cha75632_ch19_661-702.

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Questions and Problems 695

Key Words
Anode, p. 666 Electrochemistry, p. 662
Battery, p. 680 Electrolysis, p. 687
Cathode, p. 666 Electrolytic cell, p. 687
Cell voltage, p. 666 Electromotive force (emf) (E),
Corrosion, p. 685 p. 666
Faraday constant (F), p. 673
Fuel cell, p. 683
Galvanic cell, p. 665
Half-cell reaction, p. 666
Nernst equation, p. 676
Overvoltage, p. 689
Standard emf (E°), p. 668
Standard reduction potential,
p. 667

Questions and Problems

Balancing Redox Equations 19.8 After operating a Daniell cell (see Figure 19.1) for a
Problems few minutes, a student notices that the cell emf be-
gins to drop. Why?
19.1 Balance the following redox equations by the half-
reaction method: 19.9 Use the information in Table 2.1, and calculate the
(a) H2O2 1 Fe21 ¡ Fe31 1 H2O (in acidic Faraday constant.
solution) 19.10 Discuss the spontaneity of an electrochemical reac-
(b) Cu 1 HNO3 ¡ Cu21 1 NO 1 H2O (in tion in terms of its standard emf (E°cell).
acidic solution) Problems
(c) CN2 1 MnO24 ¡ CNO2 1 MnO2 (in basic 19.11 Calculate the standard emf of a cell that uses the
solution) MgyMg21 and CuyCu21 half-cell reactions at 25°C.
(d) Br2 ¡ BrO2 2
3 1 Br (in basic solution) Write the equation for the cell reaction that occurs
2
(e) S2O3 1 I2 ¡ I 1 S4O22
22
6 (in acidic under standard-state conditions.
solution) 19.12 Calculate the standard emf of a cell that uses AgyAg1
19.2 Balance the following redox equations by the half- and AlyAl31 half-cell reactions. Write the cell reac-
reaction method: tion that occurs under standard-state conditions.
(a) Mn21 1 H2O2 ¡ MnO2 1 H2O (in basic 19.13 Predict whether Fe31 can oxidize I2 to I2 under
solution) standard-state conditions.
(b) Bi(OH) 3 1 SnO22 2 ¡ SnO22 3 1 Bi (in basic 19.14 Which of the following reagents can oxidize H2O to
solution) O2(g) under standard-state conditions? H1(aq), Cl2
(c) Cr2O227 1 C2O4
22
¡ Cr31 1 CO2 (in acidic (aq), Cl2(g), Cu21(aq), Pb21(aq), MnO24 (aq) (in acid).
solution) 19.15 Consider the following half-reactions:
(d) ClO23 1 Cl2 ¡ Cl2 1 ClO2 (in acidic solution)
MnO24 (aq) 1 8H1 (aq) 1 5e2 ¡
Galvanic Cells and Standard Emfs Mn21 (aq) 1 4H2O(l)
Review Questions NO23 (aq) 1 4H1 (aq) 1 3e2 ¡ NO(g) 1 2H2O(l)
19.3 Define the following terms: anode, cathode, cell
voltage, electromotive force, standard reduction Predict whether NO23 ions will oxidize Mn21 to
potential. MnO24 under standard-state conditions.
19.4 Describe the basic features of a galvanic cell. Why 19.16 Predict whether the following reactions would occur
are the two components of the cell separated from spontaneously in aqueous solution at 25°C. Assume
each other? that the initial concentrations of dissolved species are
all 1.0 M.
19.5 What is the function of a salt bridge? What kind of
electrolyte should be used in a salt bridge? (a) Ca(s) 1 Cd21 (aq) ¡ Ca21 (aq) 1 Cd(s)
19.6 What is a cell diagram? Write the cell diagram for a (b) 2Br2 (aq) 1 Sn21 (aq) ¡ Br2 (l) 1 Sn(s)
galvanic cell consisting of an Al electrode placed in a (c) 2Ag(s) 1 Ni21 (aq) ¡ 2Ag1 (aq) 1 Ni(s)
1 M Al(NO3)3 solution and a Ag electrode placed in a (d) Cu1(aq) 1 Fe31(aq) ¡ Cu21(aq) 1 Fe21(aq)
1 M AgNO3 solution. 19.17 Which species in each pair is a better oxidizing agent
19.7 What is the difference between the half-reactions dis- under standard-state conditions? (a) Br2 or Au31,
cussed in redox processes in Chapter 4 and the half- (b) H2 or Ag1, (c) Cd21 or Cr31, (d) O2 in acidic me-
cell reactions discussed in Section 19.2? dia or O2 in basic media.
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696 CHAPTER 19 Redox Reactions and Electrochemistry
19.18 Which species in each pair is a better reducing agent
under standard-state conditions? (a) Na or Li, (b) H2
or I2, (c) Fe21 or Ag, (d) Br2 or Co21.
Spontaneity of Redox Reactions
Review Questions
19.19 Write the equations relating DG° and K to the stan-
dard emf of a cell. Define all the terms.
19.20 The E° value of one cell reaction is positive and that
of another cell reaction is negative. Which cell reac-
tion will proceed toward the formation of more prod-
ucts at equilibrium?
Problems
19.21 What is the equilibrium constant for the following
reaction at 25°C?
Mg(s) 1 Zn21 (aq) Δ Mg21 (aq) 1 Zn(s)
19.22 The equilibrium constant for the reaction
Sr(s) 1 Mg21 (aq) Δ Sr21 (aq) 1 Mg(s)
is 2.69 3 1012 at 25°C. Calculate E° for a cell made
up of SrySr21 and MgyMg21 half-cells.
19.23 Use the standard reduction potentials to find the equi-
librium constant for each of the following reactions at
25°C:
(a) Br2 (l) 1 2I2 (aq) Δ 2Br2 (aq) 1 I2 (s)
(b) 2Ce41 (aq) 1 2Cl2 (aq) Δ
Cl2 (g) 1 2Ce31 (aq)
(c) 5Fe21 (aq) 1 MnO2 1
4 (aq) 1 8H (aq) Δ
Mn21 (aq) 1 4H2O(l) 1 5Fe31 (aq)
19.24 Calculate DG° and Kc for the following reactions at
25°C:
(a) Mg(s) 1 Pb21 (aq) Δ Mg21 (aq) 1 Pb(s)
(b) Br2 (l) 1 2I2 (aq) Δ 2Br2 (aq) 1 I2 (s)
(c) O2 (g) 1 4H1 (aq) 1 4Fe21 (aq) Δ
2H2O(l) 1 4Fe31 (aq)
(d) 2Al(s) 1 3I2 (s) Δ 2Al31 (aq) 1 6I2 (aq)
19.25 Under standard-state conditions, what spontaneous
reaction will occur in aqueous solution among the
ions Ce41, Ce31, Fe31, and Fe21? Calculate DG° and
Kc for the reaction.
19.26 Given that E° 5 0.52 V for the reduction Cu1 (aq) 1 e2
¡ Cu(s) , calculate E°, DG°, and K for the
following reaction at 25°C:
2Cu1 (aq) ¡ Cu21 (aq) 1 Cu(s)
The Effect of Concentration on Cell Emf
Review Questions
19.27 Write the Nernst equation and explain all the terms.
19.28 Write the Nernst equation for the following processes
at some temperature T:
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(a) Mg(s) 1 Sn21 (aq) ¡ Mg21 (aq) 1 Sn(s)
(b) 2Cr(s) 1 3Pb21 (aq) ¡ 2Cr31 (aq) 1 3Pb(s)
Problems
19.29 What is the potential of a cell made up of ZnyZn21
and CuyCu21 half-cells at 25°C if [Zn21] 5 0.25 M
and [Cu21] 5 0.15 M?
19.30 Calculate E°, E, and DG for the following cell
reactions.
(a) Mg(s) 1 Sn21 (aq) ¡ Mg21 (aq) 1 Sn(s)
[Mg21 ] 5 0.045 M, [Sn21 ] 5 0.035 M
(b) 3Zn(s) 1 2Cr31 (aq) ¡ 3Zn21 (aq) 1 2Cr(s)
[Cr31 ] 5 0.010 M, [Zn21 ] 5 0.0085 M
19.31 Calculate the standard potential of the cell consisting
of the ZnyZn21 half-cell and the SHE. What will the
emf of the cell be if [Zn21] 5 0.45 M, PH2 5 2.0 atm,
and [H1] 5 1.8 M?
19.32 What is the emf of a cell consisting of a Pb21yPb
half-cell and a PtyH1yH2 half-cell if [Pb21] 5 0.10 M,
[H1] 5 0.050 M, and PH2 5 1.0 atm?
19.33 Referring to the arrangement in Figure 19.1, calcu-
late the [Cu21]y[Zn21] ratio at which the following
reaction is spontaneous at 25°C:
Cu(s) 1 Zn21 (aq) ¡ Cu21 (aq) 1 Zn(s)
19.34 Calculate the emf of the following concentration cell:
Mg(s) 0 Mg21 (0.24 M) 0 0 Mg21 (0.53M) 0 Mg(s)
Batteries and Fuel Cells
Review Questions
19.35 Explain the differences between a primary galvanic
cell—one that is not rechargeable—and a storage cell
(for example, the lead storage battery), which is
rechargeable.
19.36 Discuss the advantages and disadvantages of fuel
cells over conventional power plants in producing
electricity.
Problems
19.37 The hydrogen-oxygen fuel cell is described in Sec-
tion 19.6. (a) What volume of H2(g), stored at 25°C at
a pressure of 155 atm, would be needed to run an
electric motor drawing a current of 8.5 A for 3.0 h?
(b) What volume (liters) of air at 25°C and 1.00 atm
will have to pass into the cell per minute to run the
motor? Assume that air is 20 percent O2 by volume
and that all the O2 is consumed in the cell. The other
components of air do not affect the fuel-cell reac-
tions. Assume ideal gas behavior.
19.38 Calculate the standard emf of the propane fuel cell
discussed on p. 684 at 25°C, given that DG°f for pro-
pane is 223.5 kJymol.
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Corrosion
Review Questions
19.39 Steel hardware, including nuts and bolts, is often
coated with a thin plating of cadmium. Explain the
function of the cadmium layer.
19.40 “Galvanized iron” is steel sheet that has been coated
with zinc; “tin” cans are made of steel sheet coated
with tin. Discuss the functions of these coatings and
the electrochemistry of the corrosion reactions that
occur if an electrolyte contacts the scratched surface
of a galvanized iron sheet or a tin can.
19.41 Tarnished silver contains Ag2S. The tarnish can be re-
moved by placing silverware in an aluminum pan con-
taining an inert electrolyte solution, such as NaCl.
Explain the electrochemical principle for this
procedure. [The standard reduction potential for the
half-cell reaction Ag2S(s) 1 2e2 ¡ 2Ag(s) 1 S22(aq)
is 20.71 V.]
19.42 How does the tendency of iron to rust depend on the
pH of solution?
Electrolysis
Review Questions
19.43 What is the difference between a galvanic cell (such
as a Daniell cell) and an electrolytic cell?
19.44 Describe the electrolysis of an aqueous solution of
KNO3.
Problems
19.45 The half-reaction at an electrode is
Mg21 (molten) 1 2e2 ¡ Mg(s)
Calculate the number of grams of magnesium that can
be produced by supplying 1.00 F to the electrode.
19.46 Consider the electrolysis of molten barium chloride,
BaCl2. (a) Write the half-reactions. (b) How many
grams of barium metal can be produced by supplying
0.50 A for 30 min?
19.47 Considering only the cost of electricity, would it be
cheaper to produce a ton of sodium or a ton of alumi-
num by electrolysis?
19.48 If the cost of electricity to produce magnesium by the
electrolysis of molten magnesium chloride is $155 per
ton of metal, what is the cost (in dollars) of the electric-
ity necessary to produce (a) 10.0 tons of aluminum,
(b) 30.0 tons of sodium, (c) 50.0 tons of calcium?
19.49 One of the half-reactions for the electrolysis of water is
2H2O(l) ¡ O2 (g) 1 4H1 (aq) 1 4e2
If 0.076 L of O2 is collected at 25°C and 755 mmHg,
how many faradays of electricity had to pass through
the solution?
19.50 How many faradays of electricity are required to
produce (a) 0.84 L of O2 at exactly 1 atm and 25°C
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Questions and Problems 697
from aqueous H2SO4 solution; (b) 1.50 L of Cl2 at
750 mmHg and 20°C from molten NaCl; (c) 6.0 g of
Sn from molten SnCl2?
19.51 Calculate the amounts of Cu and Br2 produced in
1.0 h at inert electrodes in a solution of CuBr2 by a
current of 4.50 A.
19.52 In the electrolysis of an aqueous AgNO3 solution,
0.67 g of Ag is deposited after a certain period of time.
(a) Write the half-reaction for the reduction of Ag1.
(b) What is the probable oxidation half-reaction?
(c) Calculate the quantity of electricity used, in
coulombs.
19.53 A steady current was passed through molten CoSO4
until 2.35 g of metallic cobalt was produced. Calcu-
late the number of coulombs of electricity used.
19.54 A constant electric current flows for 3.75 h through
two electrolytic cells connected in series. One con-
tains a solution of AgNO3 and the second a solution
of CuCl2. During this time 2.00 g of silver are depos-
ited in the first cell. (a) How many grams of copper
are deposited in the second cell? (b) What is the cur-
rent flowing, in amperes?
19.55 What is the hourly production rate of chlorine gas (in
kg) from an electrolytic cell using aqueous NaCl electro-
lyte and carrying a current of 1.500 3 103 A? The anode
efficiency for the oxidation of Cl2 is 93.0 percent.
19.56 Chromium plating is applied by electrolysis to ob-
jects suspended in a dichromate solution, according
to the following (unbalanced) half-reaction:
2 1
7 (aq) 1 e 1 H (aq) ¡ Cr(s) 1 H2O(l)
Cr2O22
How long (in hours) would it take to apply a chro-
mium plating 1.0 3 1022 mm thick to a car bumper
with a surface area of 0.25 m2 in an electrolytic cell
carrying a current of 25.0 A? (The density of chro-
mium is 7.19 gycm3.)
19.57 The passage of a current of 0.750 A for 25.0 min
deposited 0.369 g of copper from a CuSO4 solution.
From this information, calculate the molar mass of
copper.
19.58 A quantity of 0.300 g of copper was deposited from a
CuSO4 solution by passing a current of 3.00 A through
the solution for 304 s. Calculate the value of the fara-
day constant.
19.59 In a certain electrolysis experiment, 1.44 g of Ag
were deposited in one cell (containing an aqueous
AgNO3 solution), while 0.120 g of an unknown metal
X was deposited in another cell (containing an aque-
ous XCl3 solution) in series with the AgNO3 cell.
Calculate the molar mass of X.
19.60 One of the half-reactions for the electrolysis of
water is
2H1 (aq) 1 2e2 ¡ H2 (g)
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698 CHAPTER 19 Redox Reactions and Electrochemistry
If 0.845 L of H2 is collected at 25°C and 782 mmHg,
how many faradays of electricity had to pass through
the solution?
Additional Problems
19.61 For each of the following redox reactions, (i) write
the half-reactions; (ii) write a balanced equation for
the whole reaction, (iii) determine in which direc-
tion the reaction will proceed spontaneously under
standard-state conditions:
(a) H2 (g) 1 Ni21 (aq) ¡ H1 (aq) 1 Ni(s)
(b) MnO24 (aq) 1 Cl2 (aq) ¡
Mn21 (aq) 1 Cl2 (g) (in acid solution)
(c) Cr(s) 1 Zn21 (aq) ¡ Cr31 (aq) 1 Zn(s)
19.62 The oxidation of 25.0 mL of a solution containing
Fe21 requires 26.0 mL of 0.0250 M K2Cr2O7 in acidic
solution. Balance the following equation and calcu-
late the molar concentration of Fe21:
7 1 Fe
Cr2O22 21
1 H1 ¡ Cr31 1 Fe31
19.63 The SO2 present in air is mainly responsible for the
phenomenon of acid rain. The concentration of SO2
can be determined by titrating against a standard per-
manganate solution as follows:
5SO2 1 2MnO24 1 2H2O ¡
4 1 2Mn
5SO22 21
1 4H1
Calculate the number of grams of SO2 in a sample of
air if 7.37 mL of 0.00800 M KMnO4 solution are re-
quired for the titration.
19.64 A sample of iron ore weighing 0.2792 g was dis-
solved in an excess of a dilute acid solution. All the
iron was first converted to Fe(II) ions. The solution
then required 23.30 mL of 0.0194 M KMnO4 for oxi-
dation to Fe(III) ions. Calculate the percent by mass
of iron in the ore.
19.65 The concentration of a hydrogen peroxide solution
can be conveniently determined by titration against a
standardized potassium permanganate solution in an
acidic medium according to the following unbalanced
equation:
MnO24 1 H2O2 ¡ O2 1 Mn21
(a) Balance the above equation. (b) If 36.44 mL
of a 0.01652 M KMnO4 solution are required
to completely oxidize 25.00 mL of a H2O2
solution, calculate the molarity of the H2O2
solution.
19.66 Oxalic acid (H2C2O4) is present in many plants and
vegetables. (a) Balance the following equation in acid
solution:
MnO24 1 C2O22
4 ¡ Mn21 1 CO2
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(b) If a 1.00-g sample of H2C2O4 requires 24.0 mL
of 0.0100 M KMnO4 solution to reach the
equivalence point, what is the percent by mass
of H2C2O4 in the sample?
19.67 Complete the following table. State whether the cell
reaction is spontaneous, nonspontaneous, or at
equilibrium.
E DG Cell Reaction
.0
.0
50
19.68 Calcium oxalate (CaC2O4) is insoluble in water. This
property has been used to determine the amount of Ca21
ions in blood. The calcium oxalate isolated from blood
is dissolved in acid and titrated against a standardized
KMnO4 solution, as described in Problem 19.66. In one
test it is found that the calcium oxalate isolated from a
10.0-mL sample of blood requires 24.2 mL of 9.56 3
1024 M KMnO4 for titration. Calculate the number of
milligrams of calcium per milliliter of blood.
19.69 From the following information, calculate the solu-
bility product of AgBr:
Ag1 (aq) 1 e2 ¡ Ag(s) E° 5 0.80 V
AgBr(s) 1 e2 ¡ Ag(s) 1 Br2 (aq) E° 5 0.07 V
19.70 Consider a galvanic cell composed of the SHE and a
half-cell using the reaction Ag1(aq) 1 e2 ¡ Ag(s).
(a) Calculate the standard cell potential. (b) What is the
spontaneous cell reaction under standard-state con-
ditions? (c) Calculate the cell potential when [H1] in
the hydrogen electrode is changed to (i) 1.0 3 1022 M
and (ii) 1.0 3 1025 M, all other reagents being held at
standard-state conditions. (d) Based on this cell
arrangement, suggest a design for a pH meter.
19.71 A galvanic cell consists of a silver electrode in contact
with 346 mL of 0.100 M AgNO3 solution and a mag-
nesium electrode in contact with 288 mL of 0.100 M
Mg(NO3)2 solution. (a) Calculate E for the cell at
25°C. (b) A current is drawn from the cell until 1.20 g
of silver have been deposited at the silver electrode.
Calculate E for the cell at this stage of operation.
19.72 Explain why chlorine gas can be prepared by electro-
lyzing an aqueous solution of NaCl but fluorine gas
cannot be prepared by electrolyzing an aqueous solu-
tion of NaF.
19.73 Calculate the emf of the following concentration cell
at 25°C:
Cu(s) 0 Cu21 (0.080 M) 0 0 Cu21 (1.2 M) 0 Cu(s)
19.74 The cathode reaction in the Leclanché cell is given by
2MnO2 (s) 1 Zn21 (aq) 1 2e2 ¡ ZnMn2O4 (s)
If a Leclanché cell produces a current of 0.0050 A,
calculate how many hours this current supply will
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last if there are initially 4.0 g of MnO2 present in the
cell. Assume that there is an excess of Zn21 ions.
19.75 Suppose you are asked to verify experimentally the
electrode reactions shown in Example 19.8. In addition
to the apparatus and the solution, you are also given two
pieces of litmus paper, one blue and the other red.
Describe what steps you would take in this experiment.
19.76 For a number of years it was not clear whether
mercury(I) ions existed in solution as Hg1 or as Hg221.
To distinguish between these two possibilities, we
could set up the following system:
Hg(l) 0 soln A 0 0 soln B 0 Hg(l)
where soln A contained 0.263 g mercury(I) nitrate
per liter and soln B contained 2.63 g mercury(I) ni-
trate per liter. If the measured emf of such a cell is
0.0289 V at 18°C, what can you deduce about the
nature of the mercury(I) ions?
19.77 An aqueous KI solution to which a few drops of phe-
nolphthalein have been added is electrolyzed using
an apparatus like the one shown here:
Describe what you would observe at the anode and
the cathode. (Hint: Molecular iodine is only slightly
soluble in water, but in the presence of I2 ions, it
forms the brown color of I23 ions.)
19.78 A piece of magnesium metal weighing 1.56 g is
placed in 100.0 mL of 0.100 M AgNO3 at 25°C. Cal-
culate [Mg21] and [Ag1] in solution at equilibrium.
What is the mass of the magnesium left? The volume
remains constant.
19.79 Describe an experiment that would enable you to de-
termine which is the cathode and which is the anode
in a galvanic cell using copper and zinc electrodes.
19.80 An acidified solution was electrolyzed using copper
electrodes. A constant current of 1.18 A caused the
anode to lose 0.584 g after 1.52 3 103 s. (a) What is
the gas produced at the cathode and what is its vol-
ume at STP? (b) Given that the charge of an electron
is 1.6022 3 10219 C, calculate Avogadro’s number.
Assume that copper is oxidized to Cu21 ions.
19.81 In a certain electrolysis experiment involving Al31
ions, 60.2 g of Al is recovered when a current of
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Questions and Problems 699
0.352 A is used. How many minutes did the electroly-
sis last?
19.82 Consider the oxidation of ammonia:
4NH3 (g) 1 3O2 (g) ¡ 2N2 (g) 1 6H2O(l)
(a) Calculate the DG° for the reaction. (b) If this
reaction were used in a fuel cell, what would the
standard cell potential be?
19.83 A galvanic cell is constructed by immersing a piece of
copper wire in 25.0 mL of a 0.20 M CuSO4 solution and
a zinc strip in 25.0 mL of a 0.20 M ZnSO4 solution.
(a) Calculate the emf of the cell at 25°C and predict
what would happen if a small amount of concentrated
NH3 solution were added to (i) the CuSO4 solution and
(ii) the ZnSO4 solution. Assume that the volume in each
compartment remains constant at 25.0 mL. (b) In a
separate experiment, 25.0 mL of 3.00 M NH3 are added
to the CuSO4 solution. If the emf of the cell is 0.68 V,
calculate the formation constant (Kf) of Cu(NH3)21 4 .
19.84 In an electrolysis experiment, a student passes the
same quantity of electricity through two electrolytic
cells, one containing a silver salt and the other a gold
salt. Over a certain period of time, she finds that 2.64 g
of Ag and 1.61 g of Au are deposited at the cathodes.
What is the oxidation state of gold in the gold salt?
19.85 People living in cold-climate countries where there is
plenty of snow are advised not to heat their garages in
the winter. What is the electrochemical basis for this
recommendation?
19.86 Given that
2Hg21 (aq) 1 2e2 ¡ Hg21
2 (aq) E° 5 0.92 V
2
2 (aq) 1 2e
Hg21 ¡ 2Hg(l) E° 5 0.85 V
calculate DG° and K for the following process at 25°C:
2 (aq) ¡ Hg (aq) 1 Hg(l)
Hg21 21
(The preceding reaction is an example of a
disproportionation reaction in which an element in
one oxidation state is both oxidized and reduced.)
19.87 Fluorine (F2) is obtained by the electrolysis of liquid
hydrogen fluoride (HF) containing potassium fluo-
ride (KF). (a) Write the half-cell reactions and the
overall reaction for the process. (b) What is the pur-
pose of KF? (c) Calculate the volume of F2 (in liters)
collected at 24.0°C and 1.2 atm after electrolyzing
the solution for 15 h at a current of 502 A.
19.88 A 300-mL solution of NaCl was electrolyzed for
6.00 min. If the pH of the final solution was 12.24,
calculate the average current used.
19.89 Industrially, copper is purified by electrolysis. The
impure copper acts as the anode, and the cathode is
made of pure copper. The electrodes are immersed in
a CuSO4 solution. During electrolysis, copper at the
anode enters the solution as Cu21 while Cu21 ions are
reduced at the cathode. (a) Write half-cell reactions
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700 CHAPTER 19 Redox Reactions and Electrochemistry
and the overall reaction for the electrolytic process.
(b) Suppose the anode was contaminated with Zn and
Ag. Explain what happens to these impurities during
electrolysis. (c) How many hours will it take to obtain
1.00 kg of Cu at a current of 18.9 A?
19.90 An aqueous solution of a platinum salt is electrolyzed
at a current of 2.50 A for 2.00 h. As a result, 9.09 g of
metallic Pt are formed at the cathode. Calculate the
charge on the Pt ions in this solution.
19.91 Consider a galvanic cell consisting of a magnesium
electrode in contact with 1.0 M Mg(NO3)2 and a cad-
mium electrode in contact with 1.0 M Cd(NO3)2. Cal-
culate E° for the cell, and draw a diagram showing
the cathode, anode, and direction of electron flow.
19.92 A current of 6.00 A passes through an electrolytic cell
containing dilute sulfuric acid for 3.40 h. If the volume
of O2 gas generated at the anode is 4.26 L (at STP),
calculate the charge (in coulombs) on an electron.
19.93 Gold will not dissolve in either concentrated nitric
acid or concentrated hydrochloric acid. However, the
metal does dissolve in a mixture of the acids (one part
HNO3 and three parts HCl by volume), called aqua
regia. (a) Write a balanced equation for this reaction.
(Hint: Among the products are HAuCl4 and NO2.)
(b) What is the function of HCl?
19.94 Explain why most useful galvanic cells give voltages
of no more than 1.5 to 2.5 V. What are the prospects
for developing practical galvanic cells with voltages
of 5 V or more?
19.95 A silver rod and a SHE are dipped into a saturated
aqueous solution of silver oxalate, Ag2C2O4, at 25°C.
The measured potential difference between the rod
and the SHE is 0.589 V, the rod being positive. Calcu-
late the solubility product constant for silver oxalate.
19.96 Zinc is an amphoteric metal; that is, it reacts with
both acids and bases. The standard reduction poten-
tial is 21.36 V for the reaction
2
4 (aq) 1 2e
Zn(OH) 22 ¡ Zn(s) 1 4OH2 (aq)
Calculate the formation constant (Kf) for the reaction
Zn21 (aq) 1 4OH2 (aq) Δ Zn(OH) 22
4 (aq)
19.97 Use the data in Table 19.1 to determine whether or
not hydrogen peroxide will undergo disproportion-
ation in an acid medium: 2H2O2 ¡ 2H2O 1 O2.
19.98 The magnitudes (but not the signs) of the standard
reduction potentials of two metals X and Y are
Y21 1 2e2 ¡ Y   0 E° 0 5 0.34 V
X21 1 2e2 ¡ X   0 E° 0 5 0.25 V
where the 0 0 notation denotes that only the magnitude
(but not the sign) of the E° value is shown. When the
half-cells of X and Y are connected, electrons flow
from X to Y. When X is connected to a SHE, electrons
/Volumes/MHDQ-New/MHDQ144/MHDQ144-19
flow from X to SHE. (a) Are the E° values of the half-
reactions positive or negative? (b) What is the stan-
dard emf of a cell made up of X and Y?
19.99 A galvanic cell is constructed as follows. One half-cell
consists of a platinum wire immersed in a solution con-
taining 1.0 M Sn21 and 1.0 M Sn41; the other half-cell
has a thallium rod immersed in a solution of 1.0 M TI1.
(a) Write the half-cell reactions and the overall reaction.
(b) What is the equilibrium constant at 25°C? (c) What
is the cell voltage if the TI1 concentration is increased
tenfold? (E°T11/T1 5 20.34 V.)
19.100 Given the standard reduction potential for Au31 in
Table 19.1 and
Au1 (aq) 1 e2 ¡ Au(s)  E° 5 1.69 V
answer the following questions. (a) Why does gold
not tarnish in air? (b) Will the following dispropor-
tionation occur spontaneously?
3Au1 (aq) ¡ Au31 (aq) 1 2Au(s)
(c) Predict the reaction between gold and fluorine gas.
19.101 Calculate E° for the reactions of mercury with (a) 1 M
HCl and (b) 1 M HNO3. Which acid will oxidize Hg
to Hg221 under standard-state conditions? Can you
identify which test tube below contains HNO3 and
Hg and which contains HCl and Hg?
Based on your answer, explain why ingestion of a
very small quantity of mercury is not considered too
harmful.
19.102 When 25.0 mL of a solution containing both Fe21 and
Fe31 ions is titrated with 23.0 mL of 0.0200 M
KMnO4 (in dilute sulfuric acid), all of the Fe21 ions
are oxidized to Fe31 ions. Next, the solution is treated
with Zn metal to convert all of the Fe31 ions to Fe21
ions. Finally, 40.0 mL of the same KMnO4 solution
are added to the solution in order to oxidize the Fe21
ions to Fe31. Calculate the molar concentrations of
Fe21 and Fe31 in the original solution.
19.103 Consider the Daniell cell in Figure 19.1. When
viewed externally, the anode appears negative and the
cathode positive (electrons are flowing from the an-
ode to the cathode). Yet in solution anions are moving
toward the anode, which means that it must appear
positive to the anions. Because the anode cannot si-
multaneously be negative and positive, give an expla-
nation for this apparently contradictory situation.
cha75632_ch19_661-702.indd Page 701 10/5/09 2:30:35 PM user-s180
19.104 Lead storage batteries are rated by ampere hours, that is,
the number of amperes they can deliver in an hour.
(a) Show that 1 A ? h 5 3600 C. (b) The lead anodes of
a certain lead storage battery have a total mass of 406 g.
Calculate the maximum theoretical capacity of the
battery in ampere hours. Explain why in practice we can
never extract this much energy from the battery. (Hint:
Assume all of the lead will be used up in the electro-
chemical reaction and refer to the electrode reactions on
p. 682.) (c) Calculate E°cell and DG° for the battery.
19.105 The concentration of sulfuric acid in the lead storage
battery of an automobile over a period of time has
decreased from 38.0 percent by mass (density 5
1.29 gymL) to 26.0 percent by mass (1.19 gymL).
Assume the volume of the acid remains constant at
724 mL. (a) Calculate the total charge in coulombs
supplied by the battery. (b) How long (in hours) will
it take to recharge the battery back to the original
sulfuric acid concentration using a current of 22.4 A.
19.106 Consider a Daniell cell operating under nonstandard-
state conditions. Suppose that the cell’s reaction is
multiplied by 2. What effect does this have on each
of the following quantities in the Nernst equation?
(a) E, (b) E°, (c) Q, (d) ln Q, and (e) n?
19.107 A spoon was silver-plated electrolytically in a AgNO3
solution. (a) Sketch a diagram for the process. (b) If
0.884 g of Ag was deposited on the spoon at a con-
stant current of 18.5 mA, how long (in minutes) did
the electrolysis take?
19.108 Comment on whether F2 will become a stronger oxi-
dizing agent with increasing H1 concentration.
19.109 In recent years there has been much interest in elec-
tric cars. List some advantages and disadvantages of
electric cars compared to automobiles with internal
combustion engines.
19.110 Calculate the pressure of H2 (in atm) required to
maintain equilibrium with respect to the following
reaction at 25°C:
Pb(s) 1 2H1 (aq) Δ Pb21 (aq) 1 H2 (g)
Given that [Pb ] 5 0.035 M and the solution is buff-
21
ered at pH 1.60.
Special Problems
19.115 Fluorine is a highly reactive gas that attacks water to
form HF and other products. Follow the procedure in
Problem 19.111, to show how you can determine in-
directly the standard reduction for fluorine as shown
in Table 19.1
19.116 A piece of magnesium ribbon and a copper wire are
partially immersed in a 0.1 M HCl solution in a bea-
ker. The metals are joined externally by another piece
/Volumes/MHDQ-New/MHDQ144/MHDQ144-19
Special Problems 701
19.111 Because all alkali metals react with water, it is not
possible to measure the standard reduction potentials
of these metals directly as in the case of, say, zinc. An
indirect method is to consider the following hypo-
thetical reaction
Li1 (aq) 1 12H2 (g) ¡ Li(s) 1 H1 (aq)
Use the appropriate equation presented in this chap-
ter and the thermodynamic data in Appendix 2, calcu-
late E° for Li1 (aq) 1 e2 ¡ Li(s) at 298 K.
Compare your result with that listed in Table 19.1.
(See back endpaper for the Faraday constant.)
19.112 A galvanic cell using MgyMg21 and CuyCu21 half-
cells operates under standard-state conditions at 25°C
and each compartment has a volume of 218 mL. The
cell delivers 0.22 A for 31.6 h. (a) How many grams of
Cu are deposited? (b) What is the [Cu21] remaining?
19.113 Shown here is a galvanic cell connected to an electro-
lytic cell. Label the electrodes (anodes and cathodes)
and show the movement of electrons along the wires
and cations and anions in solutions. For simplicity,
the salt bridge is not shown for the galvanic cell.
Galvanic cell Electrolytic cell
19.114 Given the following standard reduction potentials,
calculate the ion-product, Kw, for water at 25°C:
2H1 (aq) 1 2e2 ¡ H2 (g) E° 5 0.00 V
2H2O(l) 1 2e2 ¡ H2 (g) 1 2OH2 (aq)
E° 5 20.83 V
of metal wire. Bubbles are seen to evolve at both the
Mg and Cu surfaces. (a) Write equations representing
the reactions occurring at the metals. (b) What visual
evidence would you seek to show that Cu is not oxi-
dized to Cu21? (c) At some stage, NaOH solution is
added to the beaker to neutralize the HCl acid. Upon
further addition of NaOH, a white precipitate forms.
What is it?