AP*

Chapter 18

Electrochemistry
AP Learning Objectives

 LO 3.2 The student can translate an observed chemical change into a balanced
chemical equation and justify the choice of equation type (molecular, ionic, or
net ionic) in terms of utility for the given circumstances. (Sec 18.1)
 LO 3.8 The student is able to identify redox reactions and justify the
identification in terms of electron transfer. (Sec 18.1)
 LO 3.12 The student can make qualitative or quantitative predictions about
galvanic or electrolytic reactions based on half-cell reactions and potentials
and/or Faraday’s laws. (Sec 18.3-18.5, 18.8)
 LO 3.13 The student can analyze data regarding galvanic or electrolytic cells to
identify properties of the underlying redox reactions. (Sec 18.3-18.5, 18.8)
 LO 5.15 The student is able to explain how the application of external energy
sources or the coupling of favorable with unfavorable reactions can be used to
cause processes that are not thermodynamically favorable to become favorable.
(Sec 18.8)
AP Learning Objectives

 LO 6.1 The student is able to, given a set of experimental observations regarding
physical, chemical, biological, or environmental processes that are reversible,
construct an explanation that connects the observations to the reversibility of
the underlying chemical reactions or processes. (Sec 18.3-18.5, 18.7)
Section 18.1
Balancing Oxidation-Reduction Equations

AP Learning Objectives, Margin Notes and References

 Learning Objectives
 LO 3.2 The student can translate an observed chemical change into a balanced chemical equation and justify the
choice of equation type (molecular, ionic, or net ionic) in terms of utility for the given circumstances.
 LO 3.8 The student is able to identify redox reactions and justify the identification in terms of electron transfer.
Section 18.1
Balancing Oxidation-Reduction Equations

Review of Terms
 Electrochemistry – the study of the interchange of chemical
and electrical energy
 Oxidation–reduction (redox) reaction – involves a transfer of
electrons from the reducing agent to the oxidizing agent
 Oxidation – loss of electrons
 Reduction – gain of electrons
 Reducing agent – electron donor
 Oxidizing agent – electron acceptor

Copyright © Cengage Learning. All rights reserved 5

Section 18.1
Balancing Oxidation-Reduction Equations

Half–Reactions
 The overall reaction is split into two half–reactions, one
involving oxidation and one involving reduction.
8H+ + MnO4– + 5Fe2+ Mn2+ + 5Fe3+ + 4H2O

Reduction: 8H+ + MnO4– + 5e– Mn2+ + 4H2O

Oxidation: 5Fe2+ 5Fe3+ + 5e–

Copyright © Cengage Learning. All rights reserved 6

Section 18.1
Balancing Oxidation-Reduction Equations
The Half–Reaction Method for Balancing Equations for Oxidation–
Reduction Reactions Occurring in Acidic Solution

1. Write separate equations for the oxidation and reduction

half–reactions.
2. For each half–reaction:
A. Balance all the elements except H and O.
B. Balance O using H2O.
C. Balance H using H+.
D. Balance the charge using electrons.

Copyright © Cengage Learning. All rights reserved 7

Section 18.1
Balancing Oxidation-Reduction Equations
The Half–Reaction Method for Balancing Equations for Oxidation–
Reduction Reactions Occurring in Acidic Solution

3. If necessary, multiply one or both balanced half–

reactions by an integer to equalize the number
of electrons transferred in the two half–
reactions.
4. Add the half–reactions, and cancel identical
species.
5. Check that the elements and charges are
balanced.

Copyright © Cengage Learning. All rights reserved 8

Section 18.1
Balancing Oxidation-Reduction Equations
The Half–Reaction Method for Balancing Equations for Oxidation–
Reduction Reactions Occurring in Acidic Solution

Copyright © Cengage Learning. All rights reserved 9

Section 18.1
Balancing Oxidation-Reduction Equations

Cr2O72-(aq) + SO32-(aq) Cr3+(aq) + SO42-(aq)

 How can we balance this equation?

 First Steps:
 Separate into half-reactions.
 Balance elements except H and O.

Copyright © Cengage Learning. All rights reserved 10

Section 18.1
Balancing Oxidation-Reduction Equations

Method of Half Reactions

 Cr2O72-(aq) 2Cr3+(aq)  
 SO32-(aq) SO42-(aq)
 How many electrons are involved in each half
reaction?

Copyright © Cengage Learning. All rights reserved 11

Section 18.1
Balancing Oxidation-Reduction Equations

Method of Half Reactions (continued)

 6e- + Cr2O72-(aq) 2Cr3+(aq) 
 SO32-(aq) + SO42-(aq) + 2e-
 How can we balance the oxygen atoms?

Copyright © Cengage Learning. All rights reserved 12

Section 18.1
Balancing Oxidation-Reduction Equations

Method of Half Reactions (continued)

 6e- + Cr2O72-(aq) Cr3+(aq) + 7H2O 
 H2O +SO32-(aq) + SO42-(aq) + 2e-
 How can we balance the hydrogen atoms?

Copyright © Cengage Learning. All rights reserved 13

Section 18.1
Balancing Oxidation-Reduction Equations

Method of Half Reactions (continued)

 This reaction occurs in an acidic solution.
 14H+ + 6e- + Cr2O72- 2Cr3+ + 7H2O 
 H2O +SO32- SO42- + 2e- + 2H+
 How can we balance the electrons?

Copyright © Cengage Learning. All rights reserved 14

Section 18.1
Balancing Oxidation-Reduction Equations

Method of Half Reactions (continued)

 14H+ + 6e- + Cr2O72- 2Cr3+ + 7H2O
 3[H2O +SO32- SO42- + 2e- + 2H+]

 Final Balanced Equation:

Cr2O72- + 3SO32- + 8H+ 2Cr3+ + 3SO42- + 4H2O

Copyright © Cengage Learning. All rights reserved 15

Section 18.1
Balancing Oxidation-Reduction Equations

EXERCISE!

Balance the following oxidation–reduction reaction

that occurs in acidic solution.

Br–(aq) + MnO4–(aq) Br2(l)+ Mn2+(aq)

10Br–(aq) + 16H+(aq) + 2MnO4–(aq) 5Br2(l)+ 2Mn2+(aq) + 8H2O(l)

Copyright © Cengage Learning. All rights reserved 16

Section 18.1
Balancing Oxidation-Reduction Equations
The Half–Reaction Method for Balancing Equations for Oxidation–
Reduction Reactions Occurring in Basic Solution
1. Use the half–reaction method as specified for
acidic solutions to obtain the final balanced
equation as if H+ ions were present.
2. To both sides of the equation obtained above,
add a number of OH– ions that is equal to the
number of H+ ions. (We want to eliminate H+
by forming H2O.)

Copyright © Cengage Learning. All rights reserved 17

Section 18.1
Balancing Oxidation-Reduction Equations
The Half–Reaction Method for Balancing Equations for Oxidation–
Reduction Reactions Occurring in Basic Solution
3. Form H2O on the side containing both H+ and
OH– ions, and eliminate the number of H2O
molecules that appear on both sides of the
equation.
4. Check that elements and charges are balanced.

Copyright © Cengage Learning. All rights reserved 18

Section 18.1
Balancing Oxidation-Reduction Equations

The Half–Reaction
Method for Balancing
Equations for Oxidation–
Reduction Reactions
Occurring in Basic
Solution

Copyright © Cengage Learning. All rights reserved 19

Section 18.2
Galvanic Cells

Galvanic Cell
 Device in which chemical energy is changed to electrical
energy.
 Uses a spontaneous redox reaction to produce a current
that can be used to do work.

Copyright © Cengage Learning. All rights reserved 20

Section 18.2
Galvanic Cells

A Galvanic Cell

Copyright © Cengage Learning. All rights reserved 21

Section 18.2
Galvanic Cells

Galvanic Cell
 Oxidation occurs at the anode.
 Reduction occurs at the cathode.
 Salt bridge or porous disk – devices that allow ions to
flow without extensive mixing of the solutions.
 Salt bridge – contains a strong electrolyte held in a
Jello–like matrix.
 Porous disk – contains tiny passages that allow
hindered flow of ions.

Copyright © Cengage Learning. All rights reserved 22

Section 18.2
Galvanic Cells

Cell Potential
 A galvanic cell consists of an oxidizing agent in one
compartment that pulls electrons through a wire from a
reducing agent in the other compartment.
 The “pull”, or driving force, on the electrons is called the
cell potential (Ecell ), or the electromotive force (emf) of
the cell.
 Unit of electrical potential is the volt (V).
 1 joule of work per coulomb of charge transferred.

Copyright © Cengage Learning. All rights reserved 23

Section 18.2
Galvanic Cells

Voltaic Cell: Cathode Reaction

To play movie you must be in Slide Show Mode

PC Users: Please wait for content to load, then click to play
Mac Users: CLICK HERE
Copyright © Cengage Learning. All rights reserved 24
Section 18.2
Galvanic Cells

Voltaic Cell: Anode Reaction

To play movie you must be in Slide Show Mode

PC Users: Please wait for content to load, then click to play
Mac Users: CLICK HERE
Copyright © Cengage Learning. All rights reserved 25
Section 18.3
Standard Reduction Potentials

AP Learning Objectives, Margin Notes and References

 Learning Objectives
 LO 3.12 The student can make qualitative or quantitative predictions about galvanic or electrolytic reactions based
on half-cell reactions and potentials and/or Faraday’s laws.
 LO 3.13 The student can analyze data regarding galvanic or electrolytic cells to identify properties of the underlying
redox reactions.
 LO 6.1 The student is able to, given a set of experimental observations regarding physical, chemical, biological, or
environmental processes that are reversible, construct an explanation that connects the observations to the
reversibility of the underlying chemical reactions or processes.
Section 18.3
Standard Reduction Potentials

Galvanic Cell
 All half-reactions are given as reduction processes in standard
tables.
 Table 18.1
 1 M, 1atm, 25°C
 When a half-reaction is reversed, the sign of E° is reversed.
 When a half-reaction is multiplied by an integer, E° remains the
same.
 A galvanic cell runs spontaneously in the direction that gives a
positive value for E°cell.

Copyright © Cengage Learning. All rights reserved 27

Section 18.3
Standard Reduction Potentials

Example: Fe3+(aq) + Cu(s) → Cu2+(aq) + Fe2+(aq)

 Half-Reactions:
 Fe3+ + e– → Fe2+ E° = 0.77 V
 Cu2+ + 2e– → Cu E° = 0.34 V
 To balance the cell reaction and calculate the cell potential, we
must reverse reaction 2.
 Cu → Cu2+ + 2e– – E° = – 0.34 V
 Each Cu atom produces two electrons but each Fe3+ ion accepts
only one electron, therefore reaction 1 must be multiplied by 2.
 2Fe3+ + 2e– → 2Fe2+ E° = 0.77 V

Copyright © Cengage Learning. All rights reserved 28

Section 18.3
Standard Reduction Potentials

Overall Balanced Cell Reaction

2Fe3+ + 2e– → 2Fe2+ E° = 0.77 V (cathode)
Cu → Cu2+ + 2e– – E° = – 0.34 V (anode)
 Balanced Cell Reaction:
Cu + 2Fe3+ → Cu2+ + 2Fe2+
 Cell Potential:
E°cell = E°(cathode) – E°(anode)
E°cell = 0.77 V – 0.34 V = 0.43 V

Copyright © Cengage Learning. All rights reserved 29

Section 18.3
Standard Reduction Potentials

CONCEPT CHECK!

Order the following from strongest to weakest oxidizing

agent and justify. Of those you cannot order, explain
why.

Fe Na F- Na+ Cl2
Section 18.3
Standard Reduction Potentials

Line Notation
 Used to describe electrochemical cells.
 Anode components are listed on the left.
 Cathode components are listed on the right.
 Separated by double vertical lines which indicated salt bridge
or porous disk.
 The concentration of aqueous solutions should be specified in
the notation when known.
 Example: Mg(s)|Mg2+(aq)||Al3+(aq)|Al(s)
 Mg → Mg2+ + 2e– (anode)
 Al3+ + 3e– → Al (cathode)
Copyright © Cengage Learning. All rights reserved 31
Section 18.3
Standard Reduction Potentials

Description of a Galvanic Cell

 The cell potential (always positive for a galvanic cell
where E°cell = E°(cathode) – E°(anode)) and the balanced
cell reaction.
 The direction of electron flow, obtained by inspecting
the half–reactions and using the direction that gives a
positive E°cell.

Copyright © Cengage Learning. All rights reserved 32

Section 18.3
Standard Reduction Potentials

Description of a Galvanic Cell

 Designation of the anode and cathode.
 The nature of each electrode and the ions present in
each compartment. A chemically inert conductor is
required if none of the substances participating in the
half–reaction is a conducting solid.

Copyright © Cengage Learning. All rights reserved 33

Section 18.3
Standard Reduction Potentials

CONCEPT CHECK!

Sketch a cell using the following solutions and electrodes.

Include:
 The potential of the cell
 The direction of electron flow
 Labels on the anode and the cathode

a) Ag electrode in 1.0 M Ag+(aq) and Cu electrode in 1.0

M Cu2+(aq)

Copyright © Cengage Learning. All rights reserved 34

Section 18.3
Standard Reduction Potentials

CONCEPT CHECK!

Sketch a cell using the following solutions and electrodes.

Include:
 The potential of the cell
 The direction of electron flow
 Labels on the anode and the cathode

b) Zn electrode in 1.0 M Zn2+(aq) and Cu electrode in 1.0

M Cu2+(aq)

Copyright © Cengage Learning. All rights reserved 35

Section 18.3
Standard Reduction Potentials

CONCEPT CHECK!

Consider the cell from part b.

What would happen to the potential if you increase the

[Cu2+]?

Explain.

The cell potential should increase.

Copyright © Cengage Learning. All rights reserved 36

Section 18.4
Cell Potential, Electrical Work, and Free Energy

AP Learning Objectives, Margin Notes and References

 Learning Objectives
 LO 3.12 The student can make qualitative or quantitative predictions about galvanic or electrolytic reactions based
on half-cell reactions and potentials and/or Faraday’s laws.
 LO 3.13 The student can analyze data regarding galvanic or electrolytic cells to identify properties of the underlying
redox reactions.
 LO 6.1 The student is able to, given a set of experimental observations regarding physical, chemical, biological, or
environmental processes that are reversible, construct an explanation that connects the observations to the
reversibility of the underlying chemical reactions or processes.
Section 18.4
Cell Potential, Electrical Work, and Free Energy

Work
 Work is never the maximum possible if any current is
flowing.
 In any real, spontaneous process some energy is always
wasted – the actual work realized is always less than the
calculated maximum.

Copyright © Cengage Learning. All rights reserved 38

Section 18.4
Cell Potential, Electrical Work, and Free Energy

Maximum Cell Potential

 Directly related to the free energy difference between
the reactants and the products in the cell.
 ΔG° = –nFE°
 F = 96,485 C/mol e–

Copyright © Cengage Learning. All rights reserved 39

Section 18.5
Dependence of Cell Potential on Concentration

AP Learning Objectives, Margin Notes and References

 Learning Objectives
 LO 3.12 The student can make qualitative or quantitative predictions about galvanic or electrolytic reactions based
on half-cell reactions and potentials and/or Faraday’s laws.
 LO 3.13 The student can analyze data regarding galvanic or electrolytic cells to identify properties of the underlying
redox reactions.
 LO 6.1 The student is able to, given a set of experimental observations regarding physical, chemical, biological, or
environmental processes that are reversible, construct an explanation that connects the observations to the
reversibility of the underlying chemical reactions or processes.
Section 18.5
Dependence of Cell Potential on Concentration

A Concentration Cell

Copyright © Cengage Learning. All rights reserved 41

Section 18.5
Dependence of Cell Potential on Concentration

Nernst Equation
 The relationship between cell potential and
concentrations of cell components
 At 25°C:
0.0591
E = E  log Q 
n
or
0.0591
E= log K 
n
(at equilibrium)
Copyright © Cengage Learning. All rights reserved 42
Section 18.5
Dependence of Cell Potential on Concentration

CONCEPT CHECK!

Explain the difference between E and E°.

When is E equal to zero?
When the cell is in equilibrium ("dead" battery).
When is E° equal to zero?
E  is equal to zero for a concentration cell.

Copyright © Cengage Learning. All rights reserved 43

Section 18.5
Dependence of Cell Potential on Concentration

EXERCISE!

A concentration cell is constructed using two nickel

electrodes with Ni2+ concentrations of 1.0 M and
1.00 × 10-4 M in the two half-cells.

Calculate the potential of this cell at 25°C.

0.118 V

Copyright © Cengage Learning. All rights reserved 44

Section 18.5
Dependence of Cell Potential on Concentration

CONCEPT CHECK!

You make a galvanic cell at 25°C containing:

 A nickel electrode in 1.0 M Ni2+(aq)
 A silver electrode in 1.0 M Ag+(aq)

Sketch this cell, labeling the anode and cathode,

showing the direction of the electron flow, and
calculate the cell potential.
1.03 V

Copyright © Cengage Learning. All rights reserved 45

Section 18.6
Batteries

One of the Six Cells in a

12–V Lead Storage
Battery

Copyright © Cengage Learning. All rights reserved 46

Section 18.6
Batteries

A Common Dry Cell Battery

Section 18.6
Batteries

A Mercury Battery

Copyright © Cengage Learning. All rights reserved 48

Section 18.6
Batteries

Schematic of the
Hydrogen-Oxygen
Fuel Cell
Section 18.7
Corrosion

AP Learning Objectives, Margin Notes and References

 Learning Objectives
 LO 6.1 The student is able to, given a set of experimental observations regarding physical, chemical, biological, or
environmental processes that are reversible, construct an explanation that connects the observations to the
reversibility of the underlying chemical reactions or processes.
Section 18.7
Corrosion

 Process of returning metals to their natural state – the

ores from which they were originally obtained.
 Involves oxidation of the metal.

Copyright © Cengage Learning. All rights reserved 51

Section 18.7
Corrosion

The Electrochemical Corrosion of Iron

Copyright © Cengage Learning. All rights reserved 52

Section 18.7
Corrosion

Corrosion Prevention
 Application of a coating (like paint or metal plating)
 Galvanizing
 Alloying
 Cathodic Protection
 Protects steel in buried fuel tanks and pipelines.

Copyright © Cengage Learning. All rights reserved 53

Section 18.7
Corrosion

Cathodic Protection

Copyright © Cengage Learning. All rights reserved 54

Section 18.8
Electrolysis

AP Learning Objectives, Margin Notes and References

 Learning Objectives
 LO 3.12 The student can make qualitative or quantitative predictions about galvanic or electrolytic reactions based
on half-cell reactions and potentials and/or Faraday’s laws.
 LO 3.13 The student can analyze data regarding galvanic or electrolytic cells to identify properties of the underlying
redox reactions.
 LO 5.15 The student is able to explain how the application of external energy sources or the coupling of favorable
with unfavorable reactions can be used to cause processes that are not thermodynamically favorable to become
favorable.

 Additional AP References
 LO 5.15 (see Appendix 7.11, “Non-Spontaneous Reactions”)
Section 18.8
Electrolysis

 Forcing a current through a cell to produce a chemical

change for which the cell potential is negative.

Copyright © Cengage Learning. All rights reserved 56

Section 18.8
Electrolysis

Stoichiometry of Electrolysis
 How much chemical change occurs with the flow of a
given current for a specified time?

current and time  quantity of charge 

moles of electrons  moles of analyte 
grams of analyte

Copyright © Cengage Learning. All rights reserved 57

Section 18.8
Electrolysis

Stoichiometry of Electrolysis
 current and time  quantity of charge
Coulombs of charge = amps (C/s) × seconds (s)
 quantity of charge  moles of electrons

 1 mol e
mol e = Coulombs of charge 
96, 485 C

Copyright © Cengage Learning. All rights reserved 58

Section 18.8
Electrolysis

CONCEPT CHECK!

An unknown metal (M) is electrolyzed. It took

52.8 sec for a current of 2.00 amp to plate
0.0719 g of the metal from a solution containing
M(NO3)3.

What is the metal?

gold (Au)

Copyright © Cengage Learning. All rights reserved 59

Section 18.8
Electrolysis

CONCEPT CHECK!

Consider a solution containing 0.10 M of each of the

following: Pb2+, Cu2+, Sn2+, Ni2+, and Zn2+.

Predict the order in which the metals plate out as the

voltage is turned up from zero.
Cu2+, Pb2+, Sn2+, Ni2+, Zn2+
Do the metals form on the cathode or the anode?
Explain.

Copyright © Cengage Learning. All rights reserved 60

Section 18.9
Commercial Electrolytic Processes

 Production of aluminum
 Purification of metals
 Metal plating
 Electrolysis of sodium chloride
 Production of chlorine and sodium hydroxide

Copyright © Cengage Learning. All rights reserved 61

Section 18.9
Commercial Electrolytic Processes

Producing Aluminum by the Hall-Heroult Process

Copyright © Cengage Learning. All rights reserved 62

Section 18.9
Commercial Electrolytic Processes

Electroplating a Spoon

Copyright © Cengage Learning. All rights reserved 63

Section 18.9
Commercial Electrolytic Processes

The Downs Cell for the Electrolysis of Molten Sodium

Chloride

Copyright © Cengage Learning. All rights reserved 64