Chapter 18

Electrochemistry

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 Electrochemical Processes
Electrochemical processes are oxidation-reduction
reactions in which:
• the energy released by a spontaneous reaction is
converted to electricity or
• electrical energy is used to cause a nonspontaneous
reaction to occur

0 0 2 2
2Mg  s   O 2  g   2MgO  S 

2Mg  2Mg 2  4e  Oxidation half  reaction  lose e  

O 2  4e   2O 2 Reduction half  reaction  gain e  
© McGraw-Hill Education. 18-2
 Oxidation Number (1 of 2)
The charge the atom would have in a molecule (or an
ionic compound) if electrons were completely transferred.
1. Free elements (uncombined state) have an oxidation
number of zero.

Na, Be, K, Pb, H 2, O 2, P4  0

2. In monatomic ions, the oxidation number is equal to
the charge on the ion.
Li  , Li   1; Fe3+ , Fe  + 3; O 2 , O   2
3. The oxidation number of oxygen is usually −2. In
H 2O 2 and O 2 2 it is  1.
© McGraw-Hill Education. 18-3
 Oxidation Number (2 of 2)

4. The oxidation number of hydrogen is +1 except when it

is bonded to metals in binary compounds. In these
cases, its oxidation number is –1.

5. Group IA metals are +1, IIA metals are +2 and fluorine is

always –1.

6. The sum of the oxidation numbers of all the atoms in a

molecule or ion is equal to the charge on the molecule or
ion.

© McGraw-Hill Education. 18-4

 Balancing Redox Equations (1 of 3)
The oxidation of Fe2 to Fe3 by Cr2O7 2 in acid solution ?
1. Write the unbalanced equation for the reaction in ionic
form.
Fe 2  Cr2O 7 2  Fe3  Cr 3
2. Separate the equation into two half-reactions.
2 3
Oxidation: 2  3
Fe Fe
6 3
Reduction: 
Cr2O 7 2 Cr 3
3. Balance the atoms other than O and H in each half-
reaction.
Cr2O 7 2  2Cr 3
© McGraw-Hill Education. 18-5
 Balancing Redox Equations (2 of 3)

4. For reactions in acid, add H2O to balance O atoms and H
to balance H atoms.
Cr2O 7 2  2Cr 3  7H 2O
14H   Cr2O 7 2  2Cr 3  7H 2O
5. Add electrons to one side of each half-reaction to balance
the charges on the half-reaction.
Fe 2  Fe 3  1e 
6e   14H   Cr2O 7 2  2Cr 3  7H 2O
6. If necessary, equalize the number of electrons in the two
half-reactions by multiplying the half-reactions by
appropriate coefficients.
6Fe 2  6Fe3  6e 
6e  14H   Cr2O7 2  2Cr 3  7H 2O
© McGraw-Hill Education. 18-6
 Balancing Redox Equations (3 of 3)
7. Add the two half-reactions together and balance the final
equation by inspection. The number of electrons on both
sides must cancel.

Oxidation : 6Fe 2  6Fe 3  6 e 

Reduction : 6 e   14H   Cr2O 7 2  2Cr 3  7H 2O
14H   Cr2O 7 2  6Fe 2  6Fe 3  2Cr 3  7H 2O

8. Verify that the number of atoms and the charges are

balanced.
14 × 1 − 2 + 6 × 2 = 24 = 6 × 3 + 2 × 3
9. For reactions in basic solutions, add OH− to both sides of the
equation for every H+ that appears in the final equation.
© McGraw-Hill Education. 18-7
 Example 18.1 (1 of 7)

Write a balanced ionic equation to represent the

oxidation of iodide ion (I−) by permanganate ion (MnO4−)
in basic solution to yield molecular iodine (I2) and
manganese(IV) oxide (MnO2).

© McGraw-Hill Education. 18-8

 Example 18.1 (2 of 7)

Strategy

We follow the preceding procedure for balancing redox

equations. Note that the reaction takes place in a basic
medium.

Solution

Step 1: The unbalanced equation is

MnO 4  I   MnO2  I2
© McGraw-Hill Education. 18-9
 Example 18.1 (3 of 7)
Step 2: The two half-reactions are
1 0

Oxidation : I  I2

7 4

Reduction : MnO  MnO 2 4

Step 3: We balance each half-reaction for number and

type of atoms and charges. Oxidation half-
reaction: We first balance the I atoms:

2I   I 2
© McGraw-Hill Education. 18-10
 Example 18.1 (4 of 7)
To balance charges, we add two electrons to the right-
hand side of the equation:

2I   I 2  2e 

Reduction half-reaction: To balance the O atoms, we add

two H2O molecules on the right:

MnO 4  MnO2  2H 2O

To balance the H atoms, we add four H+ ions on the left:

MnO 4  4H   MnO 2  2H 2O
© McGraw-Hill Education. 18-11
 Example 18.1 (5 of 7)
There are three net positive charges on the left, so we add three
electrons to the same side to balance the charges:

MnO 4  4H   3e   MnO 2  2H 2O

Step 4: We now add the oxidation and reduction half reactions to give
the overall reaction. In order to equalize the number of
electrons, we need to multiply the oxidation half-reaction by 3
and the reduction half-reaction by 2 as follows:

3  2I   I 2  2e  
2  MnO 4  4H   3e   MnO 2  2H 2O 

6I  MnO 4  8H   6 e   3I 2  2MnO 2  4H 2O  6 e 

© McGraw-Hill Education. 18-12
 Example 18.1 (6 of 7)
The electrons on both sides cancel, and we are left with
the balanced net ionic equation:

6I   2MnO 4  8H   3I 2  2MnO 2  4H 2O

This is the balanced equation in an acidic medium.

However, because the reaction is carried out in a basic
medium, for every H+ ion we need to add equal number of
OH− ions to both sides of the equation:

6I   2MnO4  8H   8OH   3I 2  2MnO 2  4H 2O  8OH 

© McGraw-Hill Education. 18-13

 Example 18.1 (7 of 7)

Finally, combining the H+ and OH− ions to form water, we

obtain

6I   2MnO 4  4H 2O  3I 2  2MnO 2  8OH 

Step 5: A final check shows that the equation is

balanced in terms of both atoms and charges.

© McGraw-Hill Education. 18-14

Galvanic Cells (1 of 2)

Jump to long description

© McGraw-Hill Education. 18-15
 Galvanic Cells (2 of 2)
The difference in electrical potential
between the anode and cathode is
called:
• cell voltage
• electromotive force (emf)
• cell potential
Jump to long description
Zn  s   Cu 2  aq   Cu  s   Zn 2  aq 
 Cu 2   1 M and  Zn 2   1 M
Cell Diagram
phase boundary

© McGraw-Hill Education. 18-16

 Standard Reduction Potentials (1 of 4)
Standard reduction potential (E°) is the voltage associated
with a reduction reaction at an electrode when all solutes are
1 M and all gases are at 1 atm.

Reduction Reaction
2e   2H   1M   H 2  1 atm 

E   0V

Jump to long description

Standard hydrogen electrode (SHE)
© McGraw-Hill Education. 18-17
Standard Reduction Potentials (2 of 4)

Jump to long description

Zn  s  | Zn 2  1 M  || H   1 M  | H 2  1 atm  | Pt  s 

Anode  oxidation  : Zn  s   Zn 2  1 M   2e

Cathode  reduction  : 2e  2H   1 M   H 2  1 atm 
Zn  s   2H   1 M   Zn 2  1 M   H 2  1 atm 
© McGraw-Hill Education. 18-18
Standard Reduction Potentials (3 of 4)

Ecell

 0.76V

Standard emf  Ecell



Ecell

 Ecathodel

 Eanode


Jump to long description

Zn  s  | Zn 2  1M  || H   1M  | H 2  1atm  | Pt  s 
Ecell

 EH  H2
 EZn

2
Zn

0.76V  0  EZn

2
Zn

EZn

2
Zn
  0  76V
Zn 2  1M   2e   Zn E    0.76 V
© McGraw-Hill Education. 18-19
Standard Reduction Potentials (4 of 4)

Ecell

 0.34V
Ecell

 Ecathode

 Eanode


Ecell

 ECu

2
Cu
 E 
H H 2

0.34  ECu

2
Cu
0
ECu

2
Cu
 0.34V

Jump to long description

Pt  s  | H 2  1atm  | H   1 M  || Cu 2  1M  | Cu  s 
Anode  oxidation  : H 2  1atm   2H   1 M   2e 
Cathode  reduction  : 2e  Cu 2  1 M   Cu  s 
H 2  1atm   Cu 2  1M   Cu  s   2H   1 M 
© McGraw-Hill Education. 18-20
Standard Reduction Potentials (E°)
• E° is for the reaction as written
• The more positive E°
• The greater the tendency for the
substance to be reduced
• The half-cell reactions are
reversible
• The sign of E° changes when
the reaction is reversed
• Changing the stoichiometric
coefficients of a half-cell
reaction does not change the
value of E°

Jump to long description

© McGraw-Hill Education. 18-21
 Example 18.2 (1 of 3)

Predict what will happen if molecular bromine (Br2) is

added to a solution containing NaCl and Nal at
25°C. Assume all species are in their standard
states.

© McGraw-Hill Education. 18-22

 Example 18.2 (2 of 3)
Strategy
To predict what redox reaction(s) will take place, we need to
compare the standard reduction potentials of Cl2, Br2, and I2 and
apply the diagonal rule.

Solution
From Table 18.1, we write the standard reduction potentials as
follows:
Cl2  1atm   2e   2Cl   1 M  E   1.36 V

Br2  l   2e   2Br   1 M  E   1.07 V

I 2  s   2e   2I   1 M  E   0.53 V
© McGraw-Hill Education. 18-23
 Example 18.2 (3 of 3)
Applying the diagonal rule we see that Br2 will oxidize I− but will
not oxidize Cl− . Therefore, the only redox reaction that will
occur appreciably under standard-state conditions is

Oxidation : 2I   1 M   I 2  s   2e
Reduction : Br2  l   2e   2Br   1 M 

Overall : 2I   1M   Br2  l   I 2  s   2Br   1 M 

Check
We can confirm our conclusion by calculating E°cell. Try it. Note
that the Na+ ions are inert and do not enter into the redox
reaction.
© McGraw-Hill Education. 18-24
 Example 18.3 (1 of 4)

A galvanic cell consists of a Mg electrode in a 1.0 M

Mg(NO3)2 solution and a Ag electrode in a 1.0 M
AgNO3 solution. Calculate the standard emf of this
cell at 25°C.

© McGraw-Hill Education. 18-25

 Example 18.3 (2 of 4)
Strategy
At first it may not be clear how to assign the electrodes in the
galvanic cell. From Table 18.1 we write the standard reduction
potentials of Ag and Mg and apply the diagonal rule to
determine which is the anode and which is the cathode.

Solution
The standard reduction potentials are

Ag   1.0 M   e   Ag  s  E   0.80V

Mg 2  1.0 M   2e   Mg  s  E    2.31V
© McGraw-Hill Education. 18-26
 Example 18.3 (3 of 4)

Applying the diagonal rule, we see that Ag+ will

oxidize Mg:

Anode  oxidation  : Mg  s   Mg 2  1  0M   2e

Cathode  reduction  : 2Ag   1.0M   2e  2Ag  s 

Overall : Mg  s   2Ag   1.0M   Mg 2  1.0M   2Ag  s 

© McGraw-Hill Education. 18-27

 Example 18.3 (4 of 4)
Note that in order to balance the overall equation we multiplied
the reduction of Ag+ by 2. We can do so because, as an
intensive property, E° is not affected by this procedure. We find
the emf of the cell by using Equation (18.1) and Table 18.1:

Ecell

 Ecathode

 Eanode


 EAg


Ag
 EMg

2
Mg

 0.80V   2.37 V 
 3.17 V
Check
The positive value of E° shows that the forward reaction is
favored.
© McGraw-Hill Education. 18-28
 Spontaneity of Redox Reactions (1 of 2)
G   nFEcell n  number of molesof electronsin reaction

J
G 0   nFEcell
0
F  96,500  96,500C mol
V  mol

G 0   RT ln K  nFEcell
0

0
Ecell 
RT
ln K 
 8.314 J K  mol   298 K  ln K
nF n  96,500 J V  mol 

0.0257 V
0
Ecell  ln K
n

0.0592 V
0
Ecell  log K
n

© McGraw-Hill Education. 18-29

Spontaneity of Redox Reactions (2 of 2)


Table 18.2 Relationships Among ΔG, K, and Ecell
ΔG° K E°cell Reaction Under Standard − State
Conditions
Negative >1 Positive Favors formation of products.
0 =1 0 Reactants and products are equally
favored.
Positive <1 Negative Favors formation of reactants.

G 0   RT ln K   nFEcell


© McGraw-Hill Education. 18-30

 Example 18.4 (1 of 4)

Calculate the equilibrium constant for the following

reaction at 25°C:

Sn  s   2Cu 2  aq   Sn 2  aq   2Cu   aq 

© McGraw-Hill Education. 18-31

 Example 18.4 (2 of 4)
Strategy

The relationship between the equilibrium constant K and

the standard emf is given by Equation (18.5):

Ecell

  0.0257 V n  ln K

Thus, if we can determine the standard emf, we can

calculate the equilibrium constant. We can determine the
E°cell of a hypothetical galvanic cell made up of two
couples  Sn Sn and Cu Cu 
2 2

from the standard reduction potentials in Table 18.1.

© McGraw-Hill Education. 18-32
 Example 18.4 (3 of 4)
Solution

The half-cell reactions are

Anode  oxidation  : Sn  s   Sn 2  aq   2e

Cathode  reduction  : 2Cu 2  aq   2e  2Cu   aq 

E cell  E cathode  E anode

 E Cu 2 Cu   E Sn 2 Sn
 0.15V   0.14V 
 0.29V
© McGraw-Hill Education. 18-33
 Example 18.4 (4 of 4)
Equation (18.5) can be written

nE 
ln K 
0.0257 V

In the overall reaction we find n = 2 Therefore,

ln K 
 2   0.29V 
 22.6
0.0257 V

K  e 22.6  7  109
© McGraw-Hill Education. 18-34
 Example 18.5 (1 of 4)

Calculate the standard free-energy change for the

following reaction at 25°C:

2Au  s   3Ca 2  1.0M  M  2Au 3  1.0M   3Ca  s 

© McGraw-Hill Education. 18-35

 Example 18.5 (2 of 4)
Strategy

The relationship between the standard free energy

change and the standard emf of the cell is given by
Equation (18.3): G   nFEcell

.
Thus, if we can determine E°cell we can calculate ∆G° We
can determine the E°cell of a hypothetical galvanic cell
made up of two couples  Au 3
Au and Ca 2
Ca 
from the standard reduction potentials in Table 18.1.

© McGraw-Hill Education. 18-36

 Example 18.5 (3 of 4)
Solution

The half-cell reactions are

Anode  oxidation  : 2Au  s   2Au 3  1.0M   6e

Cathode  Reduction  : 3Ca 2  1.0M   6e  3Ca  s 

Ecell

 Ecathode

 Eanode


 ECa

2
Ca
 E 
Au 3 Au

  2.87 V  1.50V
  4.37 V

© McGraw-Hill Education. 18-37

 Example 18.5 (4 of 4)
Now we use Equation (18.3):

G    nFE 
The overall reaction shows that n = 6, so
G    6   96,500J V  mol   4.37 V 
 2.53  106 J mol
 2.53  103 kJ mol
Check
The large positive value of ΔG° tells us that the reaction
favors the reactants at equilibrium. The result is consistent
with the fact that E° for the galvanic cell is negative.
© McGraw-Hill Education. 18-38
The Effect of Concentration on Cell Emf

G  G  RT ln Q G   nFE G   nFE 

nFE   nFE   RT ln Q

Nernst equation

RT
E  E  ln Q
nF
At 298 K
0.0257 V 0.0592 V
E  E  ln Q E  E  log Q
n n
© McGraw-Hill Education. 18-39
 Example 18.6 (1 of 4)

Predict whether the following reaction would proceed

spontaneously as written at 298 K:

Co  s   Fe 2  aq   Co 2  aq   Fe  s 

given that Co 2   0.15M and  Fe 2   0.68M.

© McGraw-Hill Education. 18-40

 Example 18.6 (2 of 4)
Strategy

Because the reaction is not run under standard-state

conditions (concentrations are not 1 M), we need Nernst’s
equation [Equation (18.8)] to calculate the emf (E) of a
hypothetical galvanic cell and determine the spontaneity of
the reaction. The standard emf (E°) can be calculated using
the standard reduction potentials in Table 18.1. Remember
that solids do not appear in the reaction quotient (Q) term
in the Nernst equation. Note that 2 moles of electrons are
transferred per mole of reaction, that is, n = 2.

© McGraw-Hill Education. 18-41

 Example 18.6 (3 of 4)
Solution

The half-cell reactions are

Anode  oxidation  : Co  s   Co 2  aq   2e 
Cathode  reduction  : Fe 2  aq   2e  Fe  s 

Ecell

 E cathode  E anode
 E Fe2 Fe  E Co2 Co
  0.44V   0.28V 
  0.16V
© McGraw-Hill Education. 18-42
 Example 18.6 (4 of 4)
From Equation (18.8) we write

0.0257 V
E  E  ln Q
n
0.0257 V   Co 2

 E  ln
n  Fe 2 
0.0257 V 0.15
  0.16 V  ln
2 0.68
  0.16V  0.019V
  0.14V
Because E is negative, the reaction is not spontaneous
in the direction written.
© McGraw-Hill Education. 18-43
 Example 18.7 (1 of 4)
Consider the galvanic cell shown in Figure 18.4(a). In a
certain experiment, the emf (E) of the cell is found to be
0.54 V at 25°C. Suppose that  Zn 2   1.0M and PH2  1.0atm 
Calculate the molar concentration of H+.

Jump to long description

© McGraw-Hill Education. 18-44
 Example 18.7 (2 of 4)
Strategy

The equation that relates standard emf and nonstandard

emf is the Nernst equation. The overall cell reaction is

Zn  s   2H   ?M   Zn 2  1.0M   H 2  1.0atm 

Given the emf of the cell (E), we apply the Nernst equation
to solve for [H+]. Note that 2 moles of electrons are
transferred per mole of reaction; that is, n = 2.

© McGraw-Hill Education. 18-45

 Example 18.7 (3 of 4)
Solution
As we saw earlier, the standard emf (E°) for the cell is 0.76 V.
From Equation (18.8) we write
0.0257 V
E  E  ln Q
n
0.0257 V  Zn  PH2
2

 E  ln 2
n  H  
0.0257 V  1.0   1.0 
0.54V  0.76 V  ln 2
2  H  
0.0257 V 1
 0.22V   ln 2
2  H  
1
17.1  ln 2
 H  
1
e17.1  2
 H  

1
 H     2  10 4 M
3  10 7

© McGraw-Hill Education. 18-46

 Example 18.7 (4 of 4)

Check

The fact that the nonstandard-state emf (E) is given

in the problem means that not all the reacting
species are in their standard-state concentrations.
Thus, because both Zn 2 ions and H2 gas are in
their standard states,   is not 1 M.
 
H

© McGraw-Hill Education. 18-47

 Concentration Cells
Galvanic cell from two half-cells composed of the same
material but differing in ion concentrations.
Zn  s  | Zn 2  0.10M  || Zn 2  1.0M  | Zn  s 
Oxidation : Zn  s   Zn 2  0.10M   2e-
Reduction : Zn 2  1.0M   2e   Zn  s 
Overall : Zn 2  1.0M   Zn 2  0.10M 

0.0257 V   Zn 2

E  E  ln dil
2  Zn 2 
conc

0.0257 V 0.10
E0 ln  0.0296V
2 1.0
© McGraw-Hill Education. 18-48
 Batteries (1 of 5)

Dry cell
Leclanché cell

Jump to long description

Anode : Zn  s   Zn 2  aq   2e 
Cathode : 2NH 4  aq   2MnO 2  s   2e   Mn 2O 3  s   2NH 3  aq   H 2O  l 
Zn  s   2 NH 4  aq   2MnO2  s   Zn 2  aq   2 NH 3  aq   H 2O  l   Mn2O3  s 

© McGraw-Hill Education. 18-49

 Batteries (2 of 5)

Mercury Battery

Jump to long description

Anode : Zn  Hg   2OH   aq   ZnO  s   H 2O  l   2e 

Cathode : HgO  s   H 2O  l   2e   Hg  l   2OH   aq 
Zn  Hg   HgO  s   ZnO  s   Hg  l 
© McGraw-Hill Education. 18-50
 Batteries ( 3 of 5)

Lead storage
battery

Jump to long description

Anode : Pb  s   SO 24  aq   PbSO 4  s   2e 

Cathode : PbO 2  s   4H   aq   SO 24  aq   2e   PbSO 4  s   2H 2O  l 
Pb  s   PbO 2  s   4H   aq   2SO 24  aq   2PbSO 4  s   2H 2O  l 

© McGraw-Hill Education. 18-51

 Batteries (4 of 5)

Jump to long description

Li  Li   e  Li   CoO 2  e   LiCoO 2
Solid State Lithium Battery
© McGraw-Hill Education. 18-52
 Batteries (5 of 5)

A fuel cell is an
electrochemical cell that
requires a continuous
supply of reactants to
keep functioning

Jump to long description

Anode : 2H 2  g   4OH   aq   4H 2O  l   4e 
Cathode : O 2  g   2H 2O  l   4e   4OH   aq 
2H 2  g   O 2  g   2H 2O  l 
© McGraw-Hill Education. 18-53
Chemistry In Action: Bacteria Power
CH3COO  2O 2  H   2CO 2  2H 2O

Jump to long description

© McGraw-Hill Education. 18-54
 Corrosion
Corrosion is the term usually applied to the
deterioration of metals by an electrochemical
process.

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© McGraw-Hill Education. 18-55
Cathodic Protection of an Iron Storage
Tank

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© McGraw-Hill Education. 18-56
 Electrolysis
Electrolysis is the process in which electrical energy is
used to cause a nonspontaneous chemical reaction to
occur.

Electrolysis of molten NaCl

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© McGraw-Hill Education. 18-57
 Electrolysis of Water

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© McGraw-Hill Education. 18-58
 Example 18.8 (1 of 4)
An aqueous Na2SO4 solution is electrolyzed, using the
apparatus shown in Figure 18.18. If the products formed
at the anode and cathode are oxygen gas and hydrogen
gas, respectively, describe the electrolysis in terms of
the reactions at the electrodes.

© McGraw-Hill Education. 18-59

 Example 18.8 (2 of 4)
Strategy

Before we look at the electrode reactions, we should

consider the following facts: (1) Because NaSO4 does not
hydrolyze, the pH of the solution is close to 7. (2) The Na+
2
ions are not reduced at the cathode and the SO 4
ions are not oxidized at the anode. These conclusions are
drawn from the electrolysis of water in the presence of
sulfuric acid and in aqueous sodium chloride solution, as
discussed earlier. Therefore, both the oxidation and
reduction reactions involve only water molecules.

© McGraw-Hill Education. 18-60

 Example 18.8 (3 of 4)
Solution

The electrode reactions are

Anode : 2H 2O  l   O 2  g   4H   aq   4e 
Cathode : 2H 2O  l   2e  H 2  g   2OH   aq 

The overall reaction, obtained by doubling the cathode

reaction coefficients and adding the result to the anode
reaction, is

6H 2O  l   2H 2  g   O2  g   4H   aq   4OH   aq 
© McGraw-Hill Education. 18-61
 Example 18.8 (4 of 4)

If the H+ and OH− ions are allowed to mix, then

4H   aq   4OH   aq   4H 2O  l 

and the overall reaction becomes

2H 2O  l   2H 2  g   O 2  g 

© McGraw-Hill Education. 18-62

Electrolysis and Mass Changes

charge (C) = current (A) × time (s)

1 mol e− = 96,500 C

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© McGraw-Hill Education. 18-63
 Chemistry In Action: Dental Filling
Discomfort

Hg 22 Ag 2 Hg 3 0.85V
2
Sn Ag 3Sn  0.05V
Sn 2 Sn 8Hg  0.13V

Jump to long description

© McGraw-Hill Education. 18-64
 Example 18.9 (1 of 7)

A current of 1.26 A is passed through an electrolytic

cell containing a dilute sulfuric acid solution for 7.44
h. Write the half-cell reactions and calculate the
volume of gases generated at STP.

© McGraw-Hill Education. 18-65

 Example 18.9 (2 of 7)

Strategy

Earlier we saw that the half-cell reactions for the

process are

Anode  oxidation  : 2H 2O  l   O 2  g   4H   aq   4e 
 1 
Cathode  reduction  : 4 H   aq   e   H 2  g  
 2 
Overall : 2H 2O  l   2H 2  g   O 2  g 

© McGraw-Hill Education. 18-66

 Example 18.9 (3 of 7)

According to Figure 18.20, we carry out the following

conversion steps to calculate the quantity of O2 in
moles:

current  time  coulombs  molesof e   molesof O 2

Then, using the ideal gas equation we can calculate

the volume of O2 in liters at STP. A similar procedure
can be used for H2.

© McGraw-Hill Education. 18-67

 Example 18.9 (4 of 7)
Solution
First we calculate the number of coulombs of
electricity that pass through the cell:

3600 s 1C
?C  1.26 A  7.44 h    3.37  104 C
1h 1A  s

Next, we convert number of coulombs to number

of moles of electrons

1mol e
3.37  104 C   0.349mol e
96,500 C
© McGraw-Hill Education. 18-68
 Example 18.9 (5 of 7)
From the oxidation half-reaction we see that 1 mol
O2 = 4 mol e−.Therefore, the number of moles of O2
generated is
1 mol O 2

0.349 mol e  
 0.0873 mol O 2
4 mol e

The volume of 0.0873 mol O2 at STP is given by

nRT
V
P


 0.0873mol   0.0821L  atm K  mol   273K 
 1  96 L
1atm
© McGraw-Hill Education. 18-69
 Example 18.9 (6 of 7)
The procedure for hydrogen is similar. To simplify, we
combine the first two steps to calculate the number of
moles of H2 generated:

1 mol e 1molH 2
3.37  10 C 
4
 
 0.175mol H 2
96,500 C 2 mol e

The volume of 0.175 mol H2 at STP is given by

nRT
V
P


 0.175mol   0.00821L  atm K  mol   273K 
 3.92 L
1 atm
© McGraw-Hill Education. 18-70
 Example 18.9 (7 of 7)

Check

Note that the volume of H2 is twice that of O2 (see

Figure 18.18), which is what we would expect based on
Avogadro’s law (at the same temperature and pressure,
volume is directly proportional to the number of moles
of gases).

© McGraw-Hill Education. 18-71

Appendix of Image Long Descriptions

© 2019 McGraw-Hill Education. 18-72

Galvanic Cells (1 of 2) Long Description

A spontaneous redox reaction occurs within the galvanic

cell. In the example given, a Zn rod is placed into a
ZnSO4 solution at the anode, and a Cu rod is placed
into a CuSO4 solution at the cathode. A KCl salt bridge
is placed between the cells, allowing for ions to pass
through the bridge between the anode and cathode.
At the anode, Zn atoms are oxidized to produce zinc
ions and two electrons. The electrons are passed
externally to the cathode, creating a current that lights a
bulb. When the electrons reach the cathode, copper(II)
ions are reduced to form Cu atoms.

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© McGraw-Hill Education. 18-73
Galvanic Cells (2 of 2) Long Description
When a 1 M solution of ZnSO4 and zinc rod at the
anode and a 1 M CuSO4 solution with a Cu rod at
the cathode are measured, the voltage is 1.10 volts.

Jump to image
© McGraw-Hill Education. 18-74
Standard Reduction Potentials (1 of 4)
Long Description
The half reaction is the conversion of H2 gas to two
aqueous H+ ions and two electrons. This electrode is
known as a standard hydrogen electrode (SHE).

Jump to image
© McGraw-Hill Education. 18-75
Standard Reduction Potentials (2 of 4)
Long Description
A Zn rod produces aqueous zinc ions and produces
two electrons. At the cathode, two electrons bind to
two aqueous protons to produce H2 gas. The voltage
between the two is 0.76 volts.

Jump to image
© McGraw-Hill Education. 18-76
Standard Reduction Potentials (3 of 4)
Long Description
A Zn rod produces aqueous zinc ions and produces
two electrons. At the cathode, two electrons bind to
two aqueous protons to produce H2 gas. The voltage
between the two is 0.76 volts.

Jump to image
© McGraw-Hill Education. 18-77
Standard Reduction Potentials (4 of 4)
Long Description
At the cathode, two electrons bind with aqueous
copper(II) ions to produce solid copper atoms. At the
anode, H2 gas releases two aqueous H+ ions and
two electrons. The voltage between the two is 0.34
volts.

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© McGraw-Hill Education. 18-78
Standard Reduction Potentials (E°) Long
Description
When half-reactions have positive E° values, such as
the reduction of chlorine gas with 2 electrons to
produce two aqueous chloride ions, they are very
strong oxidizing agents. When half-reactions have
negative E° values, such as the reduction of aqueous
cadmium(II) ions with 2 electrons to produce solid
cadmium, they are very strong reducing agents.

Jump to image
© McGraw-Hill Education. 18-79
Example 18.7 (1 of 4) Long Description
A Zn rod produces aqueous zinc ions and produces
two electrons. At the cathode, two electrons bind to
two aqueous protons to produce H2 gas. The voltage
between the two is 0.76 volts.

Jump to image
© McGraw-Hill Education. 18-80
 Batteries (1 of 5) Long Description
The zinc anode is in contact with a layer of MnO2
and an electrolyte composed of ZnCl2 and NH4Cl.
The electrolyte solution is mixed with starch to create
a moist paste, making it less likely that the solution
will leak from the battery. A graphite rod serves as
the cathode of the battery and is immersed in the
electrolyte in the center of the cell.

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© McGraw-Hill Education. 18-81
 Batteries (2 of 5) Long Description
The zinc exterior of the battery serves as the
cathode, and electrons are transferred through the
electrolyte solution, which contains KOH and a paste
of zinc hydroxide and mercury(II) oxide. The cathode
is in contact with the electrolyte solution.

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© McGraw-Hill Education. 18-82
 Batteries (3 of 5) Long Description
The cathode of the series is lead(IV) oxide packed
on a metal plate, and the anode is lead. Both the
positive plates filled with PbO2 and the negative
plates of Pb are immersed in a sulfuric acid
electrolyte solution.

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© McGraw-Hill Education. 18-83
 Batteries (4 of 5) Long Description
A nonaqueous organic solvent is used as the
electrolyte because the transition metal oxide is so
reactive.
Li-ion batteries are very light, due to the low molar
mass of Li. The batteries can also be depleted and
charged multiple times, so they're ideal for use in
portable electronic devices like tablets, laptops, and
cell phones.

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© McGraw-Hill Education. 18-84
 Batteries (5 of 5) Long Description
Oxygen gas is bubbled into a hot KOH solution at the
cathode, which is a porous carbon electrode with Ni
and NiO. Hydrogen gas is bubbled into the hot KOH
solution at the anode, which is a porous carbon
electrode containing Ni.

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© McGraw-Hill Education. 18-85
Chemistry In Action: Bacteria Power
Long Description
The electrons are transferred from the bacteria to the
anode where they are moved externally to the
cathode. At the cathode, O2 reacts with protons in
solution to form water. A fritted disk separates the
anode and cathode wells but allows ions to pass
through.

Jump to image
© McGraw-Hill Education. 18-86
 Corrosion Long Description
A region of the metal's surface serves as the anode, and
oxidation occurs to produce iron(II) ions from iron metal. The
electrons produced react with atmospheric oxygen to form
water in an acidic environment on a different portion of the
metal's surface which serves as the cathode. The acid is
predicted to form from the reaction of water and carbon dioxide
to form carbonic acid. The electrical circuit is facilitated by salt
ions, which is why rust on automobiles is a problem in northern
climates (where salt is used to deice roads).
The iron(II) ions at the anode are further oxidized by oxygen
and water to produce hydrated iron(III) oxide compounds.

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© McGraw-Hill Education. 18-87
Cathodic Protection of an Iron Storage
Tank Long Description
Magnesium oxidizes more readily than iron does, so
connecting an iron tank to a Mg rod will prevent iron
oxidation. In this way, Mg is considered a sacrificial
anode, because it is depleted in the electrochemical
reaction.

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© McGraw-Hill Education. 18-88
 Electrolysis Long Description
NaCl melts at 801°C, so iron cathodes and carbon
anodes are used. At the cathode, liquid sodium atoms are
formed. Liquid sodium is less dense than molten NaCl, so
the liquid Na rises to the top and can be transported out
of the cell. At the anode, chlorine gas is formed, which
can bubble up and be transported out of the cell.
Because the electrolysis of NaCl is nonspontaneous, a
battery is needed to drive the reaction. Electrons flow
from the anode, where Cl2 gas is produced from chloride
ions, through the battery to the cathode, which forms
liquid sodium atoms from sodium ions.

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© McGraw-Hill Education. 18-89
Electrolysis of Water Long Description
Two nonreactive metals serve as electrodes and are
submerged in a dilute H2SO4 solution. At the anode,
water is oxidized to produce O2 gas, protons, and
electrons. The electrons are then circuited through
the battery to the cathode, where the reduction of
protons causes formation of H2 gas.

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© McGraw-Hill Education. 18-90
Electrolysis of Water Long Description
In an electrolysis set up, the volume of H2 produced
is twice that of O2 because twice as much H2 gas is
generated.

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© McGraw-Hill Education. 18-91
Electrolysis and Mass Changes Long
Description
By measuring the current (in amperes) and time (in
seconds), the charge (in coulombs) can be
calculated.
By dividing the charge by the Faraday constant, the
number of moles of electrons can be calculated.
Using the mole ratio of the half-cell reaction, the
moles of substance oxidized or reduced can be
found. Using the molar mass or the ideal gas
equation, the grams or liters of product can be
calculated.

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© McGraw-Hill Education. 18-92
 Chemistry In Action: Dental Filling
Discomfort Long Description
In fact, the amalgam is often a mixture of three different
metal amalgams with tin and silver.
When an amalgam filling interacts with a gold filling on an
adjacent tooth, an electrochemical circuit is closed. The
amalgam serves as the anode, and electrons are
transferred through the saliva, serving as the electrolyte,
to the gold, which serves as the cathode.
According to the reduction potentials for the three
amalgams, Sn8Hg is most likely to corrode, and tin(II)
ions are released into the mouth, causing a metallic taste.

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© McGraw-Hill Education. 18-93
 End of Presentation

© McGraw-Hill Education. All rights reserved. Authorized only for instructor use in the classroom. No
reproduction or further distribution permitted without the prior written consent of McGraw-Hill Education. 18-94