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

Electrochemical reaction always involves oxidation-reduction

reactions
Electron transfer reactions
Electrons transferred from one substance to another
Also called redox reactions
0 0 2+ 2−
2Mg 𝑠 + O2 𝑔 → 2MgO 𝑆

2Mg → 2Mg 2+ + 4e− Oxidation half − reaction lose e−

O2 + 4e− → 2O2− Reduction half − reaction gain e−

© McGraw-Hill Education. 18-2

 Oxidation Number
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, H2, O2, P4 = 0

2. In monatomic ions, the oxidation number is equal to the

charge on the ion.

Li+ , Li = + 1; Fe3+ , Fe = + 3; O2− , O = −2

3. The oxidation number of oxygen is usually −2. In

H2 O2 and O2 2− it is − 1.

© McGraw-Hill Education. 18-3

 Oxidation Number

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

 Oxidation–Reduction Reactions

• Involves two processes:

– Oxidation – loss of electrons from one reactant
Na(s) ⎯→ Na+ + e – Oxidation Half Reaction
– Reduction – gain of electrons from another reactant
Cl2(g) + 2e – ⎯→ 2Cl– Reduction Half Reaction
• Net reaction
2Na(s) + Cl2(g) ⎯→ 2Na+ + 2Cl–
– Oxidation and reduction ALWAYS occur together
– Can't have one without the other
 Oxidation-Reduction Reaction

Oxidizing Agent
• Substance that accepts the electrons
– Takes electrons from another substance
–  is itself reduced
– Electron acceptor
– Cl2(g) + 2e – ⎯→ 2 Cl–
Reducing Agent
• Substance that donates electrons
– Releases electrons to another substance
–  is itself oxidized
– Electron donor
– Na(s) ⎯→ Na+ + e –
 Electron transfer reactions

Essential features:
• one reactant is oxidized
• one reactant is reduced
• the oxidizing agent is reduced
• the reducing agent is oxidized
• an element is oxidized if its ox # increases; it is reduced if its ox # decreases.
• the extent of oxidation and reduction must balance

All redox reactions must be balanced for

both mass and charge.
© McGraw-Hill Education. 18-7
 Balancing Redox Equations
The oxidation of Fe2+ to Fe3+ by Cr2 O7 2− in acid solution?

1. Write the unbalanced equation for the reaction in ionic form.

Fe2+ + Cr2 O7 2− → Fe3+ + Cr 3+

2. Separate the equation into two half-reactions.

+2 +3
Oxidation: →
Fe2+ Fe3+
+6 +3
Reduction: →
Cr2 O7 2− Cr 3+
3. Balance the atoms other than O and H in each half-reaction.
Oxidation: Fe2+ ⟶ Fe3+
Reduction: Cr2O72− ⟶ 2Cr3+
© McGraw-Hill Education. 18-8
 Balancing Redox Equations
4. For reactions in acid, add H2O to balance O atoms and H+ to balance H atoms.

Cr2 O7 2− → 2Cr 3+ + 7H2 O

14H + + Cr2 O7 2− → 2Cr 3+ + 7H2 O

5. Add electrons to one side of each half-reaction to balance the charges on the
half-reaction.
Fe
ถ2+ ⟶ Fe3+ + 𝑒 −

+2 +2

6𝑒 − + 14H + + Cr2 O2−

7 ⟶ 2Cr
3+ + 7H O
2
+6 +6

6. If necessary, equalize the number of electrons in the two half-reactions by

multiplying the half-reactions by appropriate coefficients.
6 Fe2+ → Fe3+ + 𝑒 −
6Fe2+ → 6Fe3+ + 6𝑒 −
6e− + 14H + + Cr2 O2−
7 → 2Cr
3+ + 7H O
2
© McGraw-Hill Education. 18-9
 Balancing Redox Equations
7. Add the two half-reactions together and balance the final equation by
inspection. The number of electrons on both sides must cancel.

Oxidation: 6Fe2+ → 6Fe3+ + 6eӍ −Ӎ

Reduction: 6eӍ −Ӎ + 14H + + Cr2 O7 2− → 2Cr 3+ + 7H2 O

14H + + Cr2 O7 2− + 6Fe2+ → 6Fe3+ + 2Cr 3+ + 7H2 O

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. combining the H+ and OH– ions
to produce H2O.

© McGraw-Hill Education. 18-10

 Example 18.1
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).
Solution
Step 1: The unbalanced equation is
MnO− −
4 + I → MnO2 + I2

Step 2: The two half-reactions are

−1 0
Oxidation: I− → I2

+7 +4
Reduction: MnO−
4 → MnO2

© McGraw-Hill Education. 18-11

 Example 18.1
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 − → I2

To balance charges, we add two electrons to the right-hand side of the

equation:

2I − → I2 + 2e−

Reduction half-reaction: To balance the O atoms, we add two H2O molecules

on the right:

MnO−
4 → MnO2 + 2H2 O

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

MnO− +
4 + 4H → MnO2 + 2H2 O

© McGraw-Hill Education. 18-12

 Example 18.1
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 → MnO2 + 2H2 O

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. 18-13

 Example 18.1
The electrons on both sides cancel, and we are left with the balanced net
ionic equation:

6I − + 2MnO−
4 + 8H
+
→ 3I2 + 2MnO2 + 4H2 O

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 − + 2MnO− + −
4 + 8H + 8OH → 3I2 + 2MnO2 + 4H2 O + 8OH
−

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

6I − + 2MnO−
4 + 4H2 O → 3I2 + 2MnO2 + 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
Electrochemical cell in which spontaneous redox reactions occur
Produce electricity spontaneously
Energy released can be used to perform electrical work
Transfer of electrons takes place through an external pathway (wire) rather than
directly between reactants
The zinc and copper bars are called electrodes.

As the electrons leave the anode, the The electrons are taken by the cation,
cations formed dissolve into the and the neutral metal is deposited on the
solution in the anode compartment. cathode.

© McGraw-Hill Education. 18-15

 Galvanic Cells
The anode in a galvanic cell is the
electrode at which oxidation occurs

The cathode is the electrode at which

reduction occurs.
Each combination of container, electrode,
and solution is called a half-cell.

the half-cell reactions, that is, the oxidation and reduction reactions at the
electrodes, are

Zn electrode (anode): Zn(s) → Zn2+(aq) + 2e−

Cu electrode (cathode): Cu2+(aq) + 2e− → Cu(s)

© McGraw-Hill Education. 18-16

 Galvanic Cells

To complete the electric circuit, and allow electrons to flow through the external
wire, the solutions must be connected by a conducting medium through which
the cations and anions can move from one half-cell to the other.

This requirement is satisfied by a salt bridge .

salt bridge contains a strong electrolyte dissolved in a gel like KCl or NH4NO3

© McGraw-Hill Education. 18-17

 Galvanic Cells
Experimentally the difference in electrical
potential between the anode and the
cathode is measured by a voltmeter and the
reading (in volts) (The voltage across the
electrodes of a galvanic cell) is called:
• cell voltage
• electromotive force (emf)
• cell potential (Ecell).
Zn 𝑠 + Cu2+ 𝑎𝑞 → Cu 𝑠 + Zn2+ 𝑎𝑞
Cu2+ = 1 M and Zn2+ = 1 M

Cell Diagram

anode Salt Bridge cathode

Cu(s)|Cu2+(aq)||Ag+(aq)|Ag(s)
anode oxidation reduction cathode
electrode electrolyte(s) electrolyte(s) electrode
© McGraw-Hill Education. 18-18
 Standard Reduction Potentials
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 and at 298K.

Reduction Reaction

2e− + 2H + 1M → H2 1 atm 𝐸° = 0V

Standard hydrogen electrode (SHE)

© McGraw-Hill Education. 18-19

 Standard Reduction Potentials
∘
𝐸cell = 0.76V

Zn 𝑠 |Zn2+ 1 M ||H + 1 M |H2 1 atm |Pt 𝑠

Anode oxidation : Zn 𝑠 → Zn2+ 1 M + 2e−

Cathode reduction : 2e− + 2H + 1 M → H2 1 atm

Zn 𝑠 + 2H + 1 M → Zn2+ 1 M + H2 1 atm

Zn 𝑠 |Zn2+ 1M ||H + 1M |H2 1atm |Pt 𝑠

∘
𝐸cell = 𝐸H∘ + /H2 − 𝐸Zn
∘
2+ /Zn Standard emf 𝑬∘𝒄𝒆𝒍𝒍
∘
0.76V = 0 − 𝐸Zn2+ /Zn 𝑬∘cell = 𝑬∘cathode − 𝑬∘anode
∘
𝐸Zn 2+ /Zn = −0 ⋅ 76V

Zn2+ 1M + 2e− → Zn 𝐸° = −0.76V

© McGraw-Hill Education. 18-20

 Standard Reduction Potentials
∘
𝐸cell = 0.34V

Pt 𝑠 |H2 1atm |H + 1 M ||Cu2+ 1M |Cu 𝑠

Anode oxidation : H2 1atm → 2H + 1 M + 2e−
Cathode reduction : 2e− + Cu2+ 1 M → Cu 𝑠

H2 1atm + Cu2+ 1M → Cu 𝑠 + 2H + 1 M

∘ ∘ ∘
𝐸cell = 𝐸cathode − 𝐸anode
∘ ∘ ∘
𝐸cell = 𝐸Cu2+ /Cu − 𝐸H+ /H
2

∘
0.34 = 𝐸Cu2+ /Cu − 0

∘
𝐸Cu2+ /Cu = 0.34V

© McGraw-Hill Education. 18-21

 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 (act as an oxidizing agent such
as F2)
• The more negative E°,the greater the
tendency for the substance to be oxidize
(act as reducing agent such as Li)
• The half-cell reactions are reversible
Depending on the conditions, any
electrode can act either as an anode or
as a cathode.
• Changing the stoichiometric coefficients
of a half-cell reaction does not change
the value of E°
© McGraw-Hill Education. 18-22
Cathode

Anode
© McGraw-Hill Education. 18-23
 Standard Reduction Potentials (E°)

Under standard-state conditions, any species on

the left of a given half-cell reaction will react
spontaneously with a species that appears on the
right of any half-cell reaction located below it
in Table This principle is sometimes called
the diagonal rule.

© McGraw-Hill Education. 18-24

 Using E °cell to Predict Spontaneous
Reactions
• Given any redox reaction
• Calculate E °cell for reaction as written
• If E °cell > 0 V (positive), then reaction is spontaneous
– If E °cell < 0 V (negative), then reaction is
nonspontaneous. Another view is that it is spontaneous
in the reverse direction.
• Galvanic cell is always spontaneous
• Because it is always set up so E °cell is positive
 Predicting Reaction Spontaneity
Ex. What spontaneous reaction occurs when Cr and
Au are added to a solution of Au3+ and Cr3+?
– Cr3+(aq) + 3e – → Cr(s) E ° = –0.74 V
– Au3+(aq) + 3e – → Au(s) E ° = +1.50 V

• Au is more positive so it will be the reduction half

reaction
• Cr is least positive so it will be the oxidation half
reaction (it will be reversed below)
Au3+(aq) + 3e – → Au(s)
Cr(s) → Cr3+(aq) + 3e –
Au3+(aq) + Cr(s) → Au(s) + Cr3+(aq)
 Is this Answer Reasonable?
• Use reduction potentials to predict E °cell for the reaction.
– Cr3+(aq) + 3e – → Cr(s) E ° = –0.74 V
– Au3+(aq) + 3e – → Au(s) E ° = +1.50 V
Net Reaction = Au3+(aq) + Cr(s) → Au(s) + Cr3+(aq)
• E °cell = E °reduced – E °oxidized
• E °cell = E °Au3+ – E °Cr3+
• E °cell = +1.50 V – (–0.74 V)
• E °cell = +2.24 V (positive V means a spontaneous
reaction)
 Example 18.2
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.

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

I2 𝑠 + 2𝑒 − → 2I − 1 M 𝐸° = 0.53 V

© McGraw-Hill Education. 18-28

 Example 18.2

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 → I2 𝑠 + 2𝑒 −
Reduction: Br2 𝑙 + 2𝑒 − → 2Br − 1 M

Overall: 2I − 1M + Br2 𝑙 → I2 𝑠 + 2Br − 1 M

© McGraw-Hill Education. 18-29

 Example 18.3
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.
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

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. 18-30

 Example 18.3
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 − 𝐸Mg2+ /Mg

= 0.80V − −2.37V
= 3.17V

The positive value of E° shows that the forward reaction is favored.

© McGraw-Hill Education. 18-31

 Spontaneity of Redox Reactions
𝟏 𝑭 = 𝟗𝟔, 𝟓𝟎𝟎𝐂/𝐦𝐨𝐥 𝒆− → 𝟏𝐉 =𝟏𝐂×𝟏𝐕 → 𝟏 𝑭 = 𝟗𝟔, 𝟓𝟎𝟎 𝑱Τ𝐕 ∙ 𝐦𝐨𝐥 𝒆−

𝑤max = 𝑤electrical

= −𝑛𝐹𝐸cell total charge = 𝑛𝐹

∆𝐺 = 𝑤max
𝜟𝐆 = −𝒏𝑭𝑬cell 𝒏 = number of moles of electrons in reaction

𝜟𝑮𝟎 = −𝒏𝑭𝑬𝟎cell

0
Δ𝐺 0 = −𝑅𝑇 ln 𝐾 = −𝑛𝐹𝐸cell

0 𝑅𝑇 8.314 J/K. mol 298KӍ

𝐸cell = ln 𝐾 = ln 𝐾
𝑛𝐹 n 96,500 J/V. mol

0 0.0257V
𝐸cell = ln 𝐾
n

0 0.0592V
𝐸cell = log 𝐾
n
© McGraw-Hill Education. 18-32
 Spontaneity of Redox Reactions
DG°

Reaction Parameters at the Standard State

Reaction at standard-state
DG° K E°cell conditions
<0 >1 >0 Spontaneous (Favors
formation of products)
0 1 0 at equilibrium (Reactants
and products are equally
favored)
>0 <1 <0 Nonspontaneous (Favors
formation of reactants) E°cell K

RT ln K
E°cell =
nF

© McGraw-Hill Education. 18-33

 Example 18.4
Calculate the equilibrium constant for the following reaction at 25°C:

Sn 𝑠 + 2Cu2+ 𝑎𝑞 ↔ Sn2+ 𝑎𝑞 + 2Cu+ 𝑎𝑞

Solution

The half-cell reactions are

Anode oxidation : Sn 𝑠 → Sn2+ 𝑎𝑞 + 2𝑒 −

Cathode reduction : 2Cu2+ 𝑎𝑞 + 2𝑒 − → 2Cu+ 𝑎𝑞

𝐸 ∘cell = 𝐸 ∘cathode − 𝐸 ∘anode

∘ ∘
= 𝐸Cu2+ /Cu+ − 𝐸Sn2+ /Sn

= 0.15V − −0.14V
= 0.29V

© McGraw-Hill Education. 18-34

 Example 18.4
∘
𝐸cell = 0.0257 V/n ln 𝐾

𝑛𝐸°
ln 𝐾 =
0.0257 V

In the overall reaction we find n = 2 Therefore,

2 0.29V
ln𝐾 = = 22.6
0.0257V

𝐾 = 𝑒 22.6 = 7 × 109

© McGraw-Hill Education. 18-35

 Example 18.5
Calculate the standard free-energy change for the following reaction
at 25°C:
2Au 𝑠 + 3Ca2+ 1.0M → 2Au3+ 1.0M + 3Ca 𝑠
Solution
The half-cell reactions are

Anode oxidation : 2Au 𝑠 → 2Au3+ 1.0M + 6𝑒 −

Cathode Reduction : 3Ca2+ 1.0M + 6𝑒 − → 3Ca 𝑠

∘ ∘ ∘
𝐸cell = 𝐸cathode − 𝐸anode
∘ ∘
= 𝐸Ca2+ /Ca − 𝐸Au3+ /Au

= −2.87V − 1.50V
= −4.37V

© McGraw-Hill Education. 18-36

 Example 18.5
Δ𝐺° = −𝑛𝐹𝐸°

The overall reaction shows that n = 6, so

Δ𝐺° = − 6 96,500 J/V ⋅ mol −4.37V

= 2.53 × 106 J/mol
= 2.53 × 103 kJ/mol

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. 18-37

The Effect of Concentration on Cell Emf
𝑎A + 𝑏B ⟶ 𝑐C + 𝑑D

∆𝐺 = ∆𝐺 ° + 𝑅𝑇 ln 𝑄

∆𝐺 = −𝑛𝐹𝐸 and ∆𝐺 ° = −𝑛𝐹𝐸 °

−𝑛𝐹𝐸 = −𝑛𝐹𝐸 ° + 𝑅𝑇 ln 𝑄

𝑹𝑻
𝑬 = 𝑬° − 𝒍𝒏 𝑸 Nernst equation
𝒏𝑭
The term E °cell is used
At 298 K when the system is at
0.0257 V standard state and Ecell is
𝐸 = 𝐸° − ln 𝑄 used when the system is not
𝑛
at standard state
0.0592 V
𝐸= 𝐸° − log 𝑄
𝑛
© McGraw-Hill Education. 18-38
The Effect of Concentration on Cell Emf
𝑹𝑻
𝑬 = 𝑬° − 𝒍𝒏 𝑸 Nernst equation
𝒏𝑭

© McGraw-Hill Education. 18-39

 Example 18.6
Predict whether the following reaction would proceed spontaneously as
written at 298 K:
Co 𝑠 + Fe2+ 𝑎𝑞 → Co2+ 𝑎𝑞 + Fe 𝑠

given that Co2+ = 0.15M and Fe2+ = 0.68M.

Solution
The half-cell reactions are

Anode oxidation : Co 𝑠 → Co2+ 𝑎𝑞 + 2𝑒 −

Cathode reduction : Fe2+ 𝑎𝑞 + 2𝑒 − → Fe 𝑠

∘
𝐸cell = 𝐸 ∘cathode − 𝐸 ∘anode
∘ ∘
= 𝐸Fe 2+ /Fe − 𝐸Co2+ /Co

= −0.44V − −0.28V
= −0.16V
© McGraw-Hill Education. 18-40
 Example 18.6

0.0257V
𝐸 = 𝐸° − ln 𝑄
𝑛

0.0257V Co2+
= 𝐸° − ln
𝑛 Fe2+

0.0257V 0.15
= −0.16V − 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. 18-41
 Example 18.7
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 Zn2+ = 1.0M and PH2 = 1.0atm ⋅
Calculate the molar concentration of H+.

Zn 𝑠 + 2H + ? M → Zn2+ 1.0M + H2 1.0atm

© McGraw-Hill Education. 18-42

 Example 18.7
Solution
As we saw earlier, the standard emf (E°) for the cell is 0.76 V. From Equation
(18.8) we write
0.0257V
𝐸 = 𝐸° − ln 𝑄
𝑛
0.0257V Zn2+ PH2
= 𝐸° − ln
𝑛 H+ 2
0.0257V 1.0 1.0
0.54V = 0.76V − ln
2 H+ 2
0.0257V 1
− 0.22V = − ln + 2
2 H
1
17.1 = ln
H+ 2

1
𝑒17.1 =
H+ 2

1
H+ = 7
= 2 × 10−4 M
3 × 10
© McGraw-Hill Education. 18-43
 Electrolysis
Electrolysis is the process in which electrical energy is used to cause a
nonspontaneous chemical reaction to occur.
An electrolytic cell is one used to carry out electrolysis.
Electrolysis of molten NaCl

Anode (oxidation): 2Cl− 𝑙 ⟶ Cl2 𝑔 + 2𝑒 −

Cathode (reduction): 2Na+ 𝑙 + 2𝑒 − ⟶ 2Na 𝑙
Overall: 2Na+ 𝑙 + 2Cl− 𝑙 ⟶ 2Na 𝑙 + Cl2 𝑔
© McGraw-Hill Education. 18-44
 Electrolysis of Water

2H2 O 𝑙 ⟶ 2H2 𝑔 + O2 𝑔 ∆𝐺 ° = 474.4 kJΤmol

Anode: 2H2 O 𝑙 ⟶ O2 𝑔 + 4H + 𝑎𝑞 + 4𝑒 −
Cathode: 4H + 𝑎𝑞 + 4𝑒 − ⟶ 2H2 𝑔

Overall: 2H2 O 𝑙 ⟶ O2 𝑔 + 2H2 𝑔

© McGraw-Hill Education. 18-45
 Example 18.8
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. 18-46

 Example 18.8
Solution
The electrode reactions are

Anode: 2H2 O l → O2 g + 4H + aq + 4e−

Cathode: 2H2 O l + 2e− → H2 g + 2OH − aq

The overall reaction, obtained by doubling the cathode reaction

coefficients and adding the result to the anode reaction, is
6H2 O l → 2H2 g + O2 g + 4H + aq + 4OH − aq

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

4H + aq + 4OH − aq → 4H2 O l

and the overall reaction becomes

2H2 O l → 2H2 g + O2 g

© McGraw-Hill Education. 18-47

 Electrolysis and Mass Changes
If we know the current and how long it is applied, we can
calculate the charge. Knowing the charge enables us to
determine the number of moles of electrons. And knowing
the number of moles of electrons allows us to use
stoichiometry to determine the number of moles of product.

charge (C) = current (A) × time (s)

1 mol e− = 96500 C

𝑪 𝑨𝒕
𝒎𝒐𝒍𝒆𝒔 = =
𝒏𝑭 𝒏 𝑭
n = moles of electrons transferred in process
© McGraw-Hill Education. 18-48
 Example 18.9
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.

Anode oxidation : 2H2 O 𝑙 → O2 𝑔 + 4H + 𝑎𝑞 + 4𝑒 −

1
Cathode reduction : 4 H + 𝑎𝑞 + 𝑒 − → H2 𝑔
2
Overall: 2H2 O 𝑙 → 2H2 𝑔 + O2 𝑔

current × time → coulombs → moles of 𝑒 − → moles of O2

© McGraw-Hill Education. 18-49

 Example 18.9
Solution
First we calculate the number of coulombs of electricity that pass
through the cell:
3600s Ӎ 1C
? C = 1.26AӍ × 7.44hӍ × × = 3.37 × 104
C
1h Ӎ 1AӍ ⋅ s Ӎ

Next, we convert number of coulombs to number of moles of electrons

1mol 𝑒 −
3.37 × 104 CӍ × = 0.349mol 𝑒 −
96,500CӍ

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 O2
0.349 mol 𝑒 − × = 0.0873 mol O2
4 mol𝑒 −

© McGraw-Hill Education. 18-50

 Example 18.9
The volume of 0.0873 mol O2 at STP is given by

𝑛𝑅𝑇 0.0873mol 0.0821L. atm/K ⋅ mol 273K

𝑉 = = = 1 ⋅ 96 L
𝑃 1atm

The procedure for hydrogen is similar. To simplify, we combine the

first two steps to calculate the number of moles of H2 generated:

1mol 𝑒 −Ӎ 1molH2
3.37 × 104 CӍ × × = 0.175molH2
96,500CӍ 2mol𝑒 −Ӎ

The volume of 0.175 mol H2 at STP is given by

𝑛𝑅𝑇 0.175mol 0.00821 L. atm/K ⋅ mol 273K

𝑉 = = = 3.92 L twice that of O2
𝑃 1 atm

© McGraw-Hill Education. 18-51

 Calculations Related to Electrolysis

Faradays
(mole e–)
1 mol reactant
F n mol e -

Mol reactant
Charge (C) (or product)

MM
As=C
Mass (g) reactant
Current (or product)
and time
Calculations Related to Electrolysis

Faradays
1 mol reactant (mole e–)
n mol e - F

Mol reactant
(or product) Charge (C)

MM
As=C

Mass (g) reactant Current

(or product) and time
What mass of copper can be deposited by the passage of 12.0 A for
25.0 min through a solution of copper(II) sulfate? [1 C = 1 A·s; F =
96,500 C]
A) 5.93 g
B) 3.95 g
C) 1.97 g
D) 11.85 g
E) 29.6 g

A galvanic cell is prepared using zinc and iron. Its cell notation is as follows:
Zn|Zn2+(1 M)||Fe2+(1 M), Fe3+(1M)|Pt. Which of the following reactions occurs at
the cathode?
A) Fe3+ + e- ----> Fe2+
B) Fe2+ ----> Fe3+ + e-
C) Zn ----> Zn2+ + 2 e-
D) Zn2+ + 2e- ----> Zn

© McGraw-Hill Education. 18-54

The equilibrium constant for the reaction of Ni2+ with Cd is 1.17 x 105. Calculate
the free energy change for the reaction at 25oC.
A) -12.6 kJ
B) -28.9 kJ
C) 2.43 kJ
D) 28.9 kJ
E) 12.6 kJ

Calculate the equilibrium constant for the reaction:

2 Cr + 3 Pb2+ ----> 3 Pb + 2 Cr3+ at 25oC. Eocell = 0.61 V.
A) 4 x 1020
B) 8 x 1030
C) 9 x 1045
D) 3 x 1051
E) 8 x 1061

© McGraw-Hill Education. 18-55

Examine the following half-reactions and select the strongest oxidizing agent
among the substances:
Sr2+ + 2 e- ----> Sr, Eo = -2.89 V;
Cr2+ + 2 e- ----> Cr, Eo = -0.913 V;
Fe2+ + 2 e- ----> Fe, Eo = -0.447 V;
Co2+ + 2 e- ----> Co, Eo = -0.28 V.
A) Cr2+
B) Sr2+
C) Co2+
D) Fe2+

A cell can be prepared from zinc and iron. What is the Eocell for the cell that
forms from the following half reactions? Fe3+ + e- ----> Fe2+, Eo = 0.77 V;
Zn2+ + 2e- ----> Zn, Eo = -0.76 V
A) -1.53 V
B) -0.01 V
C) 0.78 V
D) 0.01 V
E) 1.53 V

© McGraw-Hill Education. 18-56

Calculate standard Gibbs' free energy change and equilibrium constant
Zn(s)+Pb2+↔Pb(s)+Zn2+(aq)
Zn2+↔ Zn(s) E∘= -0.76V
Pb2+↔ Pb(s) E∘= -0.13V

© McGraw-Hill Education. 18-57

A current of 5.00 A is passed through an aqueous solution of chromium (III) nitrate
for 30.0 min. How many grams of chromium metal will be deposited at the cathode?

© McGraw-Hill Education. 18-58

Calculate the current that pass through an aqueous solution of chromium (III)
nitrate for 75.0 min if 1.80 g of chromium metal deposited at the cathode?

© McGraw-Hill Education. 18-59

A current of 12.00 A is passed through an aqueous solution of chromium (III)
nitrate min if 1.65 g of chromium metal deposited at the cathode. How long will it
take for the deposition?

© McGraw-Hill Education. 18-60

Balance the following equations in basic solution.
(a) Fe(OH)2(s) + O2(g) → Fe(OH)3(s)

© McGraw-Hill Education. 18-61

Balance the following equations in acidic solution.
Cl2(g) + I–(aq) → Cl–(aq) + IO3–(aq)

© McGraw-Hill Education. 18-62

What is the value of Ecell of each of the following reactions when carried out
in a voltaic cell?
Fe(s) + 2 Ag+(aq, 0.0015 M) → Fe2+(aq, 1.33 M) + 2 Ag(s)

Fe2+(aq) + 2 e–→ Fe(s) E° = -0.440 V

Ag+(aq) + e– → Ag(s) E° = +0.800 V

© McGraw-Hill Education. 18-63