2003 John Wiley and Sons Publishers

Chapter 11: Oxidation and Reduction

Courtesy Craig Aurness/Corbis Images

The Electricity of Chemistry

 2003 John Wiley and Sons Publishers

Figure 11.6: Zinc metal in copper sulfate solution.

 2003 John Wiley and Sons Publishers

Courtesy Ken Karp

Figure 11.4: A form of the Daniell cell.

Electrochemical Cells
anode
oxidation

cathode
reduction

spontaneous
redox reaction

19.2

Batteries

Mercury Battery

Anode:
Cathode:

Zn(Hg) + 2OH- (aq)

HgO (s) + H2O (l) + 2eZn(Hg) + HgO (s)

ZnO (s) + H2O (l) + 2eHg (l) + 2OH- (aq)

ZnO (s) + Hg (l)
19.6

Batteries

Lead storage
battery

Anode:
Cathode:

Pb (s) + SO42- (aq)

PbSO4 (s) + 2e-

PbO2 (s) + 4H+ (aq) + SO42- (aq) + 2e-

Pb (s) + PbO2 (s) + 4H+ (aq) + 2SO2-4 (aq)

PbSO4 (s) + 2H2O (l)

2PbSO4 (s) + 2H2O (l)

 2003 John Wiley and Sons Publishers

Courtesy Skilcraft

Figure 11.3: A clock run by a chemical reaction.

What is the standard emf of an electrochemical cell made

of a Cd electrode in a 1.0 M Cd(NO3)2 solution and a Cr
electrode in a 1.0 M Cr(NO3)3 solution?
Cd2+ (aq) + 2e-

Cd (s) E0 = -0.40 V

Cr3+ (aq) + 3e-

Cr (s)

E0 = -0.74 V

0
0
0
Ecell
= Ecathode
- Eanode
0
Ecell
= -0.40 (-0.74)
0
Ecell
= 0.34 V

Cd is the stronger oxidizer

Cd will oxidize Cr

 2003 John Wiley and Sons Publishers

Courtesy Culver Pictures, Inc.

Alessandro Volta demonstrating his discovery to the French Academy in 1801.

Electrolysis
Electrolysis of Water: Requires an electrolyte species,
that is less easily oxidized and reduced than water, to
carry the current.
Anode: Water is oxidized to oxygen gas.
2 H2O(l) O2(g) + 4 H+(aq) + 4 e

Cathode: Water is reduced to hydrogen gas.

4 H2O(l) + 4 e 2 H2(g) + 4 OH(aq)

 2003 John Wiley and Sons Publishers

Courtesy Yoav Levy/Phototake

Figure 11.10: The electrolysis of water.

Electrolysis of Water

Niagara Falls and Typhoid

How Does Niagara Falls Helps to
Fight Typhoid ?

Electrolysis is the process in which electrical energy is used

to cause a nonspontaneous chemical reaction to occur.

19.8

Electrolysis
Electrolysis
of Aqueous
Sodium
Chloride:
uses
Electrolysis
of Molten
Sodium
Chloride:
different processes to molten sodium chloride.
The observed product at the anode is Cl2, and Na
metal at the cathod.

 2003 John Wiley and Sons Publishers

Courtesy Ken Karp

Galvanized tacks, drugstore iodine, and household bleach.

 2003 John Wiley and Sons Publishers

Courtesy Ken Karp

Figure 11.1: Color changes with galvanized tacks, iodine, and household bleach.

 2003 John Wiley and Sons Publishers

Courtesy Ken Karp

Figure 11.1: Color changes with galvanized tacks, iodine, and household bleach.

QUESTION

2003 John Wiley and Sons Publishers

What element forms the metal casing of a

common flashlight battery? Name three
compounds (other than water) that form the
black paste held within this metal casing. What
element forms the porous rod embedded in
this paste?

QUESTION

2003 John Wiley and Sons Publishers

Would a Daniell cell work equally well if the

salt bridge were replaced by a length of copper
wire? Explain.

QUESTION

2003 John Wiley and Sons Publishers

We can infer that copper ions in water produce

a blue color by noting that a solution of copper
sulfate in water, which contains copper ions
and sulfate ions, is blue and that a solution of
zinc sulfate in water, which contains zinc ions
and sulfate ions, is colorless. Why does this
observation lead us to conclude that the
copper ions of the copper sulfate solution
produce the blue color?

QUESTION

2003 John Wiley and Sons Publishers

Suppose that as the zinc metal is converted

into zinc ions (which are soluble in water) all
the copper ions in solution are converted to
copper metal. What new compound, a
combination of a cation and a balancing anion,
would then exist in the colorless solution?

QUESTION

2003 John Wiley and Sons Publishers

The reaction of calcium and chlorine described

in Section 3.12 can be rewritten as Ca + Cl2
CaCl2. In this reaction, what is being oxidized?
What is being reduced? Write reactions for the
two half-cells of this redox reaction.

QUESTION

2003 John Wiley and Sons Publishers

We prepared the salt bridge of our Daniell cell

by soaking a strip of cloth in a sodium chloride
solution. As the cell begins to operate, would
you expect the sodium and chloride ions of the
bridge to move? If your answer is yes, which
direction would the sodium ions move an in
which direction would the chloride ions move?
If your answer is no, explain why not.

QUESTION

2003 John Wiley and Sons Publishers

By increasing the areas of the zinc and copper

plates in the Daniell cell, we can increase the
amperage of the current flowing through the
circuit without affecting the voltage we
measure with the voltmeter. How does
increasing the size of the zinc and copper
plates affect the electrical pressure that moves
the electrons along? How does increasing the
size of the plates affect the rate of flow of the
electrons through the circuit?

QUESTION

2003 John Wiley and Sons Publishers

Which element, atom, molecule, or ion in Table

11.1 is the strongest oxidizing agent? Which is
the weakest?

QUESTION

2003 John Wiley and Sons Publishers

What is the most powerful reducing agent in

Table 11.1? Explain.

QUESTION

2003 John Wiley and Sons Publishers

In section 10.2 we saw that acids liberate

hydrogen gas when in contact with certain
metals, such as iron and zinc. Using the data
in Table 11.1, show that the reactions of iron,
and zinc with an acid spontaneously generate
hydrogen gas by redox reactions. Identify
three other metals that will spontaneously
liberate hydrogen gas from an acid. Identify
three metals that will not.

QUESTION

2003 John Wiley and Sons Publishers

Which, if any, of the following metals will

decolorize tincture of iodine: (a) nickel, (b)
copper, (c) silver, (d) magnesium, (e) calcium?
Explain your answer for each.

QUESTION

2003 John Wiley and Sons Publishers

Using the half-cell reactions of Table 11.1,

write the redox reaction that would release the
greatest amount of energy. That is, write the
redox reaction that produces the greatest
redox voltage.

QUESTION

2003 John Wiley and Sons Publishers

The Daniell cell itself isnt used as a

commercial battery. Suggest at least one
reason why it isnt.

QUESTION

2003 John Wiley and Sons Publishers

What change takes place in the composition of

the battery fluid the liquid that bathes the
batterys plates as the battery is recharged
by the generator or alternator?

QUESTION

2003 John Wiley and Sons Publishers

What three chemicals are produced through

the electrolysis of sodium chloride solutions?
What three chemicals would you expect to be
produced by the electrolysis of a solution of
sodium bromide?

QUESTION

2003 John Wiley and Sons Publishers

What is galvanized metal? Describe two ways

galvanizing helps keep iron from rusting.