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CHAPTER 24

Electrochemistry
The potential in volts has been measured for many different reduction
half-reactions. The potential value is measured against the standard hydrogen electrode, which is assigned a value of zero. For consistency,
these half-reactions are always written in the direction of the reduction. A
half-reaction that has a positive reduction potential proceeds in the direction of the reduction when it is coupled with a hydrogen electrode. A reaction that has a negative reduction potential proceeds in the oxidation
direction when it is coupled with a hydrogen electrode. Table 24-1 gives
some common standard reduction potentials.

TABLE 24-1

Reduction
half-reaction

Standard
electrode
potential,
E0
(in volts)

Reduction
half-reaction

Standard
electrode
potential,
E0
(in volts)

MnO4 8H 5e N
Mn2 4H2O

1.50

Fe3 3e N Fe

0.04

Au

3e N Au

Cl2 2e N 2Cl

2Cr

Br2 2e N 2Br
Hg

2e N Hg

Ag e N Ag
Hg22
3

Fe

2e N 2Hg

e N Fe

MnO4 e N MnO42

Pb

Sn2 2e N Sn

2e N Pb

0.13
0.14

1.23

Ni2 2e N Ni

0.26

1.22

Cd2 2e N Cd

0.40

1.07

Fe2 2e N Fe

0.45

MnO2 4H 2e N
Mn2 2H2O
2

1.50
1.36

14H 6e N
7H2O

Cr2O72
3

0.85

S 2e N S

0.48

0.80

Zn2 2e N Zn

0.76

0.80

Al

3e N Al

0.77

Mg

0.56

Na e N Na

2e N Mg

1.66
2.37
2.71

I2 2e N 2I

0.54

Ca

2e N Ca

2.87

Cu2 2e N Cu

0.34

Ba2 2e N Ba

2.91

0.14

K e N K

2.93

0.00

Li e N Li

3.04

S 2H (aq) 2e N
H2S(aq)
2H(aq) 2e N H2

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You can use reduction potentials to predict the direction in which any
redox reaction will be spontaneous. A spontaneous reaction occurs by itself, without outside inuence. The redox reaction will proceed in the direction for which the difference between the two half-reaction potentials
is positive. This direction is the same as the direction of the more positive
half-reaction.
General Plan for Solving Electrochemical Problems

2a

Balanced ionic
equation for the redox
reaction
Write the
individual halfreactions for both
oxidation and
reduction.

Balanced
equation for
reduction
Reduction
occurs at the
cathode.

3a

Balanced
equation for
oxidation

Oxidation
occurs at the
anode.

3b

Cathode
Look up the reduction
potential for the halfreaction in Table 24-1.

4a

2b

Anode

Look up the reduction

potential for the halfreaction in Table 24-1.

4b

E0cathode

E0anode

Substitute and
solve.

E0cell E0cathode E0anode

SAMPLE PROBLEM 1
Calculate the cell potential to determine whether the following reaction is spontaneous in the direction indicated.
Cd2(aq) 2I(aq) B Cd(s) I2(s)

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SOLUTION
1. ANALYZE
What is given in the
problem?
What are you asked to nd?

reactants and products

whether the reaction is spontaneous

Items

Data

Reactants

Cd2(aq) 2I(aq)

Products

Cd(s) I2(s)

?V

?V

?V

E
E

cathode

anode
cell

2. PLAN
What steps are needed to
determine whether the
reaction is spontaneous?

Separate into oxidation and reduction half-reactions. Find reduction

potentials for each. Solve the equation for the cell potential to determine if the reaction is spontaneous.
1

Cd2(aq) 2I(aq) : Cd(s) I2(s)

write the individual
half-reactions

2a

2b

Cd2(aq) 2e : Cd(s)

2I(aq) : I2(s) 2e

reduction occurs
at the cathode

oxidation occurs
at the anode

3a

3b

Cathode

Anode

look up the
reduction potential
for the half-reaction
in Table 24-1

look up the
reduction potential
for the half-reaction
in Table 24-1

4a

4b

E0cathode

E0anode
substitute and solve

5
E0cell E0cathode E0anode

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Write the given equation.
Cd2(aq) 2I(aq) : Cd(s) I2(s)
The oxidation number of cadmium decreases; it is reduced.
Cd2(aq) 2e : Cd(s)
The oxidation number of iodine increases; it is oxidized.
2I(aq) : I2(s) 2e
Cadmium is the cathode, and iodine is the anode.
from Table 24-1

E0cathode 0.40 V

from Table 24-1

E0anode 0.54 V
given above

given above

E0cell E0cathode E0anode

Determine spontaneity. If the cell potential is positive, the reaction is

spontaneous as written. If the cell potential is negative, the reaction is
not spontaneous as written, but the reverse reaction is spontaneous.
3. COMPUTE
E0cell 0.40 V 0.54 V 0.94 V
The reaction potential is negative. Therefore, the reaction is not spontaneous. The reverse reaction would have a positive potential and
would, therefore, be spontaneous.
Cd2(aq) 2I(aq) : Cd(s) I2(s) not spontaneous
Cd(s) I2(s) : Cd2(aq) 2I(aq) spontaneous
4. EVALUATE
Are the units correct?
Is the number of signicant
gures correct?

Is the answer reasonable?

Yes; cell potentials are in volts.

Yes; the number of signicant gures is correct because the half-cell
potentials have two significant
gures.
Yes; the reduction potential for the
half-reaction involving iodine was
more positive than the potential for
the reaction involving cadmium,
which means that I2 has a greater attraction for electrons than Cd2.
Therefore, I2 is more likely to be reduced than Cd2. The reverse reaction is favored.

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PRACTICE
Use the reduction potentials in Table 24-1 to determine whether the following reactions are spontaneous as written. Report the E0cell for the
reactions.
ans: 0.79 V; spontaneous
1. Cu2 Fe : Fe2 Cu
2
2
3
2. Pb Fe : Fe Pb
ans: 0.90 V; nonspontaneous
2
2
3. Mn 4H2O Sn :
ans: 1.64 V; nonspontaneous

MnO
4 8H Sn

4. MnO2
ans: 0.80 V; spontaneous
4 Cl2 : MnO4 2Cl
2
2
5. Hg2 2MnO4 :
ans: 0.24 V; spontaneous
2Hg 2MnO4
6. 2Li Pb : 2Li Pb2
ans: 2.91 V; nonspontaneous
7. Br2 2Cl : 2Br Cl2
ans: 0.29 V; nonspontaneous

2
8. S 2I : S I2
ans: 1.02 V; nonspontaneous
SAMPLE PROBLEM 2
A cell is constructed in which the following two half-reactions
can occur in either direction.
Zn2 2e N Zn
Br2 2e N 2Br
Write the full ionic equation for the cell in the spontaneous direction, identify the reactions occurring at the anode and cathode, and determine the cells voltage.
SOLUTION
1. ANALYZE
What is given in the
problem?
What are you asked to nd?

the reversible half-reactions of the

cell
the equation in the spontaneous direction; the voltage of the cell

Items

Data

Half-reaction 1

Zn2 2e N Zn

Half-reaction 2

Br2 2e N 2Br

Reduction potential of 1

0.76 V

Reduction potential of 2

1.07 V

Full ionic reaction

Cell voltage

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2. PLAN
What steps are needed to
determine the spontaneous
reaction of the cell and the
cell voltage?

Determine which half-reaction has

the more positive reduction potential. This will be the reduction halfreaction; it occurs at the cathode.
Reverse the other half-reaction so
that it becomes an oxidation halfreaction; it occurs at the anode.
Adjust the half-reactions so that the
same number of electrons are lost as
are gained. Add the reactions together. Compute the cell voltage
by the formula E0cell E0cathode
E0anode , using the reduction potentials for the reaction at each electrode.

Br2 2e N 2Br

Zn2 2e N Zn

look up the
reduction potential
for the half-reaction
in Table 24-1

look up the
reduction potential
for the half-reaction
in Table 24-1

E0half-reaction

E0half-reaction

the half-cell with

the larger reduction
potential is the
cathode

the half-cell with

the smaller
reduction potential
is the anode

Cathode

Anode

reduction occurs
at the cathode

oxidation occurs
at the anode

Br2 2e : 2Br

Zn : Zn2 2e
combine to write the full
ionic equation

Br2 Zn : 2Br Zn2

substitute and solve

E0cell E0cathode E0anode

First, look up the reduction potentials for the two half-reactions in

Table 24-1.
from Table 24-1

0 1.07 V
EBr
2

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from Table 24-1

0 0.76 V
EZn
Br2 has the larger reduction potential; therefore, it is the cathode. Zn
has the smaller reduction potential; therefore, it is the anode.

The cathode half-reaction is

Br2 2e : 2Br
The anode half-reaction is
Zn : Zn2 2e
The full-cell equation is
Br2 2e : 2Br
Zn : Zn2 2e
Br2 Zn : 2Br Zn2
Substitute the reduction potentials for the anode and cathode into the
cell potential equation, and solve the equation.
E0Br2

E0Zn

E0cell E0cathode E0anode

3. COMPUTE
Br2 Zn : 2Br Zn2
0
Ecell
1.07 V (0.76 V) 1.83 V
4. EVALUATE
Are the units correct?
Is the number of signicant
gures correct?
Is the answer reasonable?

Yes; the cell potential is in volts.

Yes; the half-cell potentials were
given to two decimal places.
Yes; you would expect the reaction
to have a positive cell potential because it should be spontaneous.

PRACTICE
If a cell is constructed in which the following pairs of reactions are possible, what would be the cathode reaction, the anode reaction, and the
overall cell voltage?
1. Ca2 2e N Ca
ans: cathode: Fe3 3e : Fe
3

Fe 3e N Fe
anode: Ca : Ca2 2e
E0cell 2.83 V
2. Ag e N Ag
ans: cathode: Ag e : Ag

S 2H 2e N H2S
anode: H2S : S 2H 2e
E0cell 0.66 V

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3. Fe3 e N Fe2
Sn2 2e N Sn
4. Cu2 2e N Cu
Au3 3e N Au

ans: cathode: Fe3 e : Fe2

anode: Sn : Sn2 2e
E0cell 0.91 V
ans: cathode: Au3 3e : Au
anode: Cu : Cu2 2e
E0cell 1.16 V

ADDITIONAL PROBLEMS
Use reduction potentials to determine whether the reactions in the following 10 problems are spontaneous.
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.

Ba Sn2 : Ba2 Sn
Ni Hg2 : Ni2 Hg

2
2Cr3 7 H2O 6Fe3 : Cr2O2
7 14H 6Fe

2
Cl2 Sn : 2Cl Sn
Al 3Ag : Al3 3Ag
2
Hg2
: 2Hg S
2 S

Ba 2Ag : Ba2 2Ag

2I Ca2 : I2 Ca
2
Zn 2MnO
2MnO2
4 : Zn
4

2Cr3 3Mg2 7H2O : Cr2O2

7 14H 3Mg

In the following problems, you are given a pair of reduction halfreactions. If a cell were constructed in which the pairs of half-reactions
were possible, what would be the balanced equation for the overall cell
reaction that would occur? Write the half-reactions that occur at the
cathode and anode, and calculate the cell voltage.
11. Cl2 2e N 2Cl
Ni2 2e N Ni
12. Fe3 3e N Fe
Hg2 2e N Hg
2

13. MnO
4 e N MnO4
Al3 3e N Al

2
14. MnO
4H2O
4 8H 5e N Mn

S 2H 2e N H2S
15. Ca2 2e N Ca
Li e N Li
16. Br2 2e N 2Br

2
MnO
4H2O
4 8H 5e N Mn

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17. Sn2 2e N Sn
Fe3 e N Fe2
18. Zn2 2e N Zn

3
Cr2O2
7H2O
7 14H 6e N 2Cr
2

19. Ba 2e N Ba
Ca2 2e N Ca
20. Hg22 2e N 2Hg
Cd2 2e N Cd

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