2H2O(l)
a. Calculate  at 25C for this battery when
[H2SO4]  4.5 M; that is, [H]  [HSO4]  4.5 M. [Ni2+] = 1.0 M
At 25C,   2.04 V for the lead storage battery.
b. For the cell reaction H  315.9 kJ and S 
263.5 J/K. Calculate  at 20.C. (See Exercise 39.) a. 1.0 M d. 4.0  105 M
c. Calculate  at 20.C when [H2SO4]  4.5 M. b. 2.0 M e. Calculate the potential when both
d. Based on your previous answers, why does it seem that c. 0.10 M solutions are 2.5 M in Ni2.
batteries fail more often on cold days than on warm For each case, identify the cathode, the anode, and the
days? direction in which electrons flow.
Exercises 515

56. Consider a concentration cell that has both electrodes Electrolysis


made of some metal M. Solution A in one compartment 60. How long will it take to plate out each of the following
of the cell contains 1.0 M M2. Solution B in the other with a current of 100.0 A?
cell compartment has a volume of 1.00 L. At the begin- a. 1.0 kg of Al from aqueous Al3
ning of the experiment 0.0100 mol of M(NO3)2 and b. 1.0 g of Ni from aqueous Ni2
0.0100 mol of Na2SO4 are dissolved in solution B (ignore c. 5.0 mol of Ag from aqueous Ag
volume changes), where the reaction
61. What mass of each of the following substances can be
M2(aq)  SO42(aq) 34 MSO4(s) produced in 1.0 h with a current of 15 A?
a. Co from aqueous Co2 c. I2 from aqueous KI
occurs. For this reaction equilibrium is rapidly established, b. Hf from aqueous Hf4 d. Cr from molten CrO3
whereupon the cell potential is found to be 0.44 V at
25C. Assume that the process 62. It took 2.30 min with a current of 2.00 A to plate out all
the silver from 0.250 L of a solution containing Ag. What
M2  2e 88n M was the original concentration of Ag in the solution?

has a standard reduction potential of 0.80 V and that 63. The electrolysis of BiO produces pure bismuth. How
no other redox process occurs in the cell. Calculate the long would it take to produce 10.0 g of Bi by the elec-
value of Ksp for MSO4(s) at 25C. trolysis of a BiO solution using a current of 25.0 A?

57. An electrochemical cell consists of a standard hydrogen 64. Why is the electrolysis of molten salts much easier to pre-
electrode and a copper metal electrode. dict in terms of what occurs at the anode and cathode
a. What is the potential of the cell at 25C if the copper than the electrolysis of aqueous dissolved salts?
electrode is placed in a solution in which [Cu2] 
65. What reactions take place at the cathode and the anode
2.5  104 M?
when each of the following is electrolyzed? Assume stan-
b. If the copper electrode is placed in a solution of
dard conditions.
0.10 M NaOH that is saturated with Cu(OH)2,
what is the cell potential at 25C? For Cu(OH)2,
a. molten NiBr2 d. 1.0 M NiBr2 solution
Ksp  1.6  1019. b. molten AlF3 e. 1.0 M AlF3 solution
c. The copper electrode is placed in a solution of un- c. molten MnI2 f. 1.0 M MnI2 solution
known [Cu2]. The measured potential at 25C is 66. a. In the electrolysis of an aqueous solution of Na2SO4,
0.195 V. What is [Cu2]? (Assume that Cu2 is what reactions occur at the anode and the cathode
reduced.) (assuming standard conditions)?
d. If you wish to construct a calibration curve to show
how the cell potential varies with [Cu2], what 
should you plot to obtain a straight line? What will S2O82
 2e
88n 2SO4 2
2.01 V
the slope of this line be?
O2  4H  4e 88n 2H2O 1.23 V
58. An electrochemical cell consists of a nickel metal electrode
 
immersed in a solution with [Ni2]  1.0 M separated by 2H2O  2e 88n H2  2OH 0.83 V
a porous disk from an aluminum metal electrode im- 
Na  e 
88n Na 2.71 V
mersed in a solution with [Al3]  1.0 M. Sodium hy-
droxide is added to the aluminum compartment, causing b. When water containing a small amount (0.01 M)
Al(OH)3(s) to precipitate. After precipitation of Al(OH)3 of sodium sulfate is electrolyzed, measurement of the
has ceased, the concentration of OH is 1.0  104 M, volume of gases generated consistently gives a result
and the measured cell potential is 1.82 V. Calculate the that the volume ratio of hydrogen to oxygen is not
Ksp value for Al(OH)3. quite 2:1. To what do you attribute this discrep-
ancy? Predict whether the measured ratio is greater
Al(OH)3(s) 34 Al3(aq)  3OH(aq) Ksp  ? than or less than 2:1.

59. You have a concentration cell in which the cathode has a 67. A solution at 25C contains 1.0 M Cd2, 1.0 M Ag, 1.0
silver electrode with 0.10 M Ag. The anode also has a M u3, and 1.0 M Ni2 in the cathode compartment of
silver electrode with Ag(aq), 0.050 M S2O32, and 1.0  an electrolytic cell. Predict the order in which the metals
103 M Ag(S2O3)23. You read the voltage to be 0.76 V. will plate out as the voltage is gradually increased.
a. Calculate the concentration of Ag at the anode.
b. Determine the value of the equilibrium constant for 68. An aqueous solution of an unknown salt of ruthenium is
the formation of Ag(S2O3)23. electrolyzed by a current of 2.50 A passing for 50.0 min.
If 2.618 g Ru is produced at the cathode, what is the
Ag(aq)  2S2O32(aq) 34 Ag(S2O3)23(aq) K? charge on the ruthenium ions in solution?
516 CHAPTER 11 Electrochemistry

69. Consider the following half-reactions: The NCO(CH2)4 OCN is then chemically reduced by hy-
drogen to H2NO(CH2)6 ONH2, which is used in the pro-
IrCl63  3e 88n Ir  6Cl   0.77 V
duction of nylon. What current must be used to produce
 
PtCl4 2
 2e 88n Pt  4Cl   0.73 V 150. kg of NCO(CH2)4 OCN per hour?
PdCl4 2 
 2e 88n Pd  4Cl 
  0.62 V 73. What volume of F2 gas, at 25C and 1.00 atm, is produced
when molten KF is electrolyzed by a current of 10.0 A
A hydrochloric acid solution contains platinum, palladium, for 2.00 h? What mass of potassium metal is produced?
and iridium as chloro-complex ions. The solution is a con- At which electrode does each reaction occur?
stant 1.0 M in chloride ion and 0.020 M in each complex
74. It takes 15 kWh (kilowatt hours) of electrical energy to
ion. Is it feasible to separate the three metals from this so-
produce 1.0 kg of aluminum metal from aluminum oxide
lution by electrolysis? (Assume that 99% of a metal must
by the Hall–Heroult process. Compare this value with the
be plated out before another metal begins to plate out.)
amount of energy necessary to melt 1.0 kg of aluminum
70. An unknown metal M is electrolyzed. It took 74.1 s for metal. Why is it economically feasible to recycle aluminum
a current of 2.00 A to plate out 0.107 g of the metal from cans? (The enthalpy of fusion for aluminum metal is
a solution containing M(NO3)3. Identify the metal. 10.7 kJ/mol and 1 watt  1 J/s.)
71. Electrolysis of an alkaline earth metal chloride using a 75. In the electrolysis of a sodium chloride solution, what vol-
current of 5.00 A for 748 seconds deposits 0.471 g of ume of Cl2(g) is produced in the same time it takes to
metal at the cathode. What is the identity of the alkaline produce 6.00 L of H2(g), both volumes measured at 0C
earth metal chloride? and 1.00 atm?
72. One of the few industrial-scale processes that produces 76. What volumes of H2(g) and O2(g) at STP are produced
organic compounds electrochemically is used by the Mon- from the electrolysis of water by a current of 2.50 A in
santo Company to produce 1,4-dicyanobutane. The re- 15.0 min?
duction reaction is
2CH2 PCHCN  2H  2e 88n NCO(CH2)4 OCN

Additional Exercises
77. An experimental fuel cell has been designed that uses car- The maximum work 1 mol of alcohol can yield by this
bon monoxide as fuel. The overall reaction is process is 1320 kJ. What is the theoretical maximum volt-
age this cell can achieve?
2CO(g)  O2(g) 88n 2CO2(g)
80. What is the maximum work that can be obtained from a
The two half-cell reactions are
hydrogen–oxygen fuel cell at standard conditions that
CO  O2 88n CO2  2e produces 1.00 kg of water at 25C? Why do we say that
this is the maximum work that can be obtained? What
O2  4e 88n 2O2
are the advantages and disadvantages in using fuel cells
The two half-reactions are carried out in separate com- rather than the corresponding combustion reactions to
partments connected with a solid mixture of CeO2 and produce electricity?
Gd2O3. Oxide ions can move through this solid at high
81. The overall reaction and standard cell potential at 25C
temperatures (about 800C). G for the overall reaction
for the rechargeable nickel–cadmium alkaline battery is
at 800C under certain concentration conditions is 380
kJ. Calculate the cell potential for this fuel cell at the same Cd(s)  NiO2(s)  2H2O(l)
temperature and concentration conditions.
88n Ni(OH)2(s)  Cd(OH)2(s)   1.10 V
78. Batteries are galvanic cells. What happens to cell as a
battery discharges? Does a battery represent a system at For every mole of Cd consumed in the cell, what is the
equilibrium? Explain. What is cell when a battery reaches maximum useful work that can be obtained at standard
equilibrium? How are batteries and fuel cells alike? How conditions?
are they different? The U.S. space program uses hydro-
gen–oxygen fuel cells to produce power for its spacecraft. 82. Not all spontaneous redox reactions produce wonderful
What is a hydrogen–oxygen fuel cell? results. Corrosion is an example of a spontaneous redox
process that has negative effects. What happens in the cor-
79. A fuel cell designed to react grain alcohol with oxygen
rosion of a metal such as iron? What must be present for
has the following net reaction:
the corrosion of iron to take place? How can moisture
C2H5OH(l)  3O2(g) 88n 2CO2(g)  3H2O(l) and salt increase the severity of corrosion?
Additional Exercises 517

83. Explain how the following protect metals from corrosion. ref  0.250 V and that meas  0.480 V.
a. paint d. sacrificial metal a. What is the uncertainty in the values of pH and
b. durable oxide coatings e. alloying [H] if the uncertainty in the measured potential is
c. galvanizing f. cathodic protection 1 mV ( 0.001 V)?
84. In theory, most metals should easily corrode in air. Why? b. To what accuracy must the potential be measured
A group of metals called the noble metals are relatively for the uncertainty in pH to be 0.02 pH unit?
difficult to corrode in air. Some noble metals include gold, 90. The black silver sulfide discoloration of silverware can
platinum, and silver. Reference Table 11.1 to come up easily be removed by heating the silver article in a sodium
with a possible reason why the noble metals are relatively carbonate solution in an aluminum pan. The reaction is
difficult to corrode.
85. In 1973 the wreckage of the Civil War ironclad USS Mon- 3Ag2S(s)  2Al(s) 34 6Ag(s)  3S2(aq)  2Al3(aq)
itor was discovered near Cape Hatteras, North Carolina. a. Using data in Appendix 4, calculate G, K, and 
[The Monitor and the CSS Virginia (formerly the USS for the above reaction. [For Al3(aq), Gf 
Merrimack) fought the first battle between iron-armored 480. kJ/mol.]
ships.] In 1987 investigations were begun to see whether b. Calculate the value of the standard reduction poten-
the ship could be salvaged. Time reported (June 22, 1987) tial for the following half-reaction:
that scientists were considering adding sacrificial anodes of
zinc to the rapidly corroding metal hull of the Monitor. 2e  Ag2S(s) 88n 2Ag(s)  S2(aq)
Describe how attaching zinc to the hull would protect the
Monitor from further corrosion. 91. Consider the standard galvanic cell based on the follow-
ing half-reactions
86. A standard galvanic cell is constructed so that the over-
all cell reaction is Cu2  2e 88n Cu
2Al3(aq)  3M(s) 88n 3M2(aq)  2Al(s) Ag  e 88n Ag
where M is an unknown metal. If G  411 kJ for the The electrodes in this cell are Ag(s) and Cu(s). Does the
overall cell reaction, identify the metal used to construct cell potential increase, decrease, or remain the same when
the standard cell. the following changes occur to the standard cell?
87. Consider the following half-reactions: a. CuSO4(s) is added to the copper half-cell compart-
ment (assume no volume change).
Pt2  2e 88n Pt   1.188 V b. NH3(aq) is added to the copper half-cell compart-
PtCl42  2e 88n Pt  4Cl   0.755 V ment. [Hint: Cu2 reacts with NH3 to form
Cu(NH3)42(aq).]
  
NO3  4H  3e 88n NO  2H2O   0.96 V c. NaCl(s) is added to the silver half-cell compartment.
Explain why platinum metal will dissolve in aqua regia [Hint: Ag reacts with Cl to form AgCl(s).]
(a mixture of hydrochloric and nitric acids) but not in d. Water is added to both half-cell compartments until
either concentrated nitric or concentrated hydrochloric the volume of solution is doubled.
acid individually. e. The silver electrode is replaced with a platinum electrode.
88. Consider the following reduction potentials: Pt2  2e 88n Pt   1.19 V

Co 3
 3e 88n Co   1.26 V 92. Consider a cell based on the following half-reactions:

Co2
 2e 88n Co   0.28 V Au3  3e 88n Au   1.50 V
a. When cobalt metal dissolves in 1.0 M nitric acid, Fe3  e 88n Fe2   0.77 V
will Co3 or Co2 be the primary product (assum-
ing standard conditions)? a. Draw this cell under standard conditions, labeling
b. Is it possible to change the concentration of HNO3 the anode, the cathode, the direction of electron
to get a different result in part a? flow, and the concentrations, as appropriate.
89. The measurement of pH using a glass electrode obeys the b. When enough NaCl(s) is added to the compartment
Nernst equation. The typical response of a pH meter at containing gold to make [Cl]  0.10 M, the cell
25.00C is given by the equation potential is observed to be 0.31 V. Assume that
Au3 is reduced and that the reaction in the com-
meas  ref  0.05916 pH partment containing gold is
where ref contains the potential of the reference electrode Au3(aq)  4Cl(aq) 34 AuCl4(aq)
and all other potentials that arise in the cell that are not
related to the hydrogen ion concentration. Assume that Calculate the value of K for this reaction at 25C.
518 CHAPTER 11 Electrochemistry

Challenge Problems
93. Three electrochemical cells were connected in series so the minimum pH at which 99% of the fluoride is
that the same quantity of electrical current passes through present as F and only 1% is present as HF?
all three cells. In the first cell, 1.15 g of chromium metal e. Buffering agents are added to solutions containing
was deposited from a chromium(III) nitrate solution. In fluoride before making measurements with a
the second cell, 3.15 g of osmium was deposited from fluoride-selective electrode. Why?
a solution made of Osn and nitrate ions. What is the 97. When copper reacts with nitric acid, a mixture of NO(g)
name of the salt? In the third cell, the electrical charge and NO2(g) is evolved. The volume ratio of the two
passed through a solution containing X2 ions caused product gases depends on the concentration of the ni-
deposition of 2.11 g of metallic X. Identify X. tric acid according to the equilibrium
94. An electrochemical cell is set up using the following un-
2H(aq)  2NO3(aq)  NO(g) 34 3NO2(g)  H2O(l)
balanced reaction:
Consider the following standard reduction potentials at
Ma(aq)  N(s) 88n N2(aq)  M(s)
25C:
The standard reduction potentials are
3e  4H(aq)  NO3(aq) 88n NO(g)  2H2O(l)
a 
M  ae 88n M   0.400 V   0.957 V

N 2
 2e 88n N   0.240 V e  2H(aq)  NO3(aq) 88n NO2(g)  H2O(l)
2
The cell contains 0.10 M N and produces a voltage   0.775 V
of 0.180 V. If the concentration of Ma is such that the
value of the reaction quotient Q is 9.32  103, calcu- a. Calculate the equilibrium constant for this reaction.
late [Ma]. Calculate wmax for this electrochemical cell. b. What concentration of nitric acid will produce an
NO and NO2 mixture with only 0.20% NO2 (by
95. A zinc–copper battery is constructed as follows: moles) at 25C and 1.00 atm? Assume that no
Zn⏐Zn2(0.10 M)⏐⏐Cu2(2.50 M)⏐Cu other gases are present and that the change in acid
concentration can be neglected.
The mass of each electrode is 200. g.
a. Calculate the cell potential when this battery is first 98. You make a galvanic cell with a piece of nickel, 1.0 M
connected. Ni2(aq), a piece of silver, and 1.0 M Ag(aq). Calcu-
b. Calculate the cell potential after 10.0 A of current late the concentrations of Ag(aq) and Ni2(aq) once the
has flowed for 10.0 h. (Assume each half-cell con- cell is “dead.”
tains 1.00 L of solution.) 99. A galvanic cell is based on the following half-reactions:
c. Calculate the mass of each electrode after 10.0 h.
Fe2  2e 88n Fe(s)   0.440 V
d. How long can this battery deliver a current of
 
10.0 A before it goes dead? 2H  2e 88n H2(g)   0.000 V

96. The measurement of F ion concentration by ion- In this cell the iron compartment contains an iron elec-
selective electrodes at 25.00C obeys the equation trode and [Fe2]  1.00  103 M, and the hydrogen
meas  ref  0.05916 log[F] compartment contains a platinum electrode, PH2  1.00
atm and a weak acid HA at an initial concentration of
a. For a given solution, meas is 0.4462 V. If ref is 1.00 M. If the observed cell potential is 0.333 V at 25C,
0.2420 V, what is the concentration of F in the calculate the Ka value for the weak acid HA at 25C.
solution?
b. Hydroxide ion interferes with the measurement of 100. You have a concentration cell with Cu electrodes and
F. Therefore, the response of a fluoride electrode is [Cu2]  1.00 M (right side) and 1.0  104 M (left side).
a. Calculate the potential for this cell at 25C.
meas  ref  0.05916 log([F]  k[OH]) b. The Cu2 ion reacts with NH3 to form Cu(NH3)42,
where k  1.00  101 and is called the selectivity where the stepwise formation constants are K1 
factor for the electrode response. Calculate [F] for 1.0  103, K2  1.0  104, K3  1.0  103, and
the data in part a if the pH is 9.00. What is the K4  1.0  103. Calculate the new cell potential
percent error introduced in the [F] if the hydrox- after enough NH3 is added to the left cell compart-
ide interference is ignored? ment such that at equilibrium [NH3]  2.0 M.
c. For the [F] in part b, what is the maximum pH 101. A galvanic cell is based on the following half-reactions:
such that [F]/k[OH]  50.?
Ag  e 88n Ag(s)   0.80 V
d. At low pH, F is mostly converted to HF. The
fluoride electrode does not respond to HF. What is Cu2  2e 88n Cu(s)   0.34 V
Marathon Problems 519

In this cell the silver compartment contains a silver elec- AgNH3(aq)  NH3(aq) 34 Ag(NH3)2(aq)
trode and excess AgCl(s) (Ksp  1.6  1010), and the K2  8.2  103
copper compartment contains a copper electrode and
[Cu2]  2.0 M. Calculate the cell potential after the addition of 15.0 mol
a. Calculate the potential for this cell at 25C. NH3.
b. Assuming 1.0 L of 2.0 M Cu2 in the copper com- 104. Given the following two standard reduction potentials,
partment, calculate the moles of NH3 that would
have to be added to give a cell potential of 0.52 V M3  3e 88n M   0.10 V
at 25C (assume no volume change on addition of M 2 
 2e 88n M   0.50 V
NH3).
solve for the standard reduction potential of the half-
Cu2(aq)  4NH3(aq) 34 Cu(NH3)42(aq) reaction
K  1.0  1013
M3  e 88n M2
102. Consider the following galvanic cell:
(Hint: You must use the extensive property G to de-
0.83V termine the standard reduction potential.)
105. Zirconium is one of the few metals that retains its
Pb Ag
structural integrity upon exposure to radiation. For this
reason, the fuel rods in most nuclear reactors are made of
zirconium. Answer the following questions about the re-
dox properties of zirconium based on the half-reaction
1.8 M Pb2+ ? M Ag+ ZrO2 H2O  H2O  4e 88n
? M SO42-
Zr  4OH   2.36 V
Ag2SO4 (s)
a. Is zirconium metal capable of reducing water to
Calculate the Ksp value for Ag2SO4(s). Note that to form hydrogen gas at standard conditions?
obtain silver ions in the right compartment (the cathode b. Write a balanced equation for the reduction of
compartment), excess solid Ag2SO4 was added and some water by zirconium metal.
of the salt dissolved. c. Calculate , G, and K for the reduction of
103. Consider the following galvanic cell: water by zirconium metal.
d. The reduction of water by zirconium occurred dur-
V
ing the accident at Three Mile Island, Pennsylvania,
in 1979. The hydrogen produced was successfully
Ag Cd vented and no chemical explosion occurred. If
1.00  103 kg of Zr reacts, what mass of H2 is
produced? What volume of H2 at 1.0 atm and
1000.C is produced?
e. At Chernobyl, USSR, in 1986, hydrogen was pro-
1.00 M Ag+ 1.00 M Cd 2+ duced by the reaction of superheated steam with
the graphite reactor core:
C(s)  H2O(g) 88n CO(g)  H2(g)
A 15.0-mol sample of NH3 is added to the Ag com-
partment (assume 1.00 L of total solution after the ad- A chemical explosion involving the hydrogen gas
dition). The silver ion reacts with ammonia to form com- did occur at Chernobyl. In light of this fact, do you
plex ions as shown: think it was a correct decision to vent the hydrogen
and other radioactive gases into the atmosphere at
Ag(aq)  NH3(aq) 34 AgNH3(aq) Three Mile Island? Explain.
K1  2.1  103

Marathon Problems
106. A galvanic cell is based on the following half-reactions: In this cell the copper compartment contains a copper
 electrode and [Cu2]  1.00 M, and the vanadium com-
Cu 2
 2e 88n Cu(s)   0.34 V
partment contains a vanadium electrode and V2 at an
V2  2e 88n V(s)   1.20 V unknown concentration. The compartment containing
520 CHAPTER 11 Electrochemistry

the vanadium (1.00 L of solution) was titrated with b. Calculate the value of the equilibrium constant K
0.0800 M H2EDTA2, resulting in the reaction for the titration reaction.
c. Calculate cell at the halfway point in the titration.
H2EDTA2(aq)  V2(aq)
34 VEDTA2(aq)  2H(aq) 107. The table below lists the cell potentials for the 10 pos-
K?
sible galvanic cells assembled from the metals A, B, C,
The potential of the cell was monitored to determine the D, and E and their respective 1.00 M 2 ions in solu-
stoichiometric point for the process, which occurred at tion. Using the data in the table, establish a standard re-
a volume of 500.0 mL of H2EDTA2 solution added. duction potential table similar to Table 11.1 in the text.
At the stoichiometric point, cell was observed to be 1.98 Assign a reduction potential of 0.00 V to the half-reac-
V. The solution was buffered at a pH of 10.00. tion that falls in the middle of the series. You should get
a. Calculate cell before the titration was carried out. two different tables. Explain why, and discuss what you
could do to determine which table is correct.

A(s) in A2(aq) B(s) in B2(aq) C(s) in C2(aq) D(s) in D2(aq)

E(s) in E2(aq) 0.28 V 0.81 V 0.13 V 1.00 V


D(s) in D2(aq) 0.72 V 0.19 V 1.13 V —
C(s) in C2(aq) 0.41 V 0.94 V — —
B(s) in B2(aq) 0.53 V — — —

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Video Lessons Mini-lectures from chemistry experts • Electrochemical Half-reactions in a Galvanic Cell
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• Electrochemical Cells • Galvanic (Voltaic) Cells
• Electromotive Force • Voltaic Cell: Anode Reaction
• The Activity Series of the Elements • Voltaic Cell: Cathode Reaction
• Standard Reduction Potentials • Zinc/Copper Cells (Lemon Battery)
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Galvanic Cells

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CHAPTER 11

ELECTROCHEMISTRY

Galvanic Cells, Cell Potentials, and Standard Reduction Potentials


15. Electrochemistry is the study of the interchange of chemical and electrical energy. A redox
(oxidation-reduction) reaction is a reaction in which one or more electrons are transferred. In
a galvanic cell, a spontaneous redox reaction occurs that produces an electric current. In an
electrolytic cell, electricity is used to force a nonspontaneous redox reaction to occur.

16. Magnesium is an alkaline earth metal; Mg will oxidize to Mg2+. The oxidation state of
hydrogen in HCl is +1. To be reduced, the oxidation state of H must decrease. The obvious
choice for the hydrogen product is H2(g), where hydrogen has a zero oxidation state. The
balanced reaction is Mg(s) + 2 HCl(aq) → MgCl2(aq) + H2(g). Mg goes from the 0 to the +2
oxidation state by losing two electrons. Each H atom goes from the +1 to the 0 oxidation state
by gaining one electron. Since there are two H atoms in the balanced equation, a total of two
electrons are gained by the H atoms. Hence two electrons are transferred in the balanced
reaction. When the electrons are transferred directly from Mg to H+, no work is obtained. In
order to harness this reaction to do useful work, we must control the flow of electrons through
a wire. This is accomplished by making a galvanic cell that separates the reduction reaction
from the oxidation reaction in order to control the flow of electrons through a wire to produce
a voltage.

17. A typical galvanic cell diagram is:


e e

Salt bridge

Anode Cathode
(oxidation) Cations (reduction)
Anions

413
414 CHAPTER 11 ELECTROCHEMISTRY

The diagram for all cells will look like this. The contents of each half-cell will be identified
for each reaction, with all concentrations at 1.0 M and partial pressures at 1.0 atm. Note that
cations always flow into the cathode compartment and anions always flow into the anode
compartment. This is required to keep each compartment electrically neutral.

a. Reference Table 11.1 for standard reduction potentials. Remember that E ocell =
E°(cathode) − E°(anode); in the Solutions Guide, we will represent E°(cathode) as E oc and
represent −E°(anode) as − E oa . Also remember that standard potentials are not multi-
plied by the integer used to obtain the overall balanced equation.

(Cl2 + 2 e− → 2 Cl−) × 3 E oc = 1.36 V


7 H2O + 2 Cr3+ → Cr2O72− + 14 H+ + 6 e− − E oa = −1.33 V
________________________________________________________________________
7 H2O(l) + 2 Cr3+(aq) + 3 Cl2(g) → Cr2O72− (aq) + 6 Cl− (aq) + 14 H+(aq) E ocell = 0.03 V

The contents of each compartment are:


Cathode: Pt electrode; Cl2 bubbled into solution, Cl− in solution
Anode: Pt electrode; Cr3+, H+, and Cr2O72− in solution

We need a nonreactive metal to use as the electrode in each case since all the reactants
and products are in solution. Pt is the most common choice. Another possibility is
graphite.

b. Cu2+ + 2 e− → Cu E oc = 0.34 V
Mg → Mg2+ + 2 e− − E oa = 2.37 V
______________________________________________________________
Cu2+(aq) + Mg(s) → Cu(s) + Mg2+(aq) E ocell = 2.71 V

Cathode: Cu electrode; Cu2+ in solution


Anode: Mg electrode; Mg2+ in solution

c. 5 e− + 6 H+ + IO3− → 1/2 I2 + 3 H2O E oc = 1.20 V


(Fe2+ → Fe3+ + e−) × 5 − E oa = −0.77 V
___________________________________________________________________
6 H+ + IO3− + 5 Fe2+ → 5 Fe3+ + 1/2 I2 + 3 H2O E ocell = 0.43 V

or 12 H+(aq) + 2 IO3−(aq) + 10 Fe2+(aq) → 10 Fe3+(aq) + I2(s) + 6 H2O(l) E ocell = 0.43 V

Cathode: Pt electrode; IO3−, I2, and H2SO4 (H+ source) in solution

Anode: Pt electrode; Fe2+ and Fe3+ in solution

Note: I2(s) would make a poor electrode since it sublimes.


CHAPTER 11 ELECTROCHEMISTRY 415

d. (Ag+ + e− → Ag) × 2 E oc = 0.80 V


Zn → Zn2+ + 2 e− − E oa = 0.76 V
_________________________________________________
Zn(s) + 2 Ag+(aq) → 2 Ag(s) + Zn2+(aq) E ocell = 1.56 V

Cathode: Ag electrode; Ag+ in solution

Anode: Zn electrode; Zn2+ in solution

18. a. (5 e− + 8 H+ + MnO4− → Mn2+ + 4 H2O) × 2 E oc = 1.51 V


(2 I− → I2 + 2 e−) × 5 − E oa = −0.54 V
_______________________________________________________________________
16 H+(aq) + 2 MnO4−(aq) + 10 I−(aq) → 5 I2(aq) + 2 Mn2+(aq) + 8 H2O(l) E ocell = 0.97 V

This reaction is spontaneous at standard conditions because E ocell > 0.

b. (5 e− + 8 H+ + MnO4− → Mn2+ + 4 H2O) × 2 E oc = 1.51 V


(2 F− → F2 + 2 e−) × 5 − E oa = !2.87 V
________________________________________________________________________
16 H+(aq) + 2 MnO4−(aq) + 10 F−(aq) → 5 F2(aq) + 2 Mn2+(aq) + 8 H2O(l) E ocell = −1.36 V

This reaction is not spontaneous at standard conditions because E ocell < 0.

c. H2 → 2H+ + 2 e− E oc = 0.00 V
H2 + 2 e− → 2H− − E oa = !2.23 V
___________________________________________
2H2(g) → 2H+(aq) + 2 H−(aq) E ocell = !2.23 V; not spontaneous

d. Au3+ + 3 e− → Au E oc = 1.50 V
(Ag → Ag+ + e−) × 3 − E oa = −0.80 V
_________________________________________________________________
Au3+(aq) + 3 Ag(s) → Au(s) + 3 Ag+(aq) E ocell = 0.70 V; spontaneous

19. Reference Exercise 11.17 for a typical galvanic cell design. The contents of each half-cell
compartment are identified below, with all solute concentrations at 1.0 M and all gases at 1.0
atm. For each pair of half-reactions, the half-reaction with the largest standard reduction
potential will be the cathode reaction, and the half-reaction with the smallest reduction
potential will be reversed to become the anode reaction. Only this combination gives a
spontaneous overall reaction, i.e., a reaction with a positive overall standard cell potential.
416 CHAPTER 11 ELECTROCHEMISTRY

a. Cl2 + 2 e− → 2 Cl− E oc = 1.36 V


2 Br- → Br2 + 2 e− − E oa = −1.09 V
_________________________________________________
Cl2(g) + 2 Br-(aq) → Br2(aq) + 2 Cl−(aq) E ocell = 0.27 V

The contents of each compartment are:

Cathode: Pt electrode; Cl2(g) bubbled in, Cl- in solution

Anode: Pt electrode; Br2 and Br- in solution

b. (2 e− + 2 H+ + IO4− → IO3− + H2O) × 5 E oc = 1.60 V


(4 H2O + Mn2+ → MnO4− + 8 H+ + 5 e−) × 2 − E oa = −1.51 V
________________________________________________________________________
10 H+ + 5 IO4− + 8 H2O + 2 Mn2+ → 5 IO3− + 5 H2O + 2 MnO4− + 16 H+ E ocell = 0.09 V

This simplifies to:

3 H2O(l) + 5 IO4−(aq) + 2 Mn2+(aq) → 5 IO3−(aq) + 2 MnO4−(aq) + 6 H+(aq)


E ocell = 0.09 V

Cathode: Pt electrode; IO4−, IO3−, and H2SO4 (as a source of H+) in solution

Anode: Pt electrode; Mn2+, MnO4−, and H2SO4 in solution

c. H2O2 + 2 H+ + 2 e− → 2 H2O E oc = 1.78 V


H2O2 → O2 + 2 H+ + 2 e− − E oa = −0.68 V
_______________________________________________________________________
2 H2O2(aq) → 2 H2O(l) + O2(g) E ocell = 1.10 V

Cathode: Pt electrode; H2O2 and H+ in solution

Anode: Pt electrode; O2(g) bubbled in, H2O2 and H+ in solution

d. (Fe3+ + 3 e− → Fe) × 2 E oc = −0.036 V


(Mn → Mn2+ + 2 e−) × 3 − E oa = 1.18 V
________________________________________________________________________
2 Fe3+(aq) + 3 Mn(s) → 2 Fe(s) + 3 Mn2+(aq) E ocell = 1.14 V

Cathode: Fe electrode; Fe3+ in solution; Anode: Mn electrode; Mn2+ in solution

20. Locate the pertinent half-reactions in Table 11.1, and then figure which combination will give
a positive standard cell potential. In all cases the anode compartment contains the species
CHAPTER 11 ELECTROCHEMISTRY 417

with the smallest standard reduction potential. In part a, the copper compartment is the
anode, and in part b, the cadmium compartment is the anode.

a. Au3+ + 3 e− → Au E oc = 1.50 V
(Cu+ → Cu2+ + e−) × 3 – E oa = −0.16 V
__________________________________________________________
Au3+(aq) + 3 Cu+(aq) → Au(s) + 3 Cu2+(aq) E ocell = 1.34 V

b. (VO2+ + 2 H+ + e− → VO2+ + H2O) × 2 E oc = 1.00 V


Cd → Cd2+ + 2e- – E oa = 0.40 V
_____________________________________________________________________
2 VO2+(aq) + 4 H+(aq) + Cd(s) → 2 VO2+(aq) + 2 H2O(l) + Cd2+(aq) E ocell = 1.40 V

21. In standard line notation, the anode is listed first and the cathode is listed last. A double line
separates the two compartments. By convention, the electrodes are on the ends, with all
solutes and gases toward the middle. A single line is used to indicate a phase change. We
also included all concentrations.

19a. Pt | Br− (1.0 M), Br2 (1.0 M) || Cl2 (1.0 atm) | Cl− (1.0 M) | Pt

19b. Pt | Mn2+ (1.0 M), MnO4− (1.0 M), H+ (1.0 M) | | IO4− (1.0 M), IO3− (1.0 M),
H+ (1.0 M) | Pt

19c. Pt | H2O2 (1.0 M), H+ (1.0 M) | O2 (1.0 atm) | | H2O2 (1.0 M), H+ (1.0 M) | Pt

19d. Mn | Mn2+ (1.0 M) | | Fe3+ (1.0 M) | Fe

22. The reduction half-reaction for the SCE is:

Hg2Cl2 + 2 e− → 2 Hg + 2 Cl− ESCE = 0.242 V

For a spontaneous reaction to occur, Ecell must be positive. Using the standard reduction
potentials in Table 11.1 and the given SCE potential, deduce which combination will produce
a positive overall cell potential.

a. Cu2+ + 2 e− → Cu E° = 0.34 V

Ecell = 0.34 - 0.242 = 0.10 V; SCE is the anode.

b. Fe3+ + e− → Fe2+ E° = 0.77 V

Ecell = 0.77 - 0.242 = 0.53 V; SCE is the anode.

c. AgCl + e− → Ag + Cl− E° = 0.22 V

Ecell = 0.242 − 0.22 = 0.02 V; SCE is the cathode.


418 CHAPTER 11 ELECTROCHEMISTRY

d. Al3+ + 3 e− → Al E° = −1.66 V

Ecell = 0.242 + 1.66 = 1.90 V; SCE is the cathode.

e. Ni2++ 2 e− → Ni E° = −0.23 V

Ecell = 0.242 + 0.23 = 0.47 V; SCE is the cathode.

23. a. 2 H+ + 2 e− → H2 E° = 0.00 V; Cu → Cu2+ + 2 e− −E° = -0.34 V

E ocell = −0.34 V; no, H+ cannot oxidize Cu to Cu2+ at standard conditions ( E ocell < 0).

b. Fe3+ + e− → Fe2+ E° = 0.77 V; 2 I− → I2 + 2 e− −E° = -0.54 V

E ocell = 0.77 − 0.54 = 0.23 V; yes, Fe3+ can oxidize I− to I2.

c. H2 → 2 H+ + 2 e− −E° = 0.00 V; Ag+ + e− → Ag E° = 0.80 V

E ocell = 0.80 V; yes, H2 can reduce Ag+ to Ag at standard conditions ( E ocell > 0).

d. Fe2+ → Fe3+ + e− −E° = -0.77 V; Cr3+ + e− → Cr2+ E° = −0.50 V

E ocell = −0.50 − 0.77 = −1.27 V; no, Fe2+ cannot reduce Cr3+ to Cr2+ at standard
conditions.

24. Good oxidizing agents are easily reduced. Oxidizing agents are on the left side of the
reduction half-reactions listed in Table 11.1. We look for the largest, most positive standard
reduction potentials to correspond to the best oxidizing agents. The ordering from worst to
best oxidizing agents is:
K+ < H2O < Cd2+ < I2 < AuCl4− < IO3−
E°(V) −2.92 −0.83 −0.40 0.54 0.99 1.20

25. Good reducing agents are easily oxidized. The reducing agents are on the right side of the
reduction half-reactions listed in Table 11.1. The best reducing agents have the most nega-
tive standard reduction potentials (E°); i.e., the best reducing agents have the most positive
!E° value. The ordering from worst to best reducing agents is:
F− < H2O < I2 < Cu+ < H− < K
!E°(V) !2.92 −1.23 −1.20 −0.16 2.23 2.92

26. Cl2 + 2 e− → 2 Cl− E° = 1.36 V Ag+ + e− → Ag E° = 0.80 V


Pb2+ + 2 e− → Pb E° = −0.13 V Zn2+ + 2 e− → Zn E° = −0.76 V
Na+ + e- → Na E° = −2.71 V

a. Oxidizing agents (species reduced) are on the left side of the above reduction half-
reactions. Of the species available, Ag+ would be the best oxidizing agent since it has the
most positive E° value.
CHAPTER 11 ELECTROCHEMISTRY 419

b. Reducing agents (species oxidized) are on the right side of the reduction half-reactions.
Of the species available, Zn would be the best reducing agent since it has the most
positive −E° value.

c. SO42− + 4 H+ + 2 e− → H2SO3 + H2O E oc = 0.20 V; SO42− can oxidize Pb and Zn at


standard conditions. When SO42- is coupled with these reagents, E ocell is positive.

d. Al → Al3+ + 3 e− − E oa = 1.66 V; Al can oxidize Ag+ and Zn2+ at standard conditions


since E ocell > 0.

27. a. 2 Br- → Br2 + 2 e− − E oa = −1.09 V; 2 Cl− → Cl2 + 2 e− − E oa = −1.36 V; E oc > 1.09 V


to oxidize Br−; E oc < 1.36 V to not oxidize Cl−; Cr2O72−, O2, MnO2, and IO3− are all
possible because when all these oxidizing agents are coupled with Br−, they give E ocell >
0, and when coupled with Cl−, they give E ocell < 0 (assuming standard conditions).

b. Mn → Mn2+ + 2 e− − E oa = 1.18 V; Ni → Ni2+ + 2 e− − E oa = 0.23 V; any oxidizing


agent with −0.23 V > E oc > −1.18 V will work. PbSO4, Cd2+, Fe2+, Cr3+, Zn2+, and H2O
will be able to oxidize Mn but not oxidize Ni (assuming standard conditions).

28. a. Cu2+ + 2 e− → Cu E oc = 0.34 V; Cu2+ + e− → Cu+ E oc = 0.16 V; to reduce Cu2+ to Cu


but not reduce Cu2+ to Cu+, the reducing agent must have a − E oa value between −0.34
and −0.16 V (so E ocell is positive only for the Cu2+-to-Cu reduction). The reducing agents
(species oxidized) are on the right side of the half-reactions in Table 11.1. The reagents
at standard conditions, which have a − E oa value between −0.34 and −0.16 V, are Ag (in
1.0 M Cl−) and H2SO3.

b. Br2 + 2 e− → 2 Br− E oc = 1.09 V; I2 + 2 e− → 2 I− E oc = 0.54 V; from Table 11.1, VO2+,


Au (in 1.0 M Cl−), NO, ClO2−, Hg22+, Ag, Hg, Fe2+, H2O2, and MnO4− are all capable at
standard conditions of reducing Br2 to Br− but not reducing I2 to I−. When these reagents
are coupled with Br2, E ocell > 0, and when coupled with I2, E ocell < 0.

29. ClO− + H2O + 2 e− → 2 OH− + Cl− E oc = 0.90 V


2 NH3 + 2 OH− → N2H4 + 2 H2O + 2 e− − E oa = 0.10 V
__________________________________________________________
ClO−(aq) + 2 NH3(aq) → Cl−(aq) + N2H4(aq) + H2O(l) E ocell = 1.00 V

Because E ocell is positive for this reaction, at standard conditions ClO− can spontaneously
oxidize NH3 to the somewhat toxic N2H4.

30. Consider the strongest oxidizing agent combined with the strongest reducing agent from
Table 11.1:
420 CHAPTER 11 ELECTROCHEMISTRY

F2 + 2 e− → 2 F− E oc = 2.87 V
(Li → Li+ + e−) × 2 − E oa = 3.05 V
_______________________________________________
F2(g) + 2 Li(s) → 2 Li+(aq) + 2 F−(aq) E ocell = 5.92 V

The claim is impossible. The strongest oxidizing agent and reducing agent when combined
only give E ocell of about 6 V.

Cell Potential, Free Energy, and Equilibrium


31. An extensive property is one that depends directly on the amount of substance. The free
energy change for a reaction depends on whether 1 mole of product is produced or 2 moles of
product are produced or 1 million moles of product are produced. This is not the case for cell
potentials, which do not depend on the amount of substance. The equation that relates ΔG to
E is ΔG = !nFE. It is the n term that converts the intensive property E into the extensive
property ΔG. n is the number of moles of electrons transferred in the balanced reaction that
ΔG is associated with.

32. Fe2+ + 2 e− → Fe E° = !0.44 V = !0.44 J/C

ΔG° = !nFE° = !(2 mol e−)(96,485 C/mol e−)(!0.44 J/C)(1 kJ/1000 J) = 85 kJ

85 kJ = 0 ! (ΔG of , Fe2+ + 0) , ΔG of , Fe2+ = !85 kJ

We can get ΔG of , Fe3+ two ways. Consider: Fe3+ + e− → Fe2+ E° = 0.77 V

ΔG° = !(1 mol e)(96,485 C/mol e-)(0.77 J/C) = !74,300 J = !74 kJ

Fe2+ → Fe3+ + e− ΔG° = 74 kJ


2+ −
Fe → Fe + 2 e ΔG° = !85 kJ
___________________________________________________
Fe → Fe3+ + 3 e− ΔG° = !11 kJ, ΔG of , Fe3+ = !11 kJ/mol

Or consider: Fe3+ + 3 e− → Fe E° = !0.036 V

ΔG° = !(3 mol e−)(96,485 C/mol e−)(!0.036 J/C) = 10,400 J ≈ 10. kJ

10. kJ = 0 ! (ΔG of , Fe3+ + 0) , ΔG of , Fe3+ = !10. kJ/mol; Round-off error explains the
1-kJ discrepancy.

33. Because the cells are at standard conditions, wmax = ΔG = ΔG° = − nFE ocell . See Exercise
11.20 for the balanced overall equations and E ocell .

20a. wmax = −(3 mol e−)(96,485 C/mol e−)(1.34 J/C) = −3.88 × 105 J = −388 kJ

20b. wmax = −(2 mol e−)(96,485 C/mol e−)(1.40 J/C) = −2.70 × 105 J = −270. kJ
CHAPTER 11 ELECTROCHEMISTRY 421

34. a. Possible reaction: I2(s) + 2 Cl− (aq) → 2 I−(aq) + Cl2(g)


E ocell = 0.54 V − 1.36 V = −0.82 V; this reaction is not spontaneous at standard con-
ditions since E ocell < 0. No reaction occurs.

b. Possible reaction: Cl2(g) + 2 I−(aq) → I2(s) + 2 Cl−(aq) E ocell = 0.82 V; this reaction is
spontaneous at standard conditions since E ocell > 0. The reaction will occur.

Cl2(g) + 2 I−(aq) → I2(s) + 2 Cl−(aq) E ocell = 0.82 V = 0.82 J/C

ΔG° = − nFE ocell = −(2 mol e−)(96,485 C/mol e−)(0.82 J/C) = −1.6 × 105 J = −160 kJ

0.0591 nE o 2(0.82)
E° = log K, log K = = = 27.75, K = 1027.75 = 5.6 × 1027
n 0.0591 0.0591

Note: When determining exponents, we will round off to the correct number of
significant figures after the calculation is complete in order to help eliminate excessive
round-off errors.

c. Possible reaction: 2 Ag(s) + Cu2+(aq) → Cu(s) + 2 Ag+(aq) E ocell = −0.46 V; no


reaction occurs.

d. Fe2+ can be oxidized or reduced. The other species present are H+, SO42−, H2O, and O2
from air. Only O2 in the presence of H+ has a large enough standard reduction potential
to oxidize Fe2+ to Fe3+ (resulting in E ocell > 0). All other combinations, including the
possible reduction of Fe2+, give negative cell potentials. The spontaneous reaction is:

4 Fe2+(aq) + 4 H+(aq) + O2(g) → 4 Fe3+(aq) + 2 H2O(l) E ocell = 1.23 - 0.77 = 0.46 V

ΔG° = − nFE ocell = −(4 mol e−)(96,485 C/mol e−)(0.46 J/C)(1 kJ/1000 J) = −180 kJ

4(0.46)
log K = = 31.13, K = 1.3 × 1031
0.0591

35. Reference Exercise 11.19 for the balanced reactions and standard cell potentials. The
balanced reactions are necessary to determine n, the moles of electrons transferred.

19a. Cl2(aq) + 2 Br-(aq) → Br2(aq) + 2 Cl−(aq) E ocell = 0.27 V = 0.27 J/C, n = 2 mol e−

ΔG° = − nFE ocell = −(2 mol e−)(96,485 C/mol e−)(0.27 J/C) = −5.2 × 104 J = −52 kJ

0.0591 nE o 2(0.27)
E ocell = log K, log K = = = 9.14, K = 109.14 = 1.4 × 109
n 0.0591 0.0591
422 CHAPTER 11 ELECTROCHEMISTRY

Note: When determining exponents, we will round off to the correct number of
significant figures after the calculation is complete in order to help eliminate
excessive round-off errors.

19b. ΔG° = −(10 mol e−)(96,485 C/mol e−)(0.09 J/C) = −9 × 104 J = −90 kJ

10(0.09)
log K = = 15.2, K = 1015.2 = 2 × 1015
0.0591

19c. ΔG° = −(2 mol e−)(96,485 C/mol e−)(1.10 J/C) = −2.12 × 105 J = −212 kJ

2(1.10)
log K = = 37.225, K = 1.68 × 1037
0.0591

19d. ΔG° = −(6 mol e−)(96,485 C/mol e−)(1.14 J/C) = −6.60 × 105 J = −660. kJ

6(1.14)
log K = = 115.736, K = 5.45 × 10115
0.0591

36. a. Cl2 + 2 e− → 2 Cl− E oc = 1.36 V


(ClO2− → ClO2 + e−) × 2 − E oa = −0.954 V
____________________________________________________________
2 ClO2−(aq) + Cl2(g) → 2 ClO2(aq) + 2 Cl−(aq) E ocell = 0.41 V = 0.41 J/C

ΔG° = − nFE ocell = −(2 mol e−)(96,485 C/mol e−)(0.41 J/C) = −7.91 × 104 J = −79 kJ

ΔG° = −RT ln K, so K = exp(−ΔG°/RT)

K = exp[(7.9 × 104 J)/(8.3145 J K−1 mol−1)(298 K)] = 7.0 × 1013

nE o 2(0.41)
or log K = = = 13.87, K = 1013.87 = 7.4 × 1013
0.0591 0.0591

b. (H2O + ClO2 → ClO3− + 2 H+ + e−) × 5


5 e + 4 H+ + ClO2 → Cl− + 2 H2O

________________________________________________
3 H2O(l) + 6 ClO2(g) → 5 ClO3−(aq) + Cl−(aq) + 6 H+(aq)

37. a. (4 H+ + NO3− + 3 e− → NO + 2 H2O) × 2 E oc = 0.96 V


(Mn → Mn2+ + 2 e−) × 3 − E oa = 1.18 V
_______________________________________________________________________
3 Mn(s) + 8 H+(aq) + 2 NO3−(aq) → 2 NO(g) + 4 H2O(l) + 3 Mn2+(aq) E ocell = 2.14 V
CHAPTER 11 ELECTROCHEMISTRY 423

5 × (2 e− + 2 H+ + IO4− → IO3− + H2O) E oc = 1.60 V


2 × (Mn2+ + 4 H2O → MnO4− + 8 H+ + 5 e−) − E oa = −1.51 V
________________________________________________________________________
5 IO4−(aq) + 2 Mn2+(aq) + 3 H2O(l) → 5 IO3−(aq) + 2 MnO4−(aq) + 6 H+(aq)
E ocell = 0.09 V
b. Nitric acid oxidation (see part a for E ocell ):

ΔG° = − nFE ocell = −(6 mol e−)(96,485 C/mol e−)(2.14 J/C) = −1.24 × 106 J =
−1240 kJ
o
nE 6(2.14)
log K = = = 217, K ≈ 10217
0.0591 0.0591

Periodate oxidation (see part a for E ocell ):

ΔG° = −(10 mol e−)(96,485 C/mol e−)(0.09 J/C)(1 kJ/1000 J) = −90 kJ

10(0.09)
log K = = 15.2, K = 1015.2 = 2 × 1015
0.0591

38. 2 H2(g) + O2(g) → 2 H2O(l); oxygen goes from the zero oxidation state to the -2 oxidation
state in H2O. Because two moles of O appear in the balanced reaction, n = 2(2) = 4 mol
electrons transferred.

0.0591 0.0591
a. E ocell = log K = log(1.28 × 1083), E ocell = 1.23 V
n 4

ΔG° = − nFE ocell = −(4 mol e−)(96,485 C/mol e−)(1.23 J/C) = −4.75 × 105 J = −475 kJ

b. Because moles of gas decrease as reactants are converted into products, ΔS° will be
negative (unfavorable). Because the value of ΔG° is negative, ΔH° must be negative
(ΔG° = ΔH° − TΔS°).

c. ΔG = wmax = ΔH − TΔS. Because ΔS is negative, as T increases, ΔG becomes more


positive (closer to zero). Therefore, wmax will decrease as T increases.

TΔSo ΔH o
39. ΔG° = !nFE° = ΔH° ! TΔS°, E° = −
nF nF

If we graph E° versus T, we should get a straight line (y = mx + b). The slope (m) of the line
is equal to ΔS°/nF, and the y intercept is equal to -ΔH°/nF. From the equation above, E° will
have a small temperature dependence when ΔS° is close to zero.

40. CH3OH(l) + 3/2 O2(g) → CO2(g) + 2 H2O(l)

ΔG° = ∑ n p ΔG of , products − ∑ n r ΔG of , reactants = 2(−237) + (−394) − (−166) = −702 kJ


424 CHAPTER 11 ELECTROCHEMISTRY

The balanced half-reactions are:

H2O + CH3OH → CO2 + 6 H+ + 6 e− and O2 + 4 H+ + 4 e− → 2 H2O

For 3/2 mol O2, 6 moles of electrons will be transferred (n = 6).


− ΔG o − (−702,000 J )
ΔG° = −nFE°, E° = = = 1.21 J/C = 1.21 V
nF (6 mol e − ) (96,485 C / mol e − )

For this reaction: ΔS° = 2(70.) + 214 − [127 + 3/2 (205)] = −81 J/K

TΔSo ΔH o
From Exercise 11.39, E° = − .
nF nF

Because ΔS° is negative, E° will decrease with an increase in temperature.

41. a. Cu+ + e− → Cu E oc = 0.52 V


Cu+ → Cu2+ + e− − E oa = !0.16 V
____________________________________________________________
2 Cu+(aq) → Cu2+(aq) + Cu(s) E ocell = 0.36 V; spontaneous

ΔG° = − nFE ocell = !(1 mol e−)(96,485 C/mol e−)(0.36 J/C) = !34,700 J = -35 kJ

0.0591 nE o 1(0.36)
E ocell = log K, log K = = = 6.09, K = 106.09 = 1.2 × 106
n 0.0591 0.0591

b. Fe2+ + 2 e− → Fe E oc = !0.44 V
(Fe2+ → Fe3+ + e−) × 2 − E oa = !0.77 V
_____________________________________________________________
3 Fe2+(aq) → 2 Fe3+(aq) + Fe(s) E ocell = !1.21 V; not spontaneous

c. HClO2 + 2 H+ + 2 e− → HClO + H2O E oc = 1.65 V


HClO2 + H2O → ClO3− + 3 H+ + 2 e− − E oa = !1.21 V
______________________________________________________________________
2 HClO2(aq) → ClO3−(aq) + H+(aq) + HClO(aq) E ocell = 0.44 V; spontaneous

ΔG° = − nFE ocell = !(2 mol e−)(96,485 C/mol e−)(0.44 J/C) = !84,900 J = !85 kJ

nE o 2(0.44)
log K = = = 14.89, K = 7.8 × 1014
0.0591 0.0591

42. NO3− is a spectator ion. The reaction that occurs is Ag+ reacting with Zn.
CHAPTER 11 ELECTROCHEMISTRY 425

(Ag+ + e− → Ag) × 2 E oc = 0.80 V


2+ −
Zn → Zn + 2 e ! E oa = 0.76 V
_________________________________________
2 Ag+ + Zn → 2 Ag + Zn2+ E ocell = 1.56 V

nE 2(1.56)
log K = = , K = 1052.792 = 6.19 × 1052
0.0591 0.0591

43. Al3+ + 3 e− → Al E oc = −1.66 V


Al + 6 F− → AlF63− + 3 e− − E oa = 2.07 V
___________________________________________________
Al3+(aq) + 6 F−(aq) → AlF63−(aq) E ocell = 0.41 V K=?

nE o 3(0.41)
log K = = = 20.81, K = 1020.81 = 6.5 × 1020
0.0591 0.0591

44. The Ksp reaction is FeS(s) ⇌ Fe2+(aq) + S2−(aq); K = Ksp. Manipulate the given equations
so that when they are added together, we get the Ksp reaction. Then we can use the value of
E ocell for the reaction to determine Ksp.

FeS + 2 e− → Fe + S2− E oc = !1.01 V


Fe → Fe2+ + 2 e− − E oa = 0.44 V
____________________________________________
Fe(s) → Fe2+(aq) + S2−(aq) E ocell = !0.57 V

nE o 2(−0.57)
log Ksp = = = !19.29, Ksp = 10 −19.29 = 5.1 × 10 −20
0.0591 0.0591

45. CuI + e− → Cu + I− E oCuI = ?


Cu → Cu+ + e− − E oa = −0.52 V
_________________________________________________
CuI(s) → Cu+(aq) + I−(aq) E ocell = E oCuI − 0.52 V

For this overall reaction, K = Ksp = 1.1 × 10−12:

0.0591 0.0591
E ocell = log Ksp = log(1.1 × 10−12) = −0.71 V
n 1

E ocell = −0.71 V = E oCuI − 0.52, E oCuI = −0.19 V


426 CHAPTER 11 ELECTROCHEMISTRY

Galvanic Cells: Concentration Dependence


46. Cr2O72− + 14 H+ + 6 e− → 2 Cr3+ + 7 H2O E oc = 1.33 V
3+ −
(Al → Al + 3 e ) × 2 − E oa = 1.66 V
_________________________________________________________
Cr2O72− + 14 H+ + 2 Al → 2 Al3+ + 2 Cr3+ + 7 H2O E ocell = 2.99 V

0.0591 0.0591 [Al3+ ]2 [Cr 3+ ]2


E = EE ! log Q , E = 2.99 V ! log 2−
n 6 [Cr2 O 7 ][H + ]14

0.0591 (0.30) 2 (0.15) 2 − 6(0.02) ⎛ 3.7 × 10 −3 ⎞


3.01 = 2.99 ! log , = log ⎜⎜ + 14 ⎟

n (0.55)[H + ]14 0.0591 ⎝ [H ] ⎠

3.7 × 10 −3
= 10 −2.0 = 0.01, [H+]14 = 0.37, [H+] = 0.93 = 0.9 M, pH = -log(0.9) = 0.05
[H + ]14

47. a. Au3+ + 3 e− → Au E oc = 1.50 V


(Tl → Tl+ + e−) × 3 − E oa = 0.34 V
_________________________________________________
Au3+(aq) + 3 Tl(s) → Au(s) + 3 Tl+(aq) E ocell = 1.84 V

b. ΔG° = − nFE ocell = −(3 mol e−)(96,485 C/mol e−)(1.84 J/C) = −5.33 × 105 J = −533 kJ

nE o 3(1.84)
log K = = = 93.401, K = 1093.401 = 2.52 × 1093
0.0591 0.0591

0.0591 [Tl + ]3
c. At 25°C, Ecell = E ocell − log Q, where Q = .
n [Au 3+ ]

0.0591 [Tl + ]3 0.0591 (1.0 × 10 −4 ) 3


Ecell = 1.84 V − log = 1.84 − log
3 [Au 3+ ] 3 1.0 × 10 − 2

Ecell = 1.84 − (−0.20) = 2.04 V

48. (Cr2+ → Cr3+ + e−) × 2


Co + 2 e− → Co
2+

_____________________________________
2 Cr2+(aq) + Co2+(aq) → 2 Cr3+(aq) + Co(s)

0.0591 0.0591
E ocell = log K = log(2.79 × 107) = 0.220 V
n 2
CHAPTER 11 ELECTROCHEMISTRY 427

0.0591 [Cr 3+ ]2 0.0591 ( 2 .0 ) 2


E = E° − log = 0.220 V − log = 0.151 V
n [Cr 2+ ]2 [Co 2 + ] 2 (0.30) 2 (0.20)

ΔG = −nFE = −(2 mol e−)(96,485 C/mol e−)(0.151 J/C) = −2.91 × 104 J = −29.1 kJ

49. (Pb2+ + 2 e− → Pb) × 3 E oc = −0.13 V


(Al → Al3+ + 3 e−) × 2 − E oa = 1.66 V
________________________________________________________
3 Pb2+(aq) + 2 Al(s) → 3 Pb(s) + 2 Al3+(aq) E ocell = 1.53 V

From the balanced reaction, when the [Al3+] has increased by 0.60 mol/L (Al3+ is a product
in the spontaneous reaction), then the Pb2+ concentration has decreased by 3/2 (0.60 mol/L) =
0.90 M.

0.0591 [Al3+ ]2 0.0591 (1.60) 2


Ecell = 1.53 V − log = 1.53 − log
6 [Pb 2 + ]3 6 (0.10) 3

Ecell = 1.53 V − 0.034 V = 1.50 V

RT 0.0591
50. a. E = E° − ln Q, or at 25°C, E = E° − log Q.
nF n

0.0591
For Cu2+(aq) + 2 e− → Cu(s) E° = 0.34 V; E = E° − log(1/[Cu2+])
n

0.0591
E = 0.34 V − log(1/0.10) = 0.34 V − 0.030 V = 0.31 V
2

0.0591
b. E = 0.34 − log(1/2.0) = 0.34 V − (−8.9 × 10−3 V) = 0.35 V
2

0.0591
c. E = 0.34 − log(1/1.0 × 10−4) = 0.34 − 0.12 = 0.22 V
2

d. 5 e− + 8 H+(aq) + MnO4− (aq) → Mn2+(aq) + 4 H2O(l) E° = 1.51 V

0.0591 [Mn 2 + ] 0.0591 (0.010)


E = E° − log −
= 1.51 V − log
5 [MnO 4 ][H ] + 8
5 (0.10) (1.0 × 10 −3 )8

0.0591
E = 1.51 − (23) = 1.51 V − 0.27 V = 1.24 V
5

0.0591 ⎡ (0.010) ⎤
e. E = 1.51 − log ⎢ 8⎥
= 1.51 − 0.083 = 1.43 V
5 ⎣ (0.10) (0.10) ⎦
428 CHAPTER 11 ELECTROCHEMISTRY

51. a. n = 2 for this reaction (lead goes from Pb → Pb2+ in PbSO4).

⎛ 1 ⎞
E = E ocell −
0.0591
log ⎜ + 2 ⎟ = 2.04 V − 0.0591 log 1
2 ⎜ − 2 ⎟
2 (4.5) (4.5) 2
2
⎝ [H ] [HSO 4 ] ⎠

2.04 V − (−0.077 V) = 2.12 V

b. We can calculate ΔG° from ΔG° = ΔH° − TΔS° and then E° from ΔG° = −nFE°, or we
can use the equation derived in Exercise 11.39.

o TΔS o − ΔH o (253 K )(263.5 J / K ) + 315.9 × 103 J


E − 20 = = = 1.98 J/C = 1.98 V
nF (2 mol e − )(96,485 C / mol e − )

RT RT 1
c. E − 20 = E o− 20 − ln Q = 1.98 V − ln + 2 −
nF nF [H ] [ HSO 4 ]2

(8.3145 J K −1 mol −1 )(253 K ) 1


E−20 = 1.98 V − − −
ln = 1.98 V − (−0.066 V)
(2 mol e )(96,485 C / mol e ) (4.5) (4.5) 2
2
= 2.05 V

d. As the temperature decreases, the cell potential decreases. Also, oil becomes more
viscous at lower temperatures, which adds to the difficulty of starting an engine on a cold
day. The combination of these two factors results in batteries failing more often on cold
days than on warm days.

52. a. Ag2CrO4(s) + 2 e− → 2 Ag(s) + CrO42−(aq) E° = 0.446 V


Hg2Cl2 + 2 e− → 2 Hg + 2 Cl− ESCE = 0.242 V
SCE will be the oxidation half-reaction with Ecell = 0.446 - 0.242 = 0.204 V.
ΔG = −nFEcell = −2(96,485)(0.204)J = −3.94 × 104 J = −39.4 kJ

b. In SCE, we assume all concentrations are constant. Therefore, only CrO42− appears in the
Q expression, and it will appear in the numerator since CrO42− is produced in the
reduction half-reaction. To calculate Ecell at nonstandard CrO42- concentrations, we use
the following equation.

o 0.0591 0.0591
Ecell = Ecell − log[CrO42−] = 0.204 V − log[CrO42−]
2 2

0.0591
c. Ecell = 0.204 − log(1.00 × 10−5) = 0.204 V − (−0.148 V) = 0.352 V
2

d. 0.504 V = 0.204 V − (0.0591/2) log[CrO42−]

log[CrO42−] = −10.152, [CrO42−] = 10−10.152 = 7.05 × 10−11 M


CHAPTER 11 ELECTROCHEMISTRY 429

e. Ag2CrO4 + 2 e− → 2 Ag + CrO42− Eoc = 0.446 V


o
(Ag → Ag+ + e−) × 2 − Ea = -0.80 V
_________________________________________________________________
Ag2CrO4(s) → 2 Ag+(aq) + CrO4−(aq) Eocell = −0.35 V; K = Ksp = ?

0.0591 (−0.35 V ) ( 2)
Eocell = log Ksp, log Ksp = = −11.84, Ksp = 10−11.84 = 1.4 × 10−12
n 0.0591
53. Concentration cell: a galvanic cell in which both compartments contain the same components
but at different concentrations. All concentration cells have E ocell = 0 because both compart-
ments contain the same contents. The driving force for the cell is the different ion
concentrations at the anode and cathode. The cell produces a voltage as long as the ion
concentrations are different. Equilibrium for a concentration cell is reached (E = 0) when the
ion concentrations in the two compartments are equal.

The net reaction in a concentration cell is:

Ma+(cathode, x M) → Ma+(anode, y M) E ocell = 0

and the Nernst equation is:


0.0591 0.0591 [M a + (anode)]
E = EE − log Q = − log a + , where a is the number of
n a [M (cathode)] electrons transferred.

To register a potential (E > 0), the log Q term must be a negative value. This occurs when
Ma+(cathode) > Ma+(anode). The higher ion concentration is always at the cathode, and the
lower ion concentration is always at the anode. The magnitude of the cell potential depends
on the magnitude of the differences in ion concentrations between the anode and cathode. The
larger the difference in ion concentrations, the more negative is the log Q term, and the more
positive is the cell potential. Thus, as the difference in ion concentrations between the anode
and cathode compartments increases, the cell potential increases. This can be accomplished
by decreasing the ion concentration at the anode and/or by increasing the ion concentration at
the cathode.

54. When NaCl is added to the anode compartment, Ag+ reacts with Cl− to form AgCl(s). Add-
ing Cl− lowers the Ag+ concentration, which causes an increase in the cell potential. To
determine Ksp for AgCl (Ksp = [Ag+][Cl−]), we must know the equilibrium Ag+ and Cl−
concentrations. Here, [Cl−] is given, and we use the Nernst equation to calculate the [Ag+] at
the anode.

o
55. As is the case for all concentration cells, Ecell = 0, and the smaller ion concentration is always
in the anode compartment. The general Nernst equation for the Ni | Ni2+ (x M) | | Ni2+(y M) |
Ni concentration cell is:
430 CHAPTER 11 ELECTROCHEMISTRY

o 0.0591 0.0591 [ Ni 2+ ]anode


Ecell = Ecell − log Q = log
n 2 [ Ni 2 + ]cathode

o
a. Because both compartments are at standard conditions ([Ni2+] = 1.0 M), Ecell = Ecell = 0 V.
No electron flow occurs.

b. Cathode = 2.0 M Ni2+; anode = 1.0 M Ni2+; electron flow is always from the anode to
the cathode, so electrons flow to the right in the diagram.

− 0.0591 [ Ni 2+ ]anode − 0.0591 1 .0


Ecell = log 2+
= log = 8.9 × 10−3 V
2 [ Ni ]cathode 2 2 .0

c. Cathode = 1.0 M Ni2+; anode = 0.10 M Ni2+; electrons flow to the left in the diagram.

− 0.0591 0.10
Ecell = log = 0.030 V
2 1.0
d. Cathode = 1.0 M Ni2+; anode = 4.0 × 10−5 M Ni2+; electrons flow to the left in the
diagram.

− 0.0591 4.0 × 10 −5
Ecell = log = 0.13 V
2 1.0

e. Since both concentrations are equal, log(2.5/2.5) = log(1.0) = 0, and Ecell = 0. No electron
flow occurs.

56. Cathode: M2+ + 2e− → M(s) Eoc = 0.80 V


o
Anode: M(s) → M2+ + 2e− − Ea = −0.80 V
______________________________________________________
M2+(cathode) → M2+(anode) Eocell = 0.00 V

0.0591 [M 2+ ]anode 0.0591 [M 2 + ]anode


Ecell = 0.44 V = 0.00 V − log , 0.44 = − log
2 [M 2+ ]cathode 2 1 .0

2(0.44)
log [M2+]anode = − = −14.89, [M2+]anode = 1.3 × 10−15 M
0.0591
Because we started with equal numbers of moles of SO42− and M2+, [M2+] = [SO42−] at
equilibrium.

Ksp = [M2+][SO42−] = (1.3 × 10−15)2 = 1.7 × 10−30

57. Cu2+(aq) + H2(g) → 2 H+(aq) + Cu(s) Eocell = 0.34 V − 0.00V = 0.34 V and n = 2
CHAPTER 11 ELECTROCHEMISTRY 431

o 0.0591 1
Since PH 2 = 1.0 atm and [H+] = 1.0 M: Ecell = Ecell − log
2 [Cu 2+ ]

0.0591 1
a. Ecell = 0.34 V − log = 0.34 V − 0.11 V = 0.23 V
2 2.5 × 10 − 4

b. Use the Ksp expression to calculate the Cu2+ concentration in the cell.

Cu(OH)2(s) ⇌ Cu2+(aq) + 2 OH−(aq) Ksp = 1.6 × 10−19 = [Cu2+][OH−]2

1.6 × 10 −19
From the problem, [OH−] = 0.10 M, so: [Cu2+] = 2
= 1.6 × 10−17 M
(0.10)
0.0591 1 0.0591 1
Ecell = Eocell − log = 0.34 − log = 0.34 − 0.50
2 2+
[Cu ] 2 1.6 × 10 −17 = −0.16 V

Because Ecell < 0, the forward reaction is not spontaneous, but the reverse reaction is
spontaneous. The Cu electrode becomes the anode, and Ecell = 0.16 V for the reverse
reaction. The cell reaction is 2 H+(aq) + Cu(s) → Cu2+(aq) + H2(g).
0.0591 1 1
c. 0.195 V = 0.34 V − log 2+
, log = 4.91, [Cu2+] = 10−4.91
2 [Cu ] [Cu 2+ ] = 1.2 × 10−5 M

Note: When determining exponents, we will carry extra significant figures.

o o
d. Ecell = Ecell − (0.0591/2) log (1/[Cu2+]) = Ecell + 0.0296 log [Cu2+]; this equation is in the
form of a straight-line equation, y = mx + b. A graph of Ecell versus log[Cu2+] will yield a
straight line with slope equal to 0.0296 V or 29.6 mV.

o
58. 3 Ni2+(aq) + 2 Al(s) → 2 Al3+(aq) + 3 Ni(s) Ecell = −0.23 V + 1.66 V = 1.43 V; n = 6

0.0591 [Al3+ ]2 0.0591 [Al3+ ]2


Ecell = Eocell − log , 1.82 V = 1.43 V − log
n [ Ni 2 + ]3 6 (1.0) 3

log [Al3+]2 = −39.59, [Al3+]2 = 10−39.59, [Al3+] = 1.6 × 10−20 M

Al(OH)3(s) ⇌ Al3+(aq) + 3 OH−(aq) Ksp = [Al3+] [OH−]3; from the problem, [OH−]
= 1.0 × 10−4 M.

Ksp = (1.6 × 10−20)(1.0 × 10−4)3 = 1.6 × 10−32

59. a. Ag+(x M, anode) → Ag+(0.10 M, cathode); for the silver concentration cell,
EE = 0.00 (as is always the case for concentration cells) and n = 1.
432 CHAPTER 11 ELECTROCHEMISTRY

0.0591 [Ag + ]anode


E = 0.76 V = 0.00 ! log
1 [Ag + ]cathode

[Ag + ]anode [Ag + ]anode


0.76 = -0.0591 log , = 10 −12.86 , [Ag+]anode = 1.4 × 10 −14 M
0.10 0.10
b. Ag+(aq) + 2 S2O32−(aq) ⇌ Ag(S2O3)23−(aq)
3−
[Ag(S2 O 3 ) 2 ] 1.0 × 10 −3
K= 2−
= = 2.9 × 1013
[Ag + ][S2 O 3 ]2 1.4 × 10 −14 (0.050) 2

Electrolysis

60. a. Al3+ + 3 e− → Al; 3 mol e− is needed to produce 1 mol Al from Al3+.

1 mol Al 3 mol e − 96,485 C 1s


1.0 × 103 g × × × −
× = 1.07 × 105 s
27.0 g mol Al mol e 100.0 C
= 3.0 × 101 hours

1 mol 2 mol e − 96,485 C 1s


b. 1.0 g Ni × × × −
× = 33 s
58.7 g mol Ni mol e 100.0 C

1 mol e − 96,485 C 1s
c. 5.0 mol Ag × × −
× = 4.8 × 103 s = 1.3 hours
mol Ag mol e 100.0 C

15 C 60 s 60 min
61. 15 A = × × = 5.4 × 104 C of charge passed in 1 hour
s min mol

1 mol e − 1 mol Co 58.9 g


a. 5.4 × 104 C × × × = 16 g Co
96,485 C 2 mol e − mol

1 mol e − 1 mol Hf 178.5 g


b. 5.4 × 104 C × × × = 25 g Hf
96,485 C 4 mol e − mol

1 mol e − 1 mol I 2 253.8 g I 2


c. 2 I− → I2 + 2e−; 5.4 × 104 C × × −
× = 71 g I2
96,485 C 2 mol e mol I 2

d. Cr is in the +6 oxidation state in CrO3. Six moles of e− are needed to produce 1 mol Cr
from molten CrO3.

1 mol e − 1 mol Cr 52.0 g Cr


5.4 × 104 C × × × = 4.9 g Cr
96,485 C 6 mol e − mol Cr
CHAPTER 11 ELECTROCHEMISTRY 433

60 s 2.00 C 1 mol e − 1 mol Ag


62. 2.30 min × = 138 s; 138 s × × × −
= 2.86 × 10−3 mol Ag
min s 96,485 C mol e

[Ag+] = 2.86 × 10−3 mol Ag+/0.250 L = 1.14 × 10−2 M

63. The oxidation state of bismuth in BiO+ is +3 because oxygen has a !2 oxidation state in this
ion. Therefore, 3 moles of electrons are required to reduce the bismuth in BiO+ to Bi(s).

1 mol Bi 3 mol e − 96,485 C 1s


10.0 g Bi × × × −
× = 554 s = 9.23 min
209.0 g Bi mol Bi mol e 25.0 C

64. When molten salts are electrolyzed, there is only one species present that can be oxidized (the
anion in simple salts), and there is only one species that can be reduced (the cation in simple
salts). When H2O is present, as is the case when aqueous solutions are electrolyzed, we must
consider the oxidation and reduction of water as potential reactions that can occur. When
water is present, more reactions can take place, making predictions more difficult.

65. First determine the species present, and then reference Table 11.1 to help you identify each
species as a possible oxidizing agent (species reduced) or as a possible reducing agent
(species oxidized). Of all the possible oxidizing agents, the species that will be reduced at the
cathode will have the most positive E oc value; the species that will be oxidized at the anode
will be the reducing agent with the most positive − E oa value.

a. Species present: Ni2+ and Br-; Ni2+ can be reduced to Ni, and Br− can be oxidized to Br2
(from Table 11.1). The reactions are:
Cathode: Ni2+ + 2e− → Ni E oc = −0.23 V
Anode: 2 Br- → Br2 + 2 e− − E oa = −1.09 V

b. Species present: Al3+ and F−; Al3+ can be reduced, and F− can be oxidized. The reactions
are:
Cathode: Al3+ + 3 e− → Al E oc = −1.66 V
Anode: 2 F− → F2 + 2 e− − E oa = −2.87 V

c. Species present: Mn2+ and I-; Mn2+ can be reduced, and I− can be oxidized. The reactions
are:
Cathode: Mn2+ + 2 e− → Mn E oc = −1.18 V
Anode: 2 I− → I2 + 2 e− − E oa = −0.54 V

d. For aqueous solutions, we must now consider H2O as a possible oxidizing agent and a
possible reducing agent. Species present: Ni2+, Br−, and H2O. Possible cathode reactions
are:
434 CHAPTER 11 ELECTROCHEMISTRY

Ni2+ + 2e− → Ni E oc = −0.23 V


2 H2O + 2 e− → H2 + 2 OH− E oc = −0.83 V

Because it is easier to reduce Ni2+ than H2O (assuming standard conditions), Ni2+ will be
reduced by the above cathode reaction.

Possible anode reactions are:

2 Br- → Br2 + 2 e− − E oa = −1.09 V


2 H2O → O2 + 4 H+ + 4 e− − E oa = −1.23 V

Because Br− is easier to oxidize than H2O (assuming standard conditions), Br− will be
oxidized by the above anode reaction.

e. Species present: Al3+, F−, and H2O; Al3+ and H2O can be reduced. The reduction
potentials are E oc = −1.66 V for Al3+ and E oc = −0.83 V for H2O (assuming standard
conditions). H2O should be reduced at the cathode (2 H2O + 2 e− → H2 + 2 OH−).

F− and H2O can be oxidized. The oxidation potentials are − E oa = −2.87 V for F− and
− E oa = −1.23 V for H2O (assuming standard conditions). From the potentials, we would
predict H2O to be oxidized at the anode (2 H2O → O2 + 4 H+ + 4 e−).

f. Species present: Mn2+, I−, and H2O; Mn2+ and H2O can be reduced. The possible cathode
reactions are:

Mn2+ + 2 e− → Mn E oc = −1.18 V
2 H2O + 2 e− → H2 + 2 OH− E oc = −0.83 V

Reduction of H2O should occur at the cathode because E oc for H2O is most positive.

I− and H2O can be oxidized. The possible anode reactions are:

2 I− → I2 + 2 e− − E oa = −0.54 V
2 H2O → O2 + 4 H+ + 4 e− − E oa = −1.23 V

Oxidation of I− will occur at the anode because − E oa for I− is most positive.

66. a. Species present: Na+, SO42−, and H2O. From the potentials, H2O is the most easily
oxidized and the most easily reduced species present. The reactions are:

Cathode: 2 H2O + 2 e− → H2(g) + 2 OH−; Anode: 2 H2O → O2(g) + 4 H+ + 4 e−


CHAPTER 11 ELECTROCHEMISTRY 435

b. When water is electrolyzed, a significantly higher voltage than predicted is necessary to


produce the chemical change (called overvoltage). This higher voltage is probably great
enough to cause some SO42− to be oxidized instead of H2O. Thus the volume of O2
generated would be less than expected, and the measured volume ratio would be greater
than 2:1.

67. Au3+ + 3 e− → Au E° = 1.50 V Ni2+ + 2 e− → Ni E° = −0.23 V


Ag+ + e- → Ag E° = 0.80 V Cd2+ + 2 e− → Cd E° = −0.40 V

2 H2O + 2e− → H2 + 2 OH− E° = −0.83 V

Au(s) will plate out first since it has the most positive reduction potential, followed by Ag(s),
which is followed by Ni(s), and finally, Cd(s) will plate out last since it has the most negative
reduction potential of the metals listed.

60 s 2.50 C 1 mol e −
68. Mol e− = 50.0 min × × × = 7.77 × 10−2 mol e−
min s 96,485 C

1 mol Ru
Mol Ru = 2.618 g Ru × = 2.590 × 10−2 mol Ru
101.1 g Ru

Mol e − 7.77 × 10 −2 mol e −


= = 3.00
Mol Ru 2.590 × 10 − 2 mol Ru

The charge on the ruthenium ions is +3 (Ru3+ + 3 e− → Ru).

0.0591 [Cl − ]4 0.0591 (1.0) 4


69. To begin plating out Pd: Ec = 0.62 V − log 2−
= 0 .62 − log
2 [PdCl 4 ] 2 0.020

Ec = 0.62 V − 0.050 V = 0.57 V

1
When 99% of Pd has plated out, [PdCl4−] = (0.020) = 0.00020 M.
100

0.0591 (1.0) 4
Ec = 0.62 − log = 0.62 V − 0.11V = 0.51 V
2 2.0 × 10 − 4

0.0591 (1.0) 4
To begin Pt plating: Ec = 0.73 V − log = 0.73 − 0.050 = 0.68 V
2 0.020

0.0591 (1.0) 4
When 99% of Pt is plated: Ec = 0.73 − log = 0.73 − 0.11 = 0.62 V
2 2.0 × 10 − 4

0.0591 (1.0) 4
To begin Ir plating: Ec = 0.77 V − log = 0.77 − 0.033 = 0.74 V
3 0.020
436 CHAPTER 11 ELECTROCHEMISTRY

0.0591 (1.0) 4
When 99% of Ir is plated: Ec = 0.77 − log = 0.77 − 0.073 = 0.70 V
3 2.0 × 10 − 4

Yes, since the range of potentials for plating out each metal do not overlap, we should be able
to separate the three metals. The exact potential to apply depends on the oxidation reaction.
The order of plating will be Ir(s) first, followed by Pt(s), and finally, Pd(s) as the potential is
gradually increased.

2.00 C 1 mol e − 1 mol M


70. 74.1 s × × × = 5.12 × 10 −4 mol M, where M = unknown metal
s 96,485 C 3 mol e −

0.107 g M 209 g
Molar mass = −4
= ; the element is bismuth.
5.12 × 10 mol M mol

71. Alkaline earth metals form +2 ions, so 2 mol of e− are transferred to form the metal M.

5.00 C 1 mol e − 1 mol M


Mol M = 748 s × × × = 1.94 × 10−2 mol M
s 96,485 C 2 mol e −

0.471 g M
Molar mass of M = = 24.3 g/mol; MgCl2 was electrolyzed.
1.94 × 10 − 2 mol M

150. × 103 g C 6 H 8 N 2 1h 1 min 1 mol C 6 H 8 N 2 2 mol e − 96,485 C


72. × × × × ×
h 60 min 60 s 108.14 g C 6 H 8 N 2 mol C 6 H 8 N 2 mol e −

= 7.44 × 104 C/s or a current of 7.44 × 104 A

73. F2 is produced at the anode: 2 F− → F2 + 2 e−

60 min 60 s 10.0 C 1 mol e −


2.00 h × × × × = 0.746 mol e−
h min s 96,485 C

1 mol F2 nRT
0.746 mol e− × −
= 0.373 mol F2; PV = nRT, V =
2 mol e P

(0.373 mol)(0.08206 L atm K −1 mol −1 )(298 K )


V= = 9.12 L F2
1.00 atm

K is produced at the cathode: K+ + e− → K

1 mol K 39.10 g K
0.746 mol e− × × = 29.2 g K
mol e − mol K
CHAPTER 11 ELECTROCHEMISTRY 437

15000 J h 60 s 60 min
74. 15 kWh = × × = 5.4 × 107 J or 5.4 × 104 kJ (Hall process)
s min h
1 mol Al 10.7 kJ
To melt 1.0 kg Al requires: 1.0 × 103 g Al × × = 4.0 × 102 kJ
26.98 g mol Al

It is feasible to recycle Al by melting the metal because, in theory, it takes less than 1% of the
energy required to produce the same amount of Al by the Hall process.

75. In the electrolysis of aqueous sodium chloride, H2O is reduced in preference to Na+, and Cl−
is oxidized in preference to H2O. The anode reaction is 2 Cl− → Cl2 + 2 e−, and the cathode
reaction is 2 H2O + 2 e− → H2 + 2 OH−. The overall reaction is 2 H2O(l) + 2 Cl− (aq) →
Cl2(g) + H2(g) + 2 OH− (aq).

From the 1 : 1 mole ratio between Cl2 and H2 in the overall balanced reaction, if 6.00 L of
H2(g) is produced, then 6.00 L of Cl2(g) also will be produced since moles and volume of gas
are directly proportional at constant T and P (see Chapter 5 of text).

76. The half-reactions for the electrolysis of water are:

(2 e− + 2 H2O → H2 + 2 OH−) × 2
2 H2O → 4 H+ + O2 + 4 e−
__________________________
2 H2O(l) → 2 H2(g) + O2(g)

Note: 4 H+ + 4 OH− → 4 H2O, and n = 4 for this reaction as it is written.

60 s 25.0 C 1 mol e − 2 mol H 2


15.0 min × × × × = 1.17 × 10−2 mol H2
min s 96,485 C 4 mol e −

At STP, 1 mole of an ideal gas occupies a volume of 22.42 L (see Chapter 5 of the text).

22.42 L
1.17 × 10−2 mol H2 × = 0.262 L = 262 mL H2
mol H 2

1 mol O 2 22.42 mol L


1.17 × 10−2 mol H2 × × = 0.131 L = 131 mL O2
2 mol H 2 mol O 2

Additional Exercises

77. (CO + O2− → CO2 + 2 e−) × 2


O2 + 4 e− → 2 O2−
__________________________
2 CO + O2 → 2 CO2

− ΔG − (−380 × 10 −3 J )
ΔG = −nFE, E = = = 0.98 V
nF (4 mol e − )(96,485 C / mol e − )
438 CHAPTER 11 ELECTROCHEMISTRY

78. As a battery discharges, Ecell decreases, eventually reaching zero. A charged battery is not at
equilibrium. At equilibrium, Ecell = 0 and ΔG = 0. We get no work out of an equilibrium
system. A battery is useful to us because it can do work as it approaches equilibrium.

Both fuel cells and batteries are galvanic cells that produce cell potentials to do useful work.
However, fuel cells, unlike batteries, have the reactants continuously supplied and can
produce a current indefinitely.

The overall reaction in the hydrogen-oxygen fuel cell is 2 H2(g) + O2(g) → 2 H2O(l). The
half-reactions are:

4 e− + O2 + 2 H2O → 4 OH− cathode


2 H2 + 4 OH− → 4 H2O + 4 e− anode

Utilizing the standard potentials in Table 11.1, E ocell = 0.40 V + 0.83 V = 1.23 V for the
hydrogen-oxygen fuel cell. As with all fuel cells, the H2(g) and O2(g) reactants are con-
tinuously supplied. See Figure 11.16 for a schematic of this fuel cell.

79. For C2H5OH, H has a +1 oxidation state, and O has a !2 oxidiation state. This dictates a !2
oxidation state for C. For CO2, O has a !2 oxidiation state, so carbon has a +4 oxidiation
state. Six moles of electrons are transferred per mole of carbon oxidized (C goes from !2 →
+4). Two moles of carbon are in the balanced reaction, so n = 12.

wmax = !1320 kJ = ΔG = !nFE, !1320 × 103 J = !nFE = !(12 mol e−)(96,485 C/mol e−)E

E = 1.14 J/C = 1.14 V

80. O2 + 2 H2O + 4 e− → 4 OH− E oc = 0.40 V


(H2 + 2 OH− → 2 H2O + 2 e−) × 2 ! E oa = 0.83 V
________________________________________________________
2 H2(g) + O2(g) → 2 H2O(l) E ocell = 1.23 V = 1.23 J/C

Because standard conditions are assumed, wmax = ΔG° for 2 mol H2O produced.

ΔG° = − nFE ocell = !(4 mol e−)(96,485 C/mol e−)(1.23 J/C) = !475,000 J = !475 kJ

For 1.00 × 103 g H2O produced, wmax is:

1 mol H 2 O − 475 kJ
1.00 × 103 g H2O × × = !13,200 kJ = wmax
18.02 g H 2 O 2 mol H 2 O

The work done can be no larger than the free energy change. The best that could happen is
that all the free energy released would go into doing work, but this does not occur in any real
process because there is always waste energy in a real process. Fuel cells are more efficient in
converting chemical energy into electrical energy; they are also less massive. The major
CHAPTER 11 ELECTROCHEMISTRY 439

disadvantage is that they are expensive. In addition, H2(g) and O2(g) are an explosive mixture
if ignited, much more so than fossil fuels.

81. Cadmium goes from the zero oxidation state to the +2 oxidation state in Cd(OH)2. Because
one mole of Cd appears in the balanced reaction, n = 2 mol electrons transferred. At standard
conditions:

wmax = ΔG° = −nFE°, wmax = −(2 mol e−)(96,485 C/mol e−)(1.10 J/C) = −2.12 × 105 J
= −212 kJ

82. The corrosion of a metal can be viewed as the process of returning metals to their natural
state. The natural state of metals is to have positive oxidation numbers. This corrosion is the
oxidation of a pure metal (oxidation number = 0) into its ions. For corrosion of iron to take
place, you must have:

a. exposed iron surface–a reactant

b. O2(g)–a reactant

c. H2O(l)–a reactant, but also provides a medium for ion flow (it provides the salt bridge)

d. ions–needed to complete the salt bridge

Because water is a reactant and acts as a salt bridge for corrosion, cars do not rust in dry-air
climates, whereas corrosion is a big problem in humid climates. Salting roads in the winter
also increases the severity of corrosion. The dissolution of the salt into ions on the surface of
a metal increases the conductivity of the aqueous solution and accelerates the corrosion
process.

83. a. Paint: covers the metal surface so that no contact occurs between the metal and air. This
only works as long as the painted surface is not scratched.

b. Durable oxide coatings: covers the metal surface so that no contact occurs between the
metal and air.

c. Galvanizing: coating steel with zinc; Zn forms an effective oxide coating over steel;
also, zinc is more easily oxidized than the iron in the steel.

d. Sacrificial metal: attaching a more easily oxidized metal to an iron surface; the more
active metal is preferentially oxidized instead of iron.

e. Alloying: adding chromium and nickel to steel; the added Cr and Ni form oxide coatings
on the steel surface.

f. Cathodic protection: a more easily oxidized metal is placed in electrical contact with the
metal we are trying to protect. It is oxidized in preference to the protected metal. The
protected metal becomes the cathode electrode, thus cathodic protection.
440 CHAPTER 11 ELECTROCHEMISTRY

84. Metals corrode because they oxidize easily. Referencing Table 11.1, most metals are
associated with negative standard reduction potentials. This means the reverse reactions, the
oxidation half-reactions, have positive oxidation potentials, indicating that they oxidize fairly
easily. Another key point is that the reduction of O2 (which is a reactant in corrosion
processes) has a more positive E ored than most of the metals (for O2, E ored = 0.40 V). This
means that when O2 is coupled with most metals, the reaction will be spontaneous because
E ocell > 0, so corrosion occurs.

The noble metals (Ag, Au, and Pt) all have standard reduction potentials greater than that of
O2. Therefore, O2 is not capable of oxidizing these metals at standard conditions.

Note: The standard reduction potential for Pt → Pt2+ + 2 e− is not in Table 11.1. As expected,
its reduction potential is greater than that of O2 (E oPt = 1.19 V).

85. Zn → Zn2+ + 2 e− − E oa = 0.76 V; Fe → Fe2+ + 2 e− − E oa = 0.44 V

It is easier to oxidize Zn than Fe, so the Zn will be oxidized, protecting the iron of the
Monitor's hull.

86. (Al3+ + 3 e− → Al) × 2 E oc = −1.66 V


(M → M2+ + 2 e−) × 3 − E oa = ?
_________________________________________________________________
3 M(s) + 2 Al3+(aq) → 2 Al(s) + 3 M2+(aq) E ocell = − E oa − 1.66 V

ΔG° = − nFE ocell , −411 × 103 J = −(6 mol e−)(96,485 C/mol e−)( E ocell ), E ocell = 0.71 V

E ocell = − E oa − 1.66 V = 0.71 V, − E oa = 2.37 or E oc = −2.37

From Table 11.1, the reduction potential for Mg2+ + 2 e− → Mg is −2.37 V, which fits the data.
Hence the metal is magnesium.

87. The potential oxidizing agents are NO3− and H+. Hydrogen ion cannot oxidize Pt under either
condition. Nitrate cannot oxidize Pt unless there is Cl− in the solution. Aqua regia has both Cl−
and NO3-. The overall reaction is:

(NO3− + 4 H+ + 3 e− → NO + 2 H2O) × 2 E oc = 0.96 V


(4 Cl− + Pt → PtCl42− + 2 e−) × 3 − E oa = −0.755 V
_________________________________________________________________________________
12 Cl−(aq) + 3 Pt(s) + 2 NO3−(aq) + 8 H+(aq) → 3 PtCl42-(aq) + 2 NO(g) + 4 H2O(l) E ocell = 0.21 V

88. a. 3 e− + 4 H+ + NO3− → NO + 2 H2O E° = 0.96 V

Nitric acid can oxidize Co to Co2+ ( E ocell > 0), but is not strong enough to oxidize Co to
Co3+ ( E ocell < 0). Co2+ is the primary product assuming standard conditions.
CHAPTER 11 ELECTROCHEMISTRY 441

b. Concentrated nitric acid is about 16 mol/L. [H+] = [NO3−] = 16 M; assume PNO = 1 atm.

0.0591 P 0.0591 1
E = 0.96 V − log + 4 NO − = 0.96 − log
3 [H ] [ NO 3 ] 3 (16) 5

E = 0.96 − (−0.12) = 1.08 V

No, concentrated nitric acid still will only be able to oxidize Co to Co2+.

89. a. Ecell = Eref + 0.05916 pH, 0.480 V = 0.250 V + 0.05916 pH

0.480 − 0.250
pH = = 3.888; uncertainty = ±1 mV = ± 0.001 V
0.05916

0.481 − 0.250 0.479 − 0.250


pHmax = = 3.905; pHmin = = 3.871
0.05916 0.05916

Thus if the uncertainty in potential is ±0.001 V, then the uncertainty in pH is ±0.017, or


about ±0.02 pH units. For this measurement, [H+] = 10−3.888 = 1.29 × 10−4 M. For an
error of +1 mV, [H+] = 10−3.905 = 1.24 × 10−4 M. For an error of −1 mV, [H+] = 10-3.871 =
1.35 × 10−4 M. So the uncertainty in [H+] is ±0.06 × 10−4 M = ±6 × 10−6 M.

b. From part a, we will be within ±0.02 pH units if we measure the potential to the nearest
±0.001 V (±1 mV).

90. a. ΔG° = ∑ n p ΔG of , products − ∑ n r ΔG or, reactants = 2(−480.) + 3(86) − [3(−40.)] = −582 kJ


− ΔG o − (−582,000 J )
From oxidation numbers, n = 6. ΔG° = −nFE°, E° = = = 1.01 V
nF 6(96,485) C

nE o 6(1.01)
log K = = = 102.538, K = 10102.538 = 3.45 × 10102
0.0591 0.0591

b. 3 × (2 e− + Ag2S → 2 Ag + S2−) E oAg 2S = ?


2 × (Al → Al3+ + 3 e−) − E oa = 1.66 V
___________________________________________________________
3 Ag2S(s) + 2 Al(s) → 6 Ag(s) + 3 S2−(aq) + 2 Al3+(aq) E ocell = 1.01 V

E ocell = E oAg 2S + 1.66, E oAg 2S = 1.01 − 1.66 = −0.65 V


442 CHAPTER 11 ELECTROCHEMISTRY

91. 2 Ag+(aq) + Cu(s) → Cu2+(aq) + 2 Ag(s) E ocell = 0.80 - 0.34 V = 0.46 V; A galvanic cell
produces a voltage as the forward reaction occurs. Any stress that increases the tendency of
the forward reaction to occur will increase the cell potential, whereas a stress that decreases
the tendency of the forward reaction to occur will decrease the cell potential.

a. Added Cu2+ (a product ion) will decrease the tendency of the forward reaction to occur,
which will decrease the cell potential.

b. Added NH3 removes Cu2+ in the form of Cu(NH3)42+. Because a product ion is removed,
this will increase the tendency of the forward reaction to occur, which will increase the
cell potential.

c. Added Cl− removes Ag+ in the form of AgCl(s). Because a reactant ion is removed, this
will decrease the tendency of the forward reaction to occur, which will decrease the cell
potential.

[Cu 2 + ]0
d. Q1 = ; as the volume of solution is doubled, each concentration is halved.
[Ag + ]02

1/2 [Cu 2 + ]0 2[Cu 2+ ]0


Q2 = = = 2Ql
(1/2 [ Ag + ]0 ) 2 [Ag + ]02

The reaction quotient is doubled because the concentrations are halved. Because
reactions are spontaneous when Q < K, and because Q increases when the solution
volume doubles, the reaction is closer to equilibrium, which will decrease the cell
potential.

e. Because Ag(s) is not a reactant in this spontaneous reaction, and because solids do not
appear in the reaction quotient expressions, replacing the silver electrode with a platinum
electrode will have no effect on the cell potential.

92. a.
e e

Salt bridge
Cathode
Anode

Pt Au

1.0 M Fe2+
1.0 M Au3+
1.0 M Fe3+
CHAPTER 11 ELECTROCHEMISTRY 443

b. Au3+(aq) + 3 Fe2+(aq) → 3 Fe3+(aq) + Au(s) E ocell = 1.50 − 0.77 = 0.73 V

0.0591 0.0591 [Fe3+ ]3


E cell = E ocell − log Q = 0.73 V − log
n 3 [Au 3+ ][Fe 2 + ]3

0.0591 1
Since [Fe3+] = [Fe2+] = 1.0 M: 0.31 V = 0.73 V − log
3 [Au 3+ ]

3(−0.42) 1
= − log , log [Au3+] = −21.32, [Au3+] = 10−21.32 = 4.8 × 10−22 M
0.0591 [Au 3+ ]

Au3+ + 4 Cl− ⇌ AuCl4-; because the equilibrium Au3+ concentration is so small, assume
[AuCl4−] ≈ [Au3+]0 ≈ 1.0 M; i.e., assume K is large so that the reaction essentially goes to
completion.

[AuCl −4 ] 1.0
K= 3+ − 4
= − 22 4
= 2.1 × 1025; asumption good (K is large).
[Au ][Cl ] (4.8 × 10 )(0.10)

Challenge Problems
93. Chromium(III) nitrate [Cr(NO3)3] has chromium in the +3 oxidation state.

1 mol Cr 3 mol e− 96, 485 C


1.15 g Cr × × × −
= 6.40 × 103 C of charge
52.00 g mol Cr mol e

For the Os cell, 6.40 × 103 C of charge also was passed.

1 mol Os 1 mol e −
3.15 g Os × 3
= 0.0166 mol Os; 6.40 × 10 C × = 0.0663 mol e−
190.2 g 96,485 C
Mol e − 0.0663
= = 3.99 ≈ 4
Mol Os 0.0166

This salt is composed of Os4+ and NO3− ions. The compound is Os(NO3)4, osmium(IV)
nitrate.

For the third cell, identify X by determining its molar mass. Two moles of electrons are
transferred when X2+ is reduced to X.

2.11 g X
Molar mass = = 63.6 g/mol
3 1 mol e − 1 mol X
6.40 × 10 C × ×
96,485 C 2 mol e −

This is copper (Cu).


444 CHAPTER 11 ELECTROCHEMISTRY

0.0591
94. Eocell = 0.400 V – 0.240 V = 0.160 V; E = EE ! log Q
n

0.0591 0.120
0.180 = 0.160 ! log(9.32 × 10 −3 ), 0.020 = , n=6
n n

Six moles of electrons are transferred in the overall balanced reaction. We now have to figure
out how to get 6 mol e− into the overall balanced equation. The two possibilities are to have
ion charges of +1 and +6 or +2 and +3; only these two combinations yield a 6 when common
multiples are determined when adding the reduction half-reaction to the oxidation half-react-
ion. Because N forms +2 charged ions, M must form for +3 charged ions. The overall cell
reaction can now be determined.

(M3+ + 3 e− → M) × 2 E oc = 0.400 V
(N → N2+ + 2 e−) × 3 ! E oa = !0.240 V
_____________________________________________
2 M3+ + 3 N → 3 N2+ + 2 M E ocell = 0.160 V

[ N 2+ ]0
3
−3 (0.10) 3
Q = 9.32 × 10 = = 3+ 2
, [M3+] = 0.33 M
[M 3+ ]0
2
[M ]

wmax = ΔG = !nFE = !6(96,485)(0.180) = !1.04 × 105 J = !104 kJ

The maximum amount of work this cell could produce is 104 kJ.

95. a. Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) E ocell = 1.10 V

0.0591 [ Zn 2 + ]
Ecell = 1.10 V − log
2 [Cu 2+ ]

0.0591 0.10
Ecell = 1.10 V − log = 1.10 V − (!0.041 V) = 1.14 V
2 2.50

60 min 60 s 10.0 C 1 mol e − 1 mol Cu


b. 10.0 h × × × × × = 1.87 mol Cu produced
h min s 96,485 C 2 mol e −

The Cu2+ concentration decreases by 1.87 mol/L, and the Zn2+ concentration will increase
by 1.87 mol/L.

[Cu2+] = 2.50 − 1.87 = 0.63 M; [Zn2+] = 0.10 + 1.87 = 1.97 M

0.0591 1.97
Ecell = 1.10 V − log = 1.10 V − 0.015 V = 1.09 V
2 0.63
CHAPTER 11 ELECTROCHEMISTRY 445

65.38 g Zn
c. 1.87 mol Zn consumed × = 122 g Zn
mol Zn

Mass of electrode = 200. − 122 = 78 g Zn

63.55 g Cu
1.87 mol Cu formed × = 119 g Cu
mol Cu

Mass of electrode = 200. + 119 = 319 g Cu

d. Three things could possibly cause this battery to go dead:

1. All the Zn is consumed.


2. All the Cu2+ is consumed.
3. Equilibrium is reached (Ecell = 0).

We began with 2.50 mol Cu2+ and 200. g Zn × 1 mol Zn/65.38 g Zn = 3.06 mol Zn. Cu2+
is the limiting reagent and will run out first. To react all the Cu2+ requires:

2 mol e − 96,485 C 1s 1h
2.50 mol Cu2+ × 2+
× −
× × = 13.4 h
mol Cu mol e 10.0 C 3600 s

0.0591 [ Zn 2+ ]
For equilibrium to be reached: E = 0 = 1.10 V − log
2 [Cu 2+ ]
[ Zn 2 + ]
2+
= K = 102(1.10)/0.0591 = 1.68 × 1037
[Cu ]
This is such a large equilibrium constant that virtually all the Cu2+ must react to reach
equilibrium. So the battery will go dead in 13.4 hours.

96. a. Emeas = Eref − 0.05916 log[F−], 0.4462 = 0.2420 − 0.05916 log[F−]

log[F−] = −3.4517, [F−] = 3.534 × 10−4 M

b. pH = 9.00; pOH = 5.00; [OH−] = 1.0 × 10−5 M

0.4462 = 0.2420 − 0.05916 log[[F−] + 10.0(1.0 × 10−5)]

log([F−] + 1.0 × 10−4) = −3.452, [F−] + 1.0 × 10−4 = 3.532 × 10−4, [F−] = 2.5 × 10−4 M

True value is 2.5 × 10−4, and by ignoring the [OH−], we would say [F−] was 3.5 × 10−4, so:

1.0 × 10 −4
Percent error = × 100 = 40.%
2.5 × 10 − 4
446 CHAPTER 11 ELECTROCHEMISTRY

[F − ] 2.5 × 10 −4
c. [F−] = 2.5 × 10−4 M; = 50. =
k[OH − ] 10.0[OH − ]

2.5 × 10 −4
[OH−] = = 5.0 × 10−7 M; pOH = 6.30; pH = 7.70
10.0 × 50.

[H + ][F − ]
d. HF ⇌ H+ + F− Ka = = 7.2 × 10−4; if 99% is F−, then [F−]/[HF] = 99.
[HF]

99[H+] = 7.2 × 10−4, [H+] = 7.3 × 10−6 M; pH = 5.14

e. The buffer controls the pH so that there is little HF present and there is little response to
OH−. Typically, a buffer of pH = 6.0 is used.

97. a. 3 × (e− + 2 H+ + NO3− → NO2 + H2O) E oc = 0.775 V


2 H2O + NO → NO3− + 4 H+ + 3 e− − E oa = −0.957 V
_______________________________________________________________________
2 H+(aq) + 2 NO3−(aq) + NO(g) → 3 NO2(g) + H2O(l) E ocell = −0.182 V K = ?

Eo 3(−0.182)
log K = = = −9.239, K = 10−9.239 = 5.77 × 10−10
0.0591 0.0591

b. Let C = concentration of HNO3 = [H+] = [NO3−].

3 3
PNO PNO
5.77 × 10−10 = 2
= 2

PNO × [ H + ]2 × [ NO 3− ]2 PNO × C 4

If 0.20% NO2 by moles and Ptotal = 1.00 atm:

0.20 mol NO 2
PNO 2 = × 1.00 atm = 2.0 × 10−3 atm; PNO = 1.00 − 0.0020 = 1.00 atm
100. mol total

(2.0 × 10 −3 ) 3
5.77 × 10−10 = , C = 1.9 M HNO3
(1.00)C 4

98. 2 Ag+(aq) + Ni(s) → Ni2+(aq) + Ag(s); the cell is dead at equilibrium (E = 0).

E ocell = 0.80 V + 0.23 V = 1.03 V

0.0591
0 = 1.03 V − log K, K = 7.18 × 1034
2

K is very large. Let the forward reaction go to completion.


CHAPTER 11 ELECTROCHEMISTRY 447

34
2 Ag+ + Ni → Ni2+ + 2 Ag K = [Ni2+]/[Ag+]2 = 7.18 × 10

Before 1.0 M 1.0 M


After 0 M 1.5 M

Now solve the back-equilibrium problem.

2 Ag+ + Ni ⇌ Ni2+ + 2 Ag

Initial 0 1.5 M
Change +2x ← −x
Equil. 2x 1.5 − x

34 1 .5 − x 1.5
K = 7.18 × 10 = 2
≈ ; solving, x = 2.3 × 10−18 M. Assumptions good.
(2 x) (2 x) 2

−18
[Ag+] = 2x = 4.6 × 10 M; [Ni2+] = 1.5 − 2.3 × 10−18 = 1.5 M

99. 2 H+ + 2 e− → H2 E oc = 0.000 V
Fe → Fe2+ + 2e− − E oa = −(−0.440V)
_________________________________________________
2 H+(aq) + Fe(s) → H2(g) + Fe3+(aq) E ocell = 0.440 V

0.0591 PH 2 × [Fe3+ ]
Ecell = E ocell − log Q, where n = 2 and Q =
n [ H + ]2

To determine Ka for the weak acid, first use the electrochemical data to determine the H+
concentration in the half-cell containing the weak acid.

0.0591 1.00 atm(1.00 × 10 −3 M )


0.333 V = 0.440 V − log
2 [ H + ]2

0.107(2) 1.0 × 10 −3 1.0 × 10 −3


= log + 2
, + 2
= 103.621 = 4.18 × 103, [H+] = 4.89 × 10−4 M
0.0591 [H ] [H ]

Now we can solve for the Ka value of the weak acid HA through the normal setup for a weak
acid problem.
[H + ][A − ]
HA(aq) ⇌ H+(aq) + A−(aq) Ka =
[HA]
Initial 1.00 M ~0 0
Equil. 1.00 − x x x

x2 (4.89 × 10 −4 ) 2
Ka = , where x = [H+] = 4.89 × 10-4 M, Ka = −4
= 2.39 × 10−7
1.00 − x 1.00 − 4.89 × 10
448 CHAPTER 11 ELECTROCHEMISTRY

100.
e e

Salt bridge

Anode Cathode

Cu Cu

1.0 × 10-4 M 1.00 M


Cu2+ Cu2+

0.0591 ⎛ 1.0 × 10 −4 ⎞
a. E° = 0 (concentration cell), E = 0 − log ⎜⎜ ⎟ , E = 0.12 V

2 ⎝ 1.00 ⎠
b. Cu2+(aq) + 4 NH3(aq) ⇌ Cu(NH3)42+(aq); because [Cu2+] << [NH3], [NH3]0 = 2.0 M
= [NH3]eq.

Also, Koverall = K1•K2•K3•K4 = 1.0 × 1013, so the reaction lies far to the right. Let the
reaction go to completion.

Cu2+ + 4 NH3 → Cu(NH3)42+

Before 1.0 × 10−4 M 2.0 M 0


After 0 2.0 1.0 × 10−4

Now allow the reaction to get to equilibrium.

Cu2+ + 4 NH3 → Cu(NH3)42+

Initial 0 2.0 M 1.0 × 10−4 M


Equil. x 2.0 + 4x 1.0 × 10−4 − x

(1.0 × 10 −4 − x) 1.0 × 10 −4
4
≈ 4
= 1.0 × 1013, x = [Cu2+] = 6.3 × 10−19 M
x(2.0 + 4 x) x ( 2 .0 )

0.0591 ⎛ 6.3 × 10 −19 ⎞


Thus E = 0 − log ⎜⎜ ⎟ , E = 0.54 V

2 ⎝ 1.00 ⎠

101. a. (Ag+ + e− → Ag) × 2 E oc = 0.80 V


Cu → Cu2+ + 2 e− − E oa = −0.34 V
_________________________________________________
2 Ag+(aq) + Cu(s) → 2 Ag(s) + Cu2+(aq) E ocell = 0.46 V
CHAPTER 11 ELECTROCHEMISTRY 449

0.0591 [Cu 2 + ]
Ecell = E ocell − log Q, where n = 2 and Q = .
n [Ag + ]2

To calculate Ecell, we need to use the Ksp data to determine [Ag+].

AgCl(s) ⇌ Ag+(aq) + Cl−(aq) Ksp = 1.6 × 10-10 = [Ag+][Cl−]

Initial s = solubility (mol/L) 0 0


Equil. s s

Ksp = 1.6 × 10−10 = s2, s = [Ag+] = 1.3 × 10−5 mol/L

0.0591 2 .0
Ecell = 0.46 V − log = 0.46 V − 0.30 = 0.16 V
2 (1.3 × 10 −5 ) 2

[Cu ( NH 3 ) 24+ ]
b. Cu2+(aq) + 4 NH3(aq) ⇌ Cu(NH4)42+(aq) K = 1.0 × 1013 =
[Cu 2+ ][ NH 3 ]4

Because K is very large for the formation of Cu(NH3)42+, the forward reaction is
dominant. At equilibrium, essentially all the 2.0 M Cu2+ will react to form 2.0 M
Cu(NH3)42+. This reaction requires 8.0 M NH3 to react with all the Cu2+ in the balanced
equation. Therefore, the moles of NH3 added to 1.0-L solution will be larger than 8.0
mol since some NH3 must be present at equilibrium. In order to calculate how much NH3
is present at equilibrium, we need to use the electrochemical data to determine the Cu2+
concentration.

0.0591 0.0591 [Cu 2 + ]


Ecell = E ocell − log Q, 0.52 V = 0.46 V − log
n 2 (1.3 × 10 −5 ) 2

[Cu 2+ ] − 0.06(2) [Cu 2+ ]


log = = −2.03, = 10−2.03 = 9.3 × 10−3
(1.3 × 10 −5 ) 2 0.0591 (1.3 × 10 −5 ) 2

[Cu2+] = 1.6 × 10−12 = 2 × 10−12 M

(We carried extra significant figures in the calculation.)

Note: Our assumption that the 2.0 M Cu2+ essentially reacts to completion is excellent as
only 2 × 10−12 M Cu2+ remains after this reaction. Now we can solve for the equilibrium
[NH3].

[Cu ( NH 3 ) 24+ ] ( 2.0)


K = 1.0 × 1013 = 2+
= , [NH3] = 0.6 M
[Cu ][ NH 3 ] 4
( 2 × 10 −12 ) [ NH 3 ]4

Because 1.0 L of solution is present, 0.6 mol NH3 remains at equilibrium. The total
moles of NH3 added is 0.6 mol plus the 8.0 mol NH3 necessary to form 2.0 M
Cu(NH3)42+. Therefore, 8.0 + 0.6 = 8.6 mol NH3 was added.
450 CHAPTER 11 ELECTROCHEMISTRY

102. (Ag+ + e− → Ag) × 2 E oc = 0.80 V


Pb → Pb2+ + 2 e− − E oa = −(−0.13)
______________________________________________
2 Ag+(aq) + Pb(s) → 2 Ag(s) + Pb2+(aq) E ocell = 0.93 V

0.0591 [ Pb 2+ ] 0.0591 (1.8)


E = E° − log + 2
, 0.83 V = 0.93 V − log
n [Ag ] 2 [Ag + ]2

(1.8) 0.10(2) (1.8)


log + 2
= = 3.38, + 2
= 103.38, [Ag+] = 0.027 M
[Ag ] 0.0591 [Ag ]

Ag2SO4(s) ⇌ 2 Ag+(aq) + SO42−(aq) Ksp = [Ag+]2[SO42-]

Initial s = solubility (mol/L) 0 0


Equil. 2s s

From the problem: 2s = 0.027 M, s = 0.027/2

Ksp = (2s)2(s) = (0.027)2(0.027/2) = 9.8 × 10−6

103. (Ag+ + e− → Ag) × 2 E oc = 0.80 V


Cd → Cd2+ + 2 e− − E oa = 0.40 V
_________________________________________________
2 Ag+(aq) + Cd(s) → Cd2+(aq) + 2 Ag(s) E ocell = 1.20 V

Overall complex ion reaction:


Ag+(aq) + 2 NH3(aq) → Ag(NH3)2+(aq) K = K1K2 = 2.1 × 103(8.2 × 103) = 1.7 × 107

Because K is large, we will let the reaction go to completion, and then solve the back-
equilibrium problem.
Ag+ + 2 NH3 ⇌ Ag(NH3)2+ K = 1.7 × 107
Before 1.00 M 15.0 M 0
After 0 13.0 1.00 New initial
Change x +2x ← −x
Equil. x 13.0 + 2x 1.00 − x

+
[Ag( NH 3 ) 2 ] 1.00 − x 1.00
K= + 2
; 1.7 × 10 7 = 2

[Ag ][ NH 3 ] x(13.0 + 2 x) x(13.0) 2

Solving: x = 3.5 × 10−10 M = [Ag+]; assumptions good.

0.0591 [Cd 2 + ] 0.0591 ⎡ 1.0 ⎤


E = E° − log + 2
= 1.20 V − log ⎢ −10 2 ⎥
2 [Ag ] 2 ⎣ (3.5 × 10 ) ⎦

E = 1.20 − 0.56 = 0.64 V


CHAPTER 11 ELECTROCHEMISTRY 451

104. Standard reduction potentials can only be manipulated and added together when electrons in
the reduction half-reaction exactly cancel with the electrons in the oxidation half-reaction.
We will solve this problem by applying the equation ΔGE = !nFEE to the half-reactions.

ΔG of for e− = 0.

M3+ + 3 e− → M ΔGE = !nFEE = !3(96,485)(0.10) = −2.9 × 104 J

Because M and e− have ΔG of = 0: −2.9 × 104 J = ! ΔG of , M 3+ , ΔG of , M 3+ = 2.9 × 104 J

M2+ + 2 e− → M ΔGE = !nFEE = !2(96,485)(0.50) = −9.6 × 104 J

−9.6 × 104 J = ! ΔG of , M 2+ , ΔG of , M 2+ = 9.6 × 104 J

M3+ + e− → M2+ ΔGE = 9.6 × 104 J – (2.9 × 104 J) = 6.7 × 104 J

− ΔG o − (6.7 × 10 4 )
EE = = = −0.69 V; M3+ + e− → M2+ E° = −0.69 V
nF (1)(96,485)

105. a. From Table 11.1: 2 H2O + 2 e− → H2 + 2 OH− E° = -0.83 V

E ocell = E oH 2 O − E oZr = !0.83 V + 2.36 V = 1.53 V

Yes, the reduction of H2O to H2 by Zr is spontaneous at standard conditions since


E ocell > 0.

b. (2 H2O + 2 e− → H2 + 2 OH−) × 2
Zr + 4 OH− → ZrO2•H2O + H2O + 4 e−
______________________________________
3 H2O(l) + Zr(s) → 2 H2(g) + ZrO2•H2O(s)

c. ΔG° = −nFE° = −(4 mol e−)(96,485 C/mol e−)(1.53 J/C) = −5.90 × 105 J = −590. kJ

0.0591
E = E° − log Q; at equilibrium, E = 0 and Q = K.
n

0.0591 4(1.53)
E° = log K, log K = = 104, K ≈ 10104
n 0.0591

1000 g 1 mol Zr 2 mol H 2


d. 1.00 × 103 kg Zr × × × = 2.19 × 104 mol H2
kg 91.22 g Zr mol Zr
452 CHAPTER 11 ELECTROCHEMISTRY

2.016 g H 2
2.19 × 104 mol H2 × = 4.42 × 104 g H2
mol H 2

nRT (2.19 × 10 4 mol)(0.08206 L atm K −1 mol −1 )(1273 K )


V= = = 2.3 × 106 L H2
P 1.0 atm
e. Probably yes; less radioactivity overall was released by venting the H2 than what would
have been released if the H2 had exploded inside the reactor (as happened at Chernobyl).
Neither alternative is pleasant, but venting the radioactive hydrogen is the less unpleasant
of the two alternatives.

Marathon Problems

106. a. Cu2+ + 2 e− → Cu E oc = 0.34 V


V → V2+ + 2 e− − E oa = 1.20 V
_________________________________________________
Cu2+(aq) + V(s) → Cu(s) + V2+(aq) E ocell = 1.54 V

0.0591 [V 2+ ] [V 2+ ]
Ecell = E ocell − log Q, where n = 2 and Q = = .
n [Cu 2+ ] 1.00 M
To determine Ecell, we must know the initial [V2+], which can be determined from the
stoichiometric point data. At the stoichiometric point, moles H2EDTA2− added = moles
V2+ present initially.
0.0800 mol H 2 EDTA 2− 1 mol V 2 +
Mol V2+ present initially = 0.5000 L × ×
L mol H 2 EDTA 2−
= 0.0400 mol V2+
0.0400 mol V 2+
[V2+]0 = = 0.0400 M
1.00 L

0.0591 0.0400
Ecell = 1.54 V − log = 1.54 V − (−0.0413) = 1.58 V
2 1.00

b. Use the electrochemical data to solve for the equilibrium [V2+].

0.0591 [V 2+ ] 0.0591 [V 2+ ]
Ecell = E ocell − log , 1.98 V = 1.54 V − log
n [Cu 2 + ] 2 1.00 M

[V2+] = 10−(0.44)(2)/0.0591 = 1.3 × 10−15 M

[ VEDTA 2− ][H + ]2
H2EDTA2−(aq) + V2+(aq) ⇌ VEDTA2−(aq) + 2 H+(aq) K=
[H 2 EDTA 2 − ][V 2+ ]

In this titration reaction, equal moles of V2+ and H2EDTA2− are reacted at the
stoichiometric point. Therefore, equal moles of both reactants must be present at
CHAPTER 11 ELECTROCHEMISTRY 453

equilibrium, so [H2EDTA2−] = [V2+] = 1.3 × 10−15 M. In addition, because [V2+] at


equilibrium is very small compared to the initial 0.0400 M concentration, the reaction
essentially goes to completion. The moles of VEDTA2− produced will equal the moles of
V2+ reacted (= 0.0400 mol). At equilibrium, [VEDTA2−] = 0.0400 mol/(1.00 L + 0.5000
L) = 0.0267 M. Finally, because we have a buffer solution, the pH is assumed not to
change, so [H+] = 10−10.00 = 1.0 × 10−10 M. Calculating K for the reaction:

[ VEDTA 2− ][H + ]2 (0.0267)(1.0 × 10 −10 ) 2


K= 2− 2+
= −15 −15
= 1.6 × 108
[H 2 EDTA ][V ] (1.3 × 10 )(1.3 × 10 )

c. At the halfway point, 250.0 mL of H2EDTA2− has been added to 1.00 L of 0.0400 M V2+.
Exactly one-half the 0.0400 mol of V2+ present initially has been converted into
VEDTA2−. Therefore, 0.0200 mol of V2+ remains in 1.00 + 0.2500 = 1.25 L solution.

0.0591 [V 2+ ] 0.0591 (0.0200 / 1.25)


Ecell = 1.54 V − log 2+
= 1.54 − log
2 [Cu ] 2 1.00

Ecell = 1.54 − (−0.0531) = 1.59 V

107. Begin by choosing any reduction potential as 0.00 V. For example, let’s assume
B2+ + 2 e− → B E° = 0.00 V
From the data, when B/B2+ and E/E2+ are together as a cell, EE = 0.81 V.

E2+ + 2 e− → E must have a potential of !0.81 V or 0.81 V since E may be involved in either
the reduction or the oxidation half-reaction. We will arbitrarily choose E to have a potential
of !0.81 V.

Setting the reduction potential at !0.81 for E and 0.00 for B, we get the following table of
potentials.

B2+ + 2 e− → B 0.00 V
E2+ + 2 e− → E !0.81 V
D2+ + 2 e− → D 0.19 V
C2+ + 2 e− → C !0.94 V
A2+ + 2 e− → A !0.53 V

From largest to smallest:


D2+ + 2 e− → D 0.19 V
B2+ + 2 e− → B 0.00 V
A2+ + 2 e− → A !0.53 V
E2+ + 2 e− → E !0.81 V
C2+ + 2 e− → C !0.94 V
454 CHAPTER 11 ELECTROCHEMISTRY

A2+ + 2 e− → A is in the middle. Let’s call this 0.00 V. We get:


D2+ + 2 e− → D 0.72 V
B2+ + 2 e− → B 0.53 V
A2+ + 2 e− → A 0.00 V
E2+ + 2 e− → E !0.28 V
C2+ + 2 e− → C !0.41 V

Of course, since the reduction potential of E could have been assumed to 0.81 V instead of
!0.81 V, we can also get:

C2+ + 2 e− → C 0.41 V
E2+ + 2 e− → E 0.28 V
2+ -−
A +2e →A 0.00 V
2+ −
B +2e →B !0.53 V
D2+ + 2 e− → D !0.72 V
One way to determine which table is correct is to add metal C to a solution with D2+ and
metal D to a solution with C2+. If D comes out of solution, the first table is correct. If C
comes out of solution, the second table is correct.