(a) H 2O 2 1 Fe21 Fe31 1 H 2O (in acidic

solution)
(b) Cu 1 HNO 3 Cu21 1 NO 1 H 2O (in
acidic solution)

Problems
19.1

Balance the following redox equations by the ionelectron method:

874

Electrochemistry

2
(c) CN 2 1 MnO 2
4 CNO 1 MnO 2 (in
basic solution)
2
(d) Br2 BrO 2
3 1 Br (in basic solution)
22
2
(e) S 2O 3 1 I2 I 1 S4O 22
6 (in acidic
solution)
Balance the following redox equations by the ionelectron method:
(a) Mn21 1 H 2O 2 MnO 2 1 H 2O (in basic
solution)
(b) Bi1OH2 3 1 SnO 22
SnO 22
3 1 Bi (in
2
basic solution)
22
(c) Cr2O 22
Cr31 1 CO 2 (in
7 1 C 2O 4
acidic solution)
2
(d) ClO 2
Cl2 1 ClO 2 (in acidic
3 1 Cl
solution)

19.2

Galvanic Cells and Standard Emfs

Review Questions
19.3

Define the following terms: anode, cathode, cell voltage, electromotive force, standard reduction potential.
19.4 Describe the basic features of a galvanic cell. Why
are the two components of the cell separated from
each other?
19.5 What is the function of a salt bridge? What kind of
electrolyte should be used in a salt bridge?
19.6 What is a cell diagram? Write the cell diagram for a
galvanic cell consisting of an Al electrode placed in
a 1 M Al(NO3)3 solution and a Ag electrode placed in
a 1 M AgNO3 solution.
19.7 What is the difference between the half-reactions
discussed in redox processes in Chapter 4 and the
half-cell reactions discussed in Section 19.2?
19.8 After operating a Daniell cell (see Figure 19.1) for a
few minutes, a student notices that the cell emf begins to drop. Why?
19.9 Use the information in Table 2.1, and calculate the
Faraday constant.
19.10 Discuss the spontaneity of an electrochemical reaction in terms of its standard emf (Ecell ).

Cl2(aq), Cl2(g), Cu21(aq), Pb21(aq), MnO2

4 (aq) (in
acid).
19.15 Consider the following half-reactions:
1
2
MnO2

4 (aq) 1 8H (aq) 1 5e
Mn21 (aq) 1 4H2O(l)
2
1
2
NO3 (aq) 1 4H (aq) 1 3e
NO(g) 1 2H2O(l)

Predict whether NO32 ions will oxidize Mn21 to

MnO2
4 under standard-state conditions.
19.16 Predict whether the following reactions would occur
spontaneously in aqueous solution at 25C. Assume
that the initial concentrations of dissolved species
are all 1.0 M.
(a) Ca(s) 1 Cd21 (aq) Ca21 (aq) 1 Cd(s)
(b) 2Br2 (aq) 1 Sn21 (aq) Br2 (l) 1 Sn(s)
(c) 2Ag(s) 1 Ni21(aq) 2Ag1(aq) 1 Ni(s)
(d) Cu 1 (aq) 1 Fe31 (aq)
Cu21 (aq) 1 Fe21 (aq)
19.17 Which species in each pair is a better oxidizing agent
under standard-state conditions? (a) Br2 or Au31,
(b) H2 or Ag1, (c) Cd21 or Cr31, (d) O2 in acidic
media or O2 in basic media.
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 standard 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 reaction will proceed toward the formation of more products at equilibrium?

Problems
19.21 What is the equilibrium constant for the following
reaction at 25C?
Mg(s) 1 Zn21 (aq) Mg21 (aq) 1 Zn(s)

Problems
19.11 Calculate the standard emf of a cell that uses the
Mg/Mg21and Cu/Cu21 half-cell reactions at 25C.
Write the equation for the cell reaction that occurs
under standard-state conditions.
19.12 Calculate the standard emf of a cell that uses Ag/Ag1
and Al/Al31 half-cell reactions. Write the cell reaction
that occurs under standard-state conditions.
19.13 Predict whether Fe31 can oxidize I2 to I2 under
standard-state conditions.
19.14 Which of the following reagents can oxidize H2O
to O2(g) under standard-state conditions? H1(aq),

1
(c) 5Fe21 (aq) 1 MnO 2
4 (aq) 1 8H (aq)
21
Mn (aq) 1 4H 2O(l2 1 5Fe31 (aq)
19.24 Calculate DG and Kc for the following reactions at
25C:
(a) Mg(s) 1 Pb21(aq) Mg21(aq) 1 Pb(s)
(b) Br2 (l2 1 2I2 (aq) 2Br2 (aq) 1 I2 (s)
(c) O 2 (g2 1 4H 1(aq) 1 4Fe21(aq)
2H 2O(l) 1 4Fe31(aq)
(d) 2Al(s) 1 3I2 (s) 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 Cu 1 (aq) 1
e2 S Cu(s), calculate E, DG, and K for the following reaction at 25C:

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:
(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 Zn/Zn21
and Cu/Cu21 half-cells at 25C 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 Zn/Zn21 half-cell and the SHE. What will the
emf of the cell be if [Zn21] 5 0.45 M, PH25 2.0 atm,
and [H1] 5 1.8 M?
19.32 What is the emf of a cell consisting of a Pb21/Pb
half-cell and a Pt/H1/H2 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, calculate the [Cu21]/[Zn21] ratio at which the following
reaction is spontaneous at 25C:
Cu(s) 1 Zn (aq) Cu (aq) 1 Zn(s)
21

21

19.34 Calculate the emf of the following concentration cell:

Mg(s) 0 Mg21 (0.24 M) 0 0 Mg21 (0.53 M) 0 Mg(s)

Problems
19.45 The half-reaction at an electrode is
Mg21 (molten) 1 2e2 Mg(s)

19.46

19.47

19.48

19.49

Calculate the number of grams of magnesium that can

be produced by supplying 1.00 F to the electrode.
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?
Considering only the cost of electricity, would it be
cheaper to produce a ton of sodium or a ton of aluminum by electrolysis?
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 electricity necessary to produce (a) 10.0 tons
of aluminum, (b) 30.0 tons of sodium, (c) 50.0 tons
of calcium?
One of the half-reactions for the electrolysis of
water is
1

2H2O (l) O2 (g) 1 4H (aq) 1 4e

19.50

19.51

19.52

19.53

19.54

19.55

19.22 The equilibrium constant for the reaction

Sr(s) 1 Mg21 (aq) Sr21 (aq) 1 Mg(s)

is 2.69 3 1012 at 25C. Calculate E for a cell made

up of Sr/Sr21 and Mg/Mg21 half-cells.
19.23 Use the standard reduction potentials to find the
equilibrium constant for each of the following reactions at 25C:
(a) Br2 (l) 1 2I2 (aq) 2Br2 (aq) 1 I2 (s)
(b) 2Ce41 (aq) 1 2Cl2 (aq)
Cl2 (g2 1 2Ce31 (aq)

Batteries and Fuel Cells

Review Questions
19.35 Explain the differences between a primary galvanic
cellone that is not rechargeableand 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 Section 19.6. (a) What volume of H2(g), stored at 25C
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 25C 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 reactions. Assume ideal gas behavior.
19.38 Calculate the standard emf of the propane fuel cell
discussed on p. 862 at 25C, given that DGf for
propane is 223.5 kJ/mol.

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
removed by placing silverware in an aluminum pan
containing 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 S 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.

The anode efficiency for the oxidation of Cl2 is 93.0

percent.
19.56 Chromium plating is applied by electrolysis to objects suspended in a dichromate solution, according
to the following (unbalanced) half-reaction:
2
1
Cr2O22
7 (aq) 1 e 1 H (aq) Cr(s) 1 H2O(l)

19.57

19.58

19.59

If 0.076 L of O2 is collected at 25C and 755 mmHg,

how many moles of electrons had to pass through the
solution?
How many moles of electrons are required to produce (a) 0.84 L of O2 at exactly 1 atm and 25C
from aqueous H2SO4 solution; (b) 1.50 L of Cl2 at
750 mmHg and 20C from molten NaCl; (c) 6.0 g of
Sn from molten SnCl2?
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.
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 halfreaction? (c) Calculate the quantity of electricity
used, in coulombs.
A steady current was passed through molten CoSO4
until 2.35 g of metallic cobalt was produced. Calculate the number of coulombs of electricity used.
A constant electric current flows for 3.75 h through
two electrolytic cells connected in series. One contains a solution of AgNO3 and the second a solution
of CuCl2. During this time 2.00 g of silver are deposited in the first cell. (a) How many grams of copper
are deposited in the second cell? (b) What is the current flowing, in amperes?
What is the hourly production rate of chlorine gas (in
kg) from an electrolytic cell using aqueous NaCl
electrolyte and carrying a current of 1.500 3 103A?

can be determined by titrating against a standard

permanganate solution as follows:

19.60

2H1 (aq) 1 2e2 H2 (g)

If 0.845 L of H2 is collected at 25C and 782 mmHg,

how many moles of electrons 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 direction the reaction will proceed spontaneously under
standard-state conditions:
(a) H2(g) 1 Ni21(aq) H1(aq) 1 Ni(s)
2
(b) MnO2
4 (aq) 1 Cl (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 calculate the molar concentration of Fe21:
21
Cr2O22
1 H1 Cr31 1 Fe31
7 1 Fe

19.63 The SO2 present in air is mainly responsible for the

phenomenon of acid rain. The concentration of SO2

19.69 From the following information, calculate the solubility product of AgBr:

5SO2 1 2MnO2
4 1 2H2O
21
5SO22
1 4H1
4 1 2Mn

Calculate the number of grams of SO2 in a sample of

air if 7.37 mL of 0.00800 M KMnO4 solution are required for the titration.
19.64 A sample of iron ore weighing 0.2792 g was dissolved 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
oxidation 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:
21
MnO2
4 1 H2O2 O2 1 Mn

(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:

Ag1(aq) 1 e2 Ag(s)
AgBr(s) 1 e2 Ag(s) 1 Br2 (aq)

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.

19.77 An aqueous KI solution to which a few drops of phenolphthalein have been added is electrolyzed using
an apparatus like the one shown here:

E 5 0.80 V
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 S Ag(s).
(a) Calculate the standard cell potential. (b) What is
the spontaneous cell reaction under standard-state
conditions? (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 magnesium electrode in contact with 288 mL of 0.100 M
Mg(NO3)2 solution. (a) Calculate E for the cell at
25C. (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 electrolyzing an aqueous solution of NaCl but fluorine
gas cannot be prepared by electrolyzing an aqueous
solution of NaF.
19.73 Calculate the emf of the following concentration cell
at 25C:

22
MnO2
Mn21 1 CO2
4 1 C2 O 4

(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.

How long (in hours) would it take to apply a

chromium 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 chromium is 7.19 g/cm3.)
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.
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 Faraday constant.
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
aqueous XCl3 solution) in series with the AgNO3
cell. Calculate the molar mass of X.
One of the half-reactions for the electrolysis of
water is

Cu(s) 0 Cu21 (0.080 M) 0 0 Cu21 (1.2 M) 0 Cu(s)

19.74 The cathode reaction in the Leclanch cell is given by

2MnO2 (s) 1 Zn21(aq) 1 2e2 ZnMn2O4 (s)

If a Leclanch cell produces a current of 0.0050 A,

calculate how many hours this current supply will
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)
nitrate per liter. If the measured emf of such a cell is
0.0289 V at 18C, what can you deduce about the
nature of the mercury(I) ions?

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)
2
Hg21
2Hg(l)
2 (aq) 1 2e

E 5 0.92 V
E 5 0.85 V

calculate DG and K for the following process at

25C:
21
Hg21
2 (aq) Hg (aq) 1 Hg(l)

19.78

19.79

19.80

19.81

19.82

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 I2
3 ions. See Problem 12.98.)
A piece of magnesium metal weighing 1.56 g is
placed in 100.0 mL of 0.100 M AgNO3 at 25C.
Calculate [Mg21] and [Ag1] in solution at equilibrium. What is the mass of the magnesium left? The
volume remains constant.
Describe an experiment that would enable you to determine which is the cathode and which is the anode
in a galvanic cell using copper and zinc electrodes.
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 volume at STP? (b) Given that the charge of an electron
is 1.6022 3 10219 C, calculate Avogadros number.
Assume that copper is oxidized to Cu21 ions.
In a certain electrolysis experiment involving Al31
ions, 60.2 g of Al is recovered when a current of
0.352 A is used. How many minutes did the electrolysis last?
Consider the oxidation of ammonia:

19.87

19.88

19.89

19.90

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 When an aqueous solution containing gold(III) salt
is electrolyzed, metallic gold is deposited at the
cathode and oxygen gas is generated at the anode.
(a) If 9.26 g of Au is deposited at the cathode, calculate the volume (in liters) of O2 generated at 23C
and 747 mmHg. (b) What is the current used if the
electrolytic process took 2.00 h?
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

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 25C.
The measured potential difference between the rod
and the SHE is 0.589 V, the rod being positive. Calculate 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 potential is 21.36 V for the reaction
2
Zn(OH) 22
Zn(s) 1 4OH2 (aq)
4 (aq) 1 2e

Calculate the formation constant (Kf) for the reaction

Zn21 (aq) 1 4OH2 (aq) Zn1OH2 22
4 (aq)

19.97 Use the data in Table 19.1 to determine whether or

not hydrogen peroxide will undergo disproportionation in an acid medium: 2H 2O 2 S 2H 2O 1 O 2.
19.98 The magnitudes (but not the signs) of the standard
reduction potentials of two metals X and Y are
2

Y 1 2e Y
X21 1 2e2 X
21

0 E 0 5 0.34 V
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 flow from X to SHE. (a) Are the E values of
the half-reactions positive or negative? (b) What is
the standard emf of a cell made up of X and Y?
19.99 A galvanic cell is constructed as follows. One halfcell consists of a platinum wire immersed in a solution containing 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 Tl1. (a) Write the half-cell reactions and the
overall reaction. (b) What is the equilibrium constant
at 25C? (c) What is the cell voltage if the T11 concentration is increased tenfold? (ETl1/Tl 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 disproportionation occur spontaneously?
3Au1 (aq) Au31 (aq) 1 2Au(s)

(c) Predict the reaction between gold and fluorine gas.

19.101 The ingestion of a very small quantity of mercury is
not considered too harmful. Would this statement

Given that [Pb21] 5 0.035 M and the solution is

buffered at pH 1.60.
19.111 A piece of magnesium ribbon and a copper wire are
partially immersed in a 0.1 M HCl solution in a
beaker. The metals are joined externally by another
piece 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 oxidized 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?
19.112 The zinc-air battery shows much promise for electric
cars because it is lightweight and rechargeable:

19.91

19.92

19.93

(The preceding reaction is an example of a disproportionation reaction in which an element in one

oxidation state is both oxidized and reduced.)
Fluorine (F2) is obtained by the electrolysis of liquid
hydrogen fluoride (HF) containing potassium fluoride (KF). (a) Write the half-cell reactions and the
overall reaction for the process. (b) What is the purpose of KF? (c) Calculate the volume of F2 (in liters)
collected at 24.0C and 1.2 atm after electrolyzing
the solution for 15 h at a current of 502 A.
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.
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 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?
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.
Consider a galvanic cell consisting of a magnesium
electrode in contact with 1.0 M Mg(NO3)2 and a cadmium electrode in contact with 1.0 M Cd(NO3)2. Calculate E for the cell, and draw a diagram showing
the cathode, anode, and direction of electron flow.
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.
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

still hold if the gastric juice in your stomach were

mostly nitric acid instead of hydrochloric acid?
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 anode 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
simultaneously be negative and positive, give an explanation for this apparently contradictory situation.
19.104 Use the data in Table 19.1 to show that the decomposition of H2O2 (a disproportionation reaction) is
spontaneous at 25C:
2H2O2 (aq) 2H2O(l) 1 O2 (g)

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 g/mL) to 26.0 percent by mass (1.19 g/mL).
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 amperes?
19.106 Consider a Daniell cell operating under nonstandardstate conditions. Suppose that the cells 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 constant current of 18.5 mA, how long (in minutes) did the electrolysis take?
19.108 Comment on whether F2 will become a stronger oxidizing agent with increasing H1 concentration.
19.109 In recent years there has been much interest in electric 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 25C:
Pb(s) 1 2H1 (aq) Pb21 (aq) 1 H2 (g)

19.113 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?

19.114 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 hypothetical reaction
Li1(aq) 1 12H2 (g) Li(s) 1 H1(aq)

The net transformation is Zn(s) 1 12 O 2(g) S ZnO(s).

(a) Write the half-reactions at the zinc-air electrodes
and calculate the standard emf of the battery at
25C. (b) Calculate the emf under actual operating
conditions when the partial pressure of oxygen is
0.21 atm. (c) What is the energy density (measured
as the energy in kilojoules that can be obtained from
1 kg of the metal) of the zinc electrode? (d) If a current of 2.1 3 105 A is to be drawn from a zinc-air
battery system, what volume of air (in liters) would
need to be supplied to the battery every second? Assume that the temperature is 25C and the partial
pressure of oxygen is 0.21 atm.

Use the appropriate equation presented in this chapter and the thermodynamic data in Appendix 3, calculate E for Li1 (aq) 1 e2 S Li(s) at 298 K.
Compare your result with that listed in Table 19.1.
(See back endpaper for the Faraday constant.)
19.115 A galvanic cell using Mg/Mg21 and Cu/Cu21 halfcells operates under standard-state conditions at
25C 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?
19.116 Given the following standard reduction potentials,
calculate the ion-product, Kw, for water at 25C:
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

Special Problems
19.117 Compare the pros and cons of a fuel cell, such as the
hydrogen-oxygen fuel cell, and a coal-fired power
station for generating electricity.
19.118 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

must be galvanized. This process is carried out by

first passing an iron sheet of appropriate dimensions
through an electrolytic cell containing Zn21 ions, using graphite as the anode and the iron sheet as the
cathode. If the voltage is 3.26 V, what is the cost of
electricity for depositing a layer 0.200 mm thick if
the efficiency of the process is 95 percent? The electricity rate is $0.12 per kilowatt hour (kWh), where
1 W 5 1 J/s and the density of Zn is 7.14 g/cm3.
19.121 A 9.00 3 102-mL 0.200 M MgI2 was electrolyzed.
As a result, hydrogen gas was generated at the cathode and iodine was formed at the anode. The volume
of hydrogen collected at 26C and 779 mmHg was
1.22 3 103 mL. (a) Calculate the charge in coulombs
consumed in the process. (b) How long (in min) did
the electrolysis last if a current of 7.55 A was used?
(c) A white precipitate was formed in the process.
What was it and what was its mass in grams? Assume the volume of the solution was constant.
19.122 Based on the following standard reduction potentials:
Fe21 (aq) 1 2e2 Fe(s)
Fe31 (aq) 1 e2 Fe21 (aq)

E1 5 20.44 V
E2 5 0.77 V

calculate the standard reduction potential for the

half-reaction
Fe31 (aq) 1 3e2 Fe(s)

E3 5 ?

19.123 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 25C
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 .
19.124 Calculate the equilibrium constant for the following
reaction at 298 K:
Zn(s) 1 Cu21 (aq) Zn21 (aq) 1 Cu(s)

Answers to Practice Exercises

1
31
19.1 5Fe21 1 MnO2
1 Mn21 1 4H2O.
4 1 8H S 5Fe
19.2 No. 19.3 0.34 V. 19.4 1 3 10242.
19.5 DG 5 24.1 3 102 kJ/mol. 19.6 Yes, E 5 10.01 V.
19.7 0.38 V. 19.8 Anode, O2; cathode, H2.
19.9 2.0 3 104 A.

be used up in the electrochemical reaction and refer

to the electrode reactions on p. 858.) (c) Calculate
Ecell and DG for the battery.
19.119 Use Equations (18.10) and (19.3) to calculate the
emf values of the Daniell cell at 25C and 80C.
Comment on your results. What assumptions are used
in the derivation? (Hint: You need the thermodynamic data in Appendix 3.)
19.120 A construction company is installing an iron culvert
(a long cylindrical tube) that is 40.0 m long with a
radius of 0.900 m. To prevent corrosion, the culvert

19.125 To remove the tarnish (Ag2S) on a silver spoon, a

student carried out the following steps. First, she
placed the spoon in a large pan filled with water so
the spoon was totally immersed. Next, she added a
few tablespoonful of baking soda (sodium bicarbonate), which readily dissolved. Finally, she
placed some aluminum foil at the bottom of the pan
in contact with the spoon and then heated the solution to about 80C. After a few minutes, the spoon
was removed and rinsed with cold water. The tarnish was gone and the spoon regained its original
shiny appearance. (a) Describe with equations the
electrochemical basis for the procedure. (b) Adding
NaCl instead of NaHCO3 would also work because
both compounds are strong electrolytes. What is the
added advantage of using NaHCO3? (Hint: Consider the pH of the solution.) (c) What is the purpose of heating the solution? (d) Some commercial
tarnish removers containing a fluid (or paste) that is
a dilute HCl solution. Rubbing the spoon with the
fluid will also remove the tarnish. Name two disadvantages of using this procedure compared to the
one described above.
19.126 The nitrite ion (NO2
2 ) in soil is oxidized to nitrate ion
(NO2
)
by
the
bacteria
Nitrobacter agilis in the pres3
ence of oxygen. The half-reduction reactions are
1
2
NO2
NO2
3 1 2H 1 2e
2 1 H2O E 5 0.42 V
1
2
O2 1 4H 1 4e 2H2O
E 5 1.23 V

Calculate the yield of ATP synthesis per mole of

nitrite oxidized. (Hint: See Section 18.7.)
19.127 Fluorine is a highly reactive gas that attacks water to
form HF and other products. Follow the procedure in
Problem 19.114 to show how you can determine indirectly the standard reduction for fluorine as shown
in Table 19.1.
19.128 As mentioned on p. 856, a concentration cell ceases
to operate when the concentrations of the two cell
compartments are equal. At this stage, is it possible
to generate an emf from the cell by adjusting
another parameter without changing the concentrations? Explain.