Chapter 18 Notes

CHEM 1411 General Chemistry Chemistry: A Molecular Approach by Nivaldo J. Tro

18 Electrochemistry

Objectives:
• Understand oxidation-reductions reactions, and be
able to balance a redox equation.
• Understand the operation of galvanic and
electrolytic cells.
• Understand how to calculate the potential of a cell,
and how this quantity is related to other
thermodynamic quantities.
Mr. Kevin A. Boudreaux
Angelo State University 1
[Link]/faculty/kboudrea

Electrochemistry
• Electrochemistry is the study of the relationship
between chemical and electrical energy.
– Galvanic or voltaic cells convert chemical
energy into electrical energy (batteries).
– Electrolytic cells use electrical energy to drive
chemical changes.
– Many essential chemicals and materials are made
through electrochemical processes.
• Electrochemistry is also deeply connected to
thermodynamics.

2
Chapter 18 Notes

A Review of Oxidation
and Reduction

Oxidation and Reduction

• An oxidation-reduction (redox) reaction is a
process in which electrons are transferred from one
substance to another.
– Oxidation is the loss of electron(s).
– Reduction is the gain of electron(s).
Oxidation: Zn → Zn2+ + 2e- half-reactions
Reduction: 2H+ + 2e- → H2
– Oxidation always accompanies reduction.
oxidation

Zn(s) + 2H+(aq) ⎯⎯→ Zn2+(aq) + H2(g)

reduction 4
Chapter 18 Notes

Oxidizing and Reducing Agents

• The oxidizing agent is the substance that causes
oxidation to occur by accepting electrons. The
oxidizing agent itself becomes reduced.
• The reducing agent is the substance that causes
reduction to occur by losing electrons. The reducing
agent itself becomes oxidized.
• The number of electrons gained by the oxidizing
agent always equals the number lost by the reducing
agent. This is important when balancing redox
equations.
oxidation

Zn(s) + 2H+(aq) ⎯⎯→ Zn2+(aq) + H2(g)

reduction 5

Balancing Redox Reactions

• Since oxidation and reduction reactions always
occur together, balancing a redox reaction also
requires balancing the number of electrons which are
transferred.
– A redox reaction may look balanced, but if the
charges are not the same on both sides, it isn’t:
Al(s) + Cu2+(aq) → Al3+(aq) + Cu(s)
[not balanced]
• Simple redox reactions can often be balanced by
inspection, but more complicated ones require a
systematic approach. There are two methods for
balancing redox reactions:
– the oxidation number method
– the half-reaction method 6
Chapter 18 Notes

The Half-Reaction Method

Step 1. Divide the skeleton reaction into two half-
reactions, each of which contains the oxidized
and reduced forms of one of the species.
Step 2. Balance atoms and charges in each half-
reaction.
a. Balance atoms other than O and H.
b. Balance O atoms by adding H2O.
c. Balance H atoms by adding H+ ions.
d. Balance charge by adding electrons (e-).
Step 3. Multiply each half-reaction by some integer to
make the number of e- gained in the reduction
equal the number of e- lost in the oxidation.
7

The Half-Reaction Method

Step 4. Add the balanced half-reactions and include
states of matter.
Step 4a. If the reaction occurs in basic solution, add
one OH- to both sides of the equation for
every H+ ion present; combine H+ and OH-
ions to form waters, and cancel out those that
appear on both sides.
Step 5. Double-check that the atoms and charges are
balanced.

8
Chapter 18 Notes

The Oxidation Number Method

Step 1. Assign oxidation numbers to all elements in
the reaction.
Step 2. Identify the oxidized and reduced species.
Step 3. Compute the number of electrons lost in the
oxidation and gained in the reduction from the
oxidation number changes.
Step 4. Multiply one or both of these numbers by
appropriate factors to make the electrons lost
equal the electrons gained, and use the factors
as balancing coefficients.
Step 5. Complete the balancing by inspection, adding
phase labels.

Examples: Balancing Redox Reactions

1. Use the half-reaction method to balance the
following redox reactions. (sim. to Ex. 18.1-18.3)
a. Cr2O72-(aq) + I-(aq) → Cr3+(aq) + I2(s)
[acidic solution]

b. Sn(s) + NO3-(aq) → SnO2(aq) + NO(g)

[acidic solution]

c. MnO4-(aq) + C2O42-(aq) → MnO2(s) + CO32-(aq)

[basic solution]

Rules
10
Chapter 18 Notes

Galvanic (Voltaic)
Cells

11

An Overview of Electrochemical Cells

• There are two types of electrochemical cells:
• A galvanic cell (or voltaic cell) uses a spontaneous
reaction (ΔG° < 0) to generate electrical energy.
– The difference in potential energy between higher
energy reactants and lower energy products is
converted into electrical energy.
– The reactants do work on the surroundings.
• An electrolytic cell uses electrical energy to drive a
nonspontaneous reaction (ΔG° > 0).
– Lower energy reactants are converted into higher
energy products by electrical energy.
– The surroundings do work on the reactants.

12
Chapter 18 Notes

An Overview of Electrochemical Cells

13

A Zn Bar in a Cu2+ Solution

• If a bar of zinc metal is placed in a solution of Cu2+
ions, a spontaneous reaction takes place:
Zn(s) → Zn2+(aq) + 2e- [oxidation]
Cu2+(aq) + 2e- → Cu(s) [reduction]
——————————————————————————————————
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) [overall]

• When this is done in a beaker (Fig. 18.1), the zinc

slowly dissolves as it is oxidized into soluble Zn2+
ions, and the blue color of the solution fades as Cu2+
is reduced to copper metal and deposits on the bar.
• However, no electrical energy is generated because
the oxidizing and reducing agents are in physical
contact; the enthalpy of the reaction escapes into the
surroundings as heat. 14
Chapter 18 Notes

A Zn Bar in a Cu2+ Solution

15
Figure 18.1

A Zn - Cu2+ Galvanic Cell

• If, however, the oxidation and reduction processes
are separated from each other in two separate half-
cells (Fig. 18.2), electrical energy can be generated:
– A rod of zinc metal (the anode) is immersed in a
Zn2+ solution and connected by a wire to a rod of
copper metal (the cathode) in a Cu2+ solution.
– The zinc is oxidized, releasing electrons which
travel through the wire and reduce Cu2+ in the
other half-cell, producing and electrical current.
– A salt bridge between the half-cells maintains
electrical neutrality and completes the circuit.
– The chemical energy in the reactants can then be
used to light a bulb or run an electrical device.
– This type of galvanic cell is called a Daniell cell. 16
Chapter 18 Notes

A Zn - Cu2+ Galvanic Cell

17
Figure 18.2 MOV: Copper-Zinc Cell movie

Fig. 18.2 Galvanic Cells — Electrolytes

• In a galvanic (voltaic) cell, the components of each
half-reaction are placed in separate containers called
half-cells, consisting of an electrode dipping into an
electrolyte solution; the cells are joined by a wire
and a salt bridge.
• The electrolyte solutions are solutions of ions
(usually dissolved in water) that are involved in the
reaction or that carry the charge between the
electrodes.
– Unless an inert electrode is being used, the
electrolyte is usually a soluble ionic compound
containing a cation of the electrode metal.
– In this example, the zinc half-cell electrolyte
could be any soluble zinc compound, such as zinc
nitrate, zinc chloride, zinc sulfate, etc. 18
Chapter 18 Notes

Fig. 18.2 Galvanic Cells — Electrodes

• The electrodes are usually metal rods or sheets that
are immersed in the electrolyte solutions of each
half-cell; they conduct the electricity between the
cell and the surroundings. An electrode is classified
by the half-reaction which takes place there:
– The anode is where the oxidation half-reaction
takes place. Electrons are given up by the
substance being oxidized (reducing agent) and
leave the cell at the anode.
– The cathode is where the reduction half-reaction
takes place. Electrons are taken up by the
substance being reduced (oxidizing agent) and
enter the cell at the cathode.

19

Fig. 18.2 Galvanic Cells — Electrodes

• In this example, the oxidation half-cell consists of a
Zn metal bar acting as the anode, which is immersed
in a Zn2+ electrolyte solution [Zn(NO3)2].
– The Zn anode will dissolve as it is oxidized into
Zn2+, and will conduct e-’s out of its half-cell.
Zn(s) → Zn2+(aq) + 2e-
• In this example, the reduction half-cell consists of a
Cu metal bar acting as the cathode, which is
immersed in a Cu2+ electrolyte solution [Cu(NO3)2].
– The Cu cathode will gain more Cu metal as Cu2+
is reduced, and will conduct e-’s into its half-cell.
Cu2+(aq) + 2e- → Cu(s)
• By convention, the anode compartment is always
drawn on the left. 20
Chapter 18 Notes

Fig. 18.2 Galvanic Cells — Electrodes

• The relative charges on the electrodes are
determined by the source of the electrons and the
direction of the electron flow.
– Electrons are generated at the anode and
consumed at the cathode, therefore:
– In any voltaic cell, the anode is negative and the
cathode is positive.

CPR ANO
Cathode Anode
Positive Negative
Reduction Oxidation
21

Fig. 18.2 Galvanic Cells — The Salt Bridge

• The salt bridge consists of a non-reactive electrolyte
suspended in a gel. It completes the circuit between
the half-cells by maintaining charge neutrality in the
electrolyte solutions.
– As Zn is oxidized to Zn2+, anions (NO3-) diffuse
out of the salt bridge into its electrolyte solution,
balancing out the charge.
– As Cu2+ is reduced to Cu, cations (K+) diffuse out
of the salt bridge into its electrolyte solution.
– As electrons move left to right through the wire,
anions move right to left (towards the anode) and
cations move left to right (toward the cathode)
through the salt bridge.
– Thus, the overall charge in each solution is
maintained, and the circuit is completed. 22
Chapter 18 Notes

Fig. 18.2 Galvanic Cells — Summary

23

Active and Inactive Electrodes

• In this example, active electrodes are used, which
are active participants in the half-reactions. The
electrodes are consumed or added to during the
course of the reaction.
• Often, inactive (or inert) electrodes are used,
usually made of graphite or platinum:

2I-(aq) → I2(s) + 2e- [anode]

MnO4-(aq) + 8H+(aq) + 5e- → Mn2+(aq) + 4H2O(l)
[cathode]

– In this case, the species involved can’t act as

electrodes, and so something else must be used.
The electrolyte solutions must contain all of the
species involved in the half-reaction. (Fig 21.6) 24
Chapter 18 Notes

Active and Inactive Electrodes

Active Electrodes:
anode: Zn(s) → Zn2+(aq) + 2e-
cathode: Cu2+(aq) + 2e- → Cu(s)
overall: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

Inactive Electrodes:
anode: 2I-(aq) → I2(s) + 2e-
cathode: MnO4-(aq) + 8H+(aq) + 5e- →
Mn2+(aq) + 4H2O(l)
overall: 2MnO4-(aq) + 16H+(aq) + 10I-(aq)
→ 2Mn2+(aq) + 5I2(s) + 8H2O(l)
25

Active and Inactive Electrodes

• This examples uses both an active and an inactive
electrode:

anode: Fe(s) → Fe2+(aq) + 2e-

cathode: MnO4-(aq) + 8H+(aq) + 5e- → Mn2+(aq) + 4H2O(l)
overall: 5Fe(s) + 2MnO4-(aq) + 16H+(aq) →
5Fe2+(s) + 2Mn2+(aq) + 8H2O(l)
26
Figure 18.4
Chapter 18 Notes

Cell Notation
• Cell notation is a useful shorthand description for
the components of a voltaic cell:

Anode | electrolyte
Anode
|| electrolyte
Cathode
| Cathode
electron flow

– The anode components are always written on the

left and the cathode components on the right
– A vertical line | represents a boundary between
two phases. Two or more components in the
same phase are separated by commas.
– A double vertical line || represents the salt bridge.
– The electron flow is left to right in this notation.
27

Cell Notation
• In the Zn-Cu2+ voltaic cell, the cell notation is:
Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)
– The order in which the cell notation is written
suggests the overall reaction: Zn is oxidized to
Zn2+, and Cu2+ is reduced to Cu.

• In the I--MnO4- cell, where inert electrodes are used,

and the electrolyte solutions contain all of the
reacting species, the cell notation is
Graphite(s) |I2(s) | I-(aq) ||
H+(aq), MnO4-(aq), Mn2+(aq) | Graphite(s)

28
Chapter 18 Notes

Examples: Galvanic Cells

2. Diagram, show balanced equations, and write the
cell notation for a voltaic cell that consists of one
half-cell with a Cr bar in a Cr(NO3)3 solution,
another half-cell with an Ag bar in an AgNO3
solution, and a KNO3 salt bridge. Measurement
indicates that the Cr electrode is negative relative to
the Ag electrode.

29

Examples: Galvanic Cells

3. Design a galvanic cell that uses the redox reaction
Fe(s) + 2Fe3+(aq) → 3Fe2+(aq)
Identify the anode and cathode half-reactions, and
sketch the experimental setup. Label the anode and
cathode, indicate the direction of electron and ion
flow, and identify the sign of each electrode.

30
Chapter 18 Notes

Examples: Galvanic Cells

4. Given the following cell notations, write balanced
equations for the cell reactions, and give a brief
description of the cells.

a. Pt(s)|Sn2+(aq),Sn4+(aq)||Ag+(aq)|Ag(s)

b. Cu(s)|Cu2+(aq)||Cl2(g)|Cl-(aq)|C(s)

31

Examples: Galvanic Cells

5. Write the shorthand notations for galvanic cells that
use the reactions shown below.

a. Fe(s) + Sn2+(aq) → Fe2+(aq) + Sn(s)

b. Pb(s) + Br2(l) → Pb2+(aq) + 2Br-(aq)

32
Chapter 18 Notes

Cell Potentials

33

Cell Potential
• The driving force that causes electrons to move from
anode to the cathode is the electromotive force
(emf), or cell potential (Ecell). This represents the
potential energy difference between the materials in
the anode and cathode compartments.
• Electrical units in the SI system:
– electrical charge: coulomb, C

1J
– electrical potential: volt, V 1V =
1C

1C
– electrical current: ampere, A 1A =
1s
34
Chapter 18 Notes

The Standard Hydrogen Electrode (SHE)

• Since it is not possible to measure the potential of a
half-cell without connecting it to another cell, a
standard reference half-cell has been defined to
have a potential of 0 V. All other cell potentials are
combined with the reference half-cell, and measured
relative to that value.
• The standard hydrogen electrode (SHE)
consists of a platinum electrode in a 1 M
H+(aq) solution at 25°C, through which
H2(g) at 1 atm is bubbled:
2H+(aq, 1 M) + 2e- → H2(g, 1 atm); E° = 0 V
H2(g, 1 atm) → 2H+(aq, 1 M) + 2e-; E° = 0 V

35
Figure 18.6 MOV: Zinc-Hydrogen Cell movie

Using the SHE to Obtain a Reduction Potential

• If we connect a Zn/Zn2+ half-cell to a SHE half-cell
(Fig. 18.7), the cell potential is found to be +0.76 V,
with the zinc half-cell acting as the anode:
Zn(s) → Zn2+(aq) + 2e-; E° = ? V
2H+(aq) + 2e- → H2(g); E° = 0 V
_______________________________________________________________________________________________________

Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g); E° = +0.76 V

36
Figure 18.7
Chapter 18 Notes

Using the SHE to Obtain a Reduction Potential

• The cell potential is obtained from the formula:
E°cell = E°red + E°ox
• Since E°cell = +0.76 V, and E°red = 0 V (SHE); E°ox
for the zinc cell is 0.76 V.
• If the Zn/Zn2+ half-cell instead runs as a reduction,
we would write the reaction backwards and reverse
the sign on the cell potential. Its standard
reduction potential would be -0.76 V:
Zn2+(aq) + 2e- → Zn(s); E° = -0.76 V
• By convention, tables of half-cell potentials are
written as reductions; the reaction for the cell which
occurs as an oxidation is reversed.
37

Using the SHE to Obtain a Reduction Potential

• If we connect a Cu/Cu2+ half-cell to a SHE half-cell,
the overall cell potential is found to be +0.34 V, with
the copper half-cell acting as the cathode:
H2(g) → 2H+(aq) + 2e-; E° = 0 V
Cu2+(aq) + 2e- → Cu(s); E° = ? V
_______________________________________________________________________________________________________

H2(g) + Cu2+(aq) → 2H+(aq) + Cu(s); E° = +0.34 V

• Since E°cell = +0.34 V, and E°ox = 0 V (SHE); E°red

for the copper cell is +0.34 V:
Cu2+(aq) + 2e- → Cu(s); E° = +0.34 V

38
Chapter 18 Notes

Standard Reduction Potentials

• In the following charts, the standard reduction
potentials (or standard electrode potentials) for a
number of half-cells are listed. In all cases, the half-
reactions are written as reductions. In other words,
the potential listed is the potential that the half-cell
has if the half-cell reactions occurs as a reduction.
• Oxidizing agents (which get reduced) and electrons
are on the left side of each half-reaction; reducing
agents (which get oxidized) are on the right.
• The half-reactions are listed by decreasing standard
reduction potential. Thus, the strongest oxidizing
agents are located in the upper left (F2, H2O2,
MnO4-, etc.) and the strongest reducing agents are
found in the lower right (Li, Na, Mg, etc.).
– This list is essentially where the activity series for single displacement
reactions is derived. 39

Standard Reduction Potentials

40
Chapter 18 Notes

Standard Reduction Potentials

41

Standard Reduction Potentials

42
more standard reduction potentials are listed in Appendix IID, p. A-15
Chapter 18 Notes

Standard Reduction Potentials

Standard Reduction Potentials at 25°C
Half-Reaction E° (V)
F2(g) + 2e- h 2F-(aq) +2.87
O3(g) + 2H+(aq) + 2e- h O2(g) + 2H2O(l) +2.07
Co3+(aq) + e- h Co2+(aq) +1.82
H2O2(aq) + 2H+(aq) + 2e- h 2H2O(l) +1.77
PbO2(s) + SO42-(aq) + 4H+(aq) + 2e- h PbSO4(s) + 2H2O(l) +1.69
2HOCl(aq) + 2H+(aq) + 2e- h Cl2(g) + 2H2O(l) +1.63
Ce4+(aq) + e- h Ce3+(aq) +1.61
MnO4-(aq) + 8H+(aq) + 5e- h Mn2+(aq) + 4H2O(l) +1.51
Au3+(aq) + 3e- h Au(s) +1.50
BrO3-(aq) + 6H+(aq) + 6e- h Br-(aq) + 3H2O +1.44
Cl2(g) + 2e- h 2Cl-(aq) +1.36
Cr2O72-(aq) + 14H+(aq) + 6e- h 2Cr3+(aq) + 7H2O(l) +1.33
MnO2(s) + 4H+(aq) + 2e- h Mn2+(aq) + 2H2O(l) +1.23
O2(g) + 4H+(aq) + 4e- h 2H2O +1.23
Br2(g) + 2e- h 2Br-(aq) +1.07
NO3-(aq) + 4H+(aq) + 3e- h NO(g) + 2H2O +0.96
2Hg2+(aq) + 2e- h Hg22+(aq) +0.92
Hg22+(aq) + 2e- h Hg(l) +0.85
Ag+(aq) + e- h Ag(s) +0.80
Fe3+(aq) + e- h Fe2+(aq) +0.77
O2(g) + 2H+(aq) + 2e— h H2O2(aq) +0.70
MnO4-(aq) + 2H2O(l) + 3e- h MnO2(s) + 4OH-(aq) +0.59
I2(g) + 2e- h 2I-(aq) +0.53
NiO2(s) + 2H2O + 2e- h Ni(OH)2(s) + 2OH-(aq) +0.49
O2(g) + 2H2O(l) + 4e- h 4OH-(aq) +0.40
Cu2+(aq) + 2e- h Cu(s) +0.34
AgCl(s) + e- h Ag(s) + Cl-(aq) +0.22
SO42- + 4H+(aq) + 2e- h SO2(g) + 2H2O(l) +0.20
Cu2+(aq) + e- h Cu+(aq) +0.15
Sn4+(aq) + 2e- h Sn2+(aq) +0.15
2H+(aq) + 2e- h H2(g) 0.00 43

Standard Reduction Potentials

Standard Reduction Potentials at 25°C
Half-Reaction E° (V)
2H+(aq) + 2e- h H2(g) 0.00
Pb2+(aq) + 2e- h Pb(s) -0.13
Sn2+(aq) + 2e- h Sn(s) -0.14
N2(g) + 5H+(aq) + 4e- h N2H5+(aq) -0.23
Ni2+(aq) + 2e- h Ni(s) -0.25
Co2+(aq) + 2e- h Co(s) -0.28
PbSO4(s) + 2e- h Pb(s) + SO42-(aq) -0.31
Cd2+(aq) + 2e- h Cd(s) -0.40
Fe2+(aq) + 2e- h Fe(s) -0.44
Cr3+(aq) + 3e- h Cr(s) -0.74
Zn2+(aq) + 2e- h Zn(s) -0.76
2H2O + 2e- h H2(g) + 2OH-(aq) -0.83
Mn2+(aq) + 2e- h Mn(s) -1.18
Al3+(aq) + 3e- h Al(s) -1.66
Mg2+(aq) + 2e- h Mg(s) -2.37
Na+(aq) + e- h Na(s) -2.71
Ca2+(aq) + 2e- h Ca(s) -2.87
Sr2+(aq) + 2e- h Sr(s) -2.89
Ba2+(aq) + 2e- h Ba(s) -2.90
K+(aq) + e- h K(s) -2.93
Li+(aq) + e- h Li(s) -3.05

44
Chapter 18 Notes

Using Standard Reduction Potentials

• An overall redox reaction is the sum of the half-
reactions associated with each half-cell process:
– one occurs as a reduction (at the cathode), written
in the forward direction.
– the other occurs as an oxidation (at the anode),
written in the reverse direction.
– The potential of the cell (E°cell) is the difference
between the standard half-cell potentials of the
cathode and the anode:
E°cell = E°cathode + (- E°anode)
E°cell = E°red + (- E°ox)
• NOTE: Do NOT multiply E°half-cell values by the coefficient;
it is an intensive property, since it is the ratio of J/C. 45

Using Standard Reduction Potentials

• For example, to calculate the cell potential (E°cell)
for the oxidation of Zn(s) by Ag+(aq):
2Ag+(aq) + Zn(s) → 2Ag(s) + Zn2+(aq)
consider the relevant half-reactions:

reduction (cathode):
2 [Ag+(aq) + e- → Ag(s)] E° = 0.80 V
oxidation (anode):
Zn(s) → Zn2+(aq) + 2e- -E° = -(-0.76 V)

E°cell = E°cathode + (- E°anode)

E°cell = 0.80 V + 0.76 V = 1.56 V
46
Chapter 18 Notes

Relative Strengths of Oxidizing & Reducing Agents

Cu2+(aq) + 2e- → Cu(s) E°cell = +0.34 V
2H+(aq) + 2e- → H2(g) E°cell = 0.00 V
Zn2+(aq) + 2e- → Zn(s) E°cell = -0.76 V
• The more positive the E°cell value, the more the
reaction tends to occur as written. Thus, Cu2+ gains
two electrons more easily than H+, and H+ gains
electrons more easily than Zn2+.
– Therefore, Cu2+ is the strongest oxidizing agent,
and Zn2+ is the weakest oxidizing agent.
– Since reversing the reaction reverses the sign of
E°cell, Zn is the strongest reducing agent and Cu is
the weakest reducing agent.
47

Writing and Predicting Spontaneous Reactions

• Table 18.1 can be used as a guide to writing
spontaneous redox reactions, which is useful when
trying to construct electrochemical cells.
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
stronger stronger weaker weaker
reducing oxidizing oxidizing reducing
agent agent agent agent

• The members of a redox couple (such as Zn and

Zn2+) differ by one or more electrons.
• A spontaneous reaction (E°cell > 0) will occur
between an oxidizing agent and a reducing agent
that lies below it on Table 18.1.

48
Chapter 18 Notes

Writing and Predicting Spontaneous Reactions

• In other words, if the overall reaction is split into
half reactions, the half-reaction with the more
positive reduction potential takes place as a
reduction, while the other one runs in reverse as an
oxidation.
• To determine whether a given reaction is
spontaneous, look at the oxidation (anode) and
reduction (cathode) processes, and calculate the cell
potential. If the cell potential is positive, the
reaction is spontaneous; if negative it is
nonspontaneous (or spontaneous in the reverse
direction).
E°cell = E°cathode + -E°anode
E°cell = E°red + -E°ox
49

Metals Dissolving in Acids

• Some metals, such as Zn, dissolve in acidic solutions:
Zn2+(aq) + 2e- → Zn(s); E° = -0.76 V
2H+(aq) + 2e- → H2(g); E° = 0 V
Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g); E° = +0.76 V
• Cu, however, does not dissolve in most acids:
Cu2+(aq) + 2e- → Cu(s); E° = +0.34 V
Cu(s) + 2H+(aq) → Cu2+(aq) + H2(g); E° = -0.34 V
• An important exception is nitric acid, which oxidizes
metals through the redox reaction
NO3-(aq) + 4H+(aq) + 3e- → NO(g) + 2H2O(l);
Ered° = 0.96 V
50
Chapter 18 Notes

Examples: Using Reduction Potentials

6. Arrange the following oxidizing agents in order of
increasing strength under standard-state conditions:
Br2(l), Fe3+(aq), Cr2O72-(aq).

51

Examples: Using Reduction Potentials

7. Arrange the following reducing agents in order of
increasing strength under standard-state conditions:
Al(s), Na(s), Zn(s).

52
Chapter 18 Notes

Examples: Using Reduction Potentials

8. Use the following half-reactions to predict the
spontaneous reaction that occurs when Br-, SO42-,
H2SO3, and Br2 are mixed in an acidic solution.
Br2(aq) + 2e- → 2Br-(aq); E° = +1.07 V
SO42-(aq) + 4H+(aq) + 2e- → H2SO3(aq) +
H2O
E° = +0.17 V

53

Examples: Using Reduction Potentials

9. What spontaneous reaction occurs if Cl2 and Br2
are added to a solution that contains both Cl- and
Br-?

54
Chapter 18 Notes

Examples: Using Reduction Potentials

10. Predict from Table 18.1 whether Pb2+(aq) can
oxidize Al(s) or Cu(s) under standard-state
conditions. Calculate E° for each reaction at 25°C.

55

Examples: Using Reduction Potentials

11. What is the overall cell reaction and the standard
cell potential of a galvanic cell employing the
following half-reactions?
Cr3+(aq) + 3e- h Cr(s); E°Cr3+ = -0.74 V
MnO4-(aq) + 8H+(aq) + 5e- h Mn2+(aq) +
4H2O
E°MnO4- = +1.51 V

56
Chapter 18 Notes

Examples: Using Reduction Potentials

12. Which of the following reactions occur
spontaneously in the forward direction? (sim. to Ex.
18.5)
Br2(aq) + Cl2(g) + 2H2O → 2Br-(aq) + 2HOCl(aq) + 2H+(aq)

3Zn(s) + 2Cr3+(aq) → 3Zn2+(aq) + 2Cr(s)

57

A Shocking Dental Galvanic Cell

• Biting on aluminum foil produces pain if you have fillings in

your teeth. Al acts as the anode (-1.66 V), saliva as the
electrolyte, and the silver/tin/mercury alloy filling as an inert
cathode. O2 is reduced to water (1.23 V), and the short
circuit between the foil in contact with the filling creates a
current that jolts the nerve in the tooth. 58
Chapter 18 Notes

Cell Potentials and

Thermodynamics

59

Cell Potential and Free Energy

• In the examples we’ve seen of spontaneous cell
reactions, the cell potentials have been positive.
There must then be some connection between the
cell potential and the free energy change.
• The cell potential (Ecell) and the free energy change
(∆G) are related by the equation
∆G = - n F Ecell
n = the number of moles of electrons transferred in
the reaction.
F = the faraday, F , the charge on one mole of
electrons (named for Michael Faraday):
1 F = 96,485 C / mol e-
1 F = 96,485 J V-1 mol e-1
60
Chapter 18 Notes

Cell Potential and Free Energy

• This gives us a connection between cell potential
and spontaneity:
∆G Ecell Spontaneity
- + spontaneous
+ - nonspontaneous
0 0 at equilibrium

• The more positive the Ecell, the more work the cell
can do, and the farther the reaction proceeds to the
right as written.
• If Ecell = 0, the reaction has reached equilibrium, and
the cell can do no more work (“dead battery”).

61

Standard Cell Potentials

• Since Ecell is affected by concentration, pressure, and
temperature, a standard cell potential, E°cell is
defined, in which all components are at standard
thermodynamic conditions (25°C, 1 atm, pure solids
for electrodes, ions at 1.00 M).
• When all components are at standard conditions,
ΔG° = - nFE°cell

62
Chapter 18 Notes

Examples: Cell Potential and Free Energy

13. Calculate the standard free-energy change at 25°C
for the following reaction. (sim. to Ex. 18.6)
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

63

Examples: Cell Potential and Free Energy

14. Calculate the standard cell potential at 25°C for the
following reaction, which has a standard free-
energy change of -266.3 kJ.
Al(s) + Cr3+(aq) → Al3+(aq) + Cr(s)

64
Chapter 18 Notes

The Relationship Between E°cell, ΔG°, and K

• When all components are in their standard states,
ΔG° = - nFE°cell
• Using the relationship between K and ΔG°,
ΔG° = - RT ln K
- RT ln K = - nFE°cell

RT
o
Ecell = ln K
nF
o
0.0592 V nEcell
E o
cell = log K log K =
n 0.0592 V
65

Examples: Calculating K and ΔG° from E°

15. Lead can displace silver from solution:
Pb(s) + 2Ag+(aq) → Pb2+(aq) + 2Ag(s)
As a consequence, silver is a valuable by-product in
the industrial extraction of lead from its ore.
Calculate K and ΔG° at 25°C for this reaction.
(sim. to Ex. 18.7)

66
Chapter 18 Notes

The Nernst Equation

• Most electrochemical cells do not start out with all
of their components in their standard states or at
their standard concentrations, and even if they did,
would not remain that way for long.
• In order to obtain Ecell, the cell potential under
nonstandard conditions, we start with the expression
for ΔG under nonstandard conditions:
∆G = ∆G° + RT ln Q
-nFEcell = -nFE°cell + RT ln Q
• Solving for Ecell gives the Nernst equation (W. H.
Nernst, 1889)
RT
Ecell = Ecell
o
- ln Q
nF
67

The Nernst Equation

0.0592 V
Ecell = Ecell
o
- log Q (at 25o C)
n
If Q < 1 [product] < [reactant] log Q < 0 Ecell > E°cell
If Q > 1 [product] > [reactant] log Q > 0 Ecell < E°cell
If Q = 1 [product] = [reactant] log Q = 0 Ecell = E°cell

• Remember when calculating the value of Q, solids

(even solid electrodes) do not appear in the mass-
action expression:
Cd(s) + 2Ag+(aq) → Cd2+(aq) + 2Ag(s)
Q = [Cd2+] / [Ag+]2
68
Chapter 18 Notes

Examples: Using the Nernst Equation

16. Consider a galvanic cell that uses the reaction
Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g)
Calculate Ecell at 25°C when [H+] = 1.0 M, [Zn2+] =
0.0010 M, and PH2 = 0.10 atm. (sim. to Ex. 18.8)

69

Examples: Using the Nernst Equation

17. A galvanic cell was constructed by connecting a
nickel electrode that was dipped into 1.20 M NiSO4
solution to a chromium electrode that was dipping
into a solution containing Cr3+ at an unknown
concentration. The potential of the cell was
measured to be 0.552 V, with the chromium
serving as the anode. The standard cell potential
for this system was determined to be 0.487 V.
What was the concentration of Cr3+ in the solution
of unknown concentration?

70
Chapter 18 Notes

Concentration Cells
• Because cell potentials change with concentration,
two of the same half-cells at different concentrations
can be joined to produce a current:
– In cell A, two Cu/Cu2+ half-cells are connected,
with all of the components at standard conditions.
There is no voltage difference, and no current.
A B

71
Figure 18.12

Concentration Cells
– In cell B, the left half-cell has a concentration
0.010 M and the right half-cell is at 2.0 M. This
concentration difference causes electrons to flow
from the half-cell with the dilute Cu2+ to the half-
cell with the concentrated Cu2+, and produces a
voltage of 0.068 V.
– The flow of electrons increases the concentration
of Cu2+ in the dilute cell (as Cu gets oxidized) and
decreases the concentration of Cu2+ in the
concentrated cell (as Cu2+ is reduced to Cu).
– Nerve cells use a concentration gradient to cause
Na+ and K+ ions to diffuse into or out of a nerve
cell, creating a spike in the electrochemical
potential across the membrane, which travels
down the nerve cell.
72
Chapter 18 Notes

The Nernst Equation and pH

• pH meters are electronic devices that are used for
measuring pH (duuuh!). They are based on a cell
which is similar to the SHE half-cell, which dips
into a solution of unknown pH, and a calomel
reference electrode:
Pt(s) | H2(1 atm) | H+(? M) || Reference cathode
• The potential for the hydrogen half-reaction is
obtained from the Nernst equation:
H2(g) → 2H+(aq) + 2e-
0.0592 V ⎛ [H + ]2 ⎞
EH = E o
- log ⎜ ⎟
→ H+ H2 → H+
n ⎜ ⎟
⎝ PH 2 ⎠
2

73

The Nernst Equation and pH

• Since E° = 0 V, n = 2, and PH2 = 1 atm, this
simplifies to:
0.0592 V
EH →H + = - log [H + ]2
2
2
0.0592 V
= - (2) log [H + ]
2
= (0.0592 V)(-log [H + ])
= (0.0592 V)(pH)

• The overall cell potential is

Ecell = (0.0592 V)(pH) + Eref

• and therefore Ecell − Eref

pH =
0.0592 V 74
Chapter 18 Notes

The pH Meter
• In practice, a glass electrode containing a silver wire
coated with silver chloride immersed in a solution of
HCl is used as the test electrode; the solution in the
cell is separated from the test solution by a thin glass
membrane (Figure 18.6).
• The reference electrode is a calomel (Hg2Cl2)
electrode in contact with liquid mercury and
KCl(aq):
Hg2Cl2(s) + 2e- → 2Hg(l) + 2Cl-(aq); E° = +0.28 V
• A typical pH meter measures the cell potential, and
electronically converts the potential to the pH value:
Ecell − 0.28 V
pH =
0.0592 V
75

The pH Meter

76
Chapter 18 Notes

Batteries

77

Electrochemical Processes in Batteries

• A battery is a self-contained group of voltaic cells
arranged in series (plus-to-minus-to-plus) so that
their individual voltages are added together. The
term is also sometimes used to refer to single voltaic
cells.
– A primary battery cannot be recharged, and
must be disposed of when it is “dead.”
– A secondary, or rechargeable, battery can be
restored to use by supplying electricity to reverse
the cell reactions and regenerate the reactants.
– A fuel cell, or flow battery, is not self-contained;
the reactants (usually a combustible fuel and
oxygen) enter the cell and the products leave,
generating electricity through controlled
oxidation of the fuel. 78
Chapter 18 Notes

Dry Cell (Leclanché cell) (primary)

A common household battery
Anode: Zn(s) → Zn2+(aq) + 2e-
Cathode: 2MnO2(s) + 2NH4+(aq) + 2e- → Mn2O3(s) + 2NH3(aq) + H2O(l) etc.

Ecell = 1.5 V

79

Alkaline Battery (primary)

A modified form of the Leclanché cell, using a basic (alkaline) electrolyte;
corrodes more slowly, and produces higher power and a more stable current

Anode: Zn(s) + 2OH-(aq) → ZnO(s) + H2O(l) + 2e-

Cathode: 2MnO2(s) + 2H2O(l) + 2e- → 2Mn(OH)2(s) + 2OH-(aq)

Ecell = 1.5 V

80
Chapter 18 Notes

Lead-Acid Battery (rechargeable)

Six cells in series, each of which delivers about 2 V.
The electrolyte solution is ~4.5 M H2SO4.
The reactions can be run in reverse, thus recharging the battery,
by using current from the alternator.
Anode: Pb(s) + HSO4-(aq) → PbSO4(s) + H+(aq) + 2e-
Cathode: PbO2(s) + 3H+(aq) + HSO4-(aq) + 2e- → PbSO4(s) + 2H2O(l)

81

Mercury and Silver (Button) Batteries (primary)

Anode: Zn(s) + 2OH-(aq) → ZnO(s) + H2O(l) + 2e-
Cathode (mercury): HgO(s) + H2O(l) + 2e- → Hg(l) + 2OH-(aq)
Cathode (silver): Ag2O(s) + H2O(l) + 2e- → 2Ag(s) + 2OH-(aq)
Ecell = 1.3 V (mercury); 1.6 V (silver)

82
Chapter 18 Notes

Nickel-Cadmium (Nicad) Battery (rechargeable)

Anode: Cd(s) + 2OH-(aq) → Cd(OH)2(s) + 2e-
Cathode: 2NiO(OH)(s) + 2H2O(l) + 2e- → 2Ni(OH)2(s) + 2OH-(aq)
Ecell = 1.4 V

83

Nickel-Metal-Hydride (NiMH) Battery (rechargeable)

Replaces the toxic cadmium anode with a metal matrix impregnated with
hydrogen atoms in a strongly basic electrolyte. At the anode, hydrogen
atoms are released as water molecules; supplying external current reverses
the reactions and recharges the battery.

Anode: MH(s) + OH-(aq) → M(s) + H2O(l) + e-

Cathode: NiO(OH)(s) + H2O(l) + e- → Ni(OH)2(s) + OH-(aq)

Ecell = 1.2 V

84
Chapter 18 Notes

Lithium Solid-State Battery (rechargeable)

Lightweight batteries which produce high
voltages; common in computers, digital
camereas, cell phones, etc.
Anode: Li(s) → Li+(in solid electrolyte) + e-
Cathode: MnO2(s) + Li+ + e- → LiMnO2(s)
Ecell = 3 V

85

Fuel Cells
Differs from an ordinary battery in that the reactants are not contained within the
cell, but are continually supplied from outside. In a hydrogen-oxygen fuel cell, the
reactants are H2 and O2 gases; there are no pollutants formed, but the electrode
materials are expensive and short-lived.
Anode: 2H2(g) + 4OH-(aq) → 4H2O(l) + 4e-
Cathode: O2(g) + 2H2O(l) + 4e- → 4OH-(aq)
Overall: 2H2(g) + O2(g) → 2H2O(l)
Ecell = 1.2 V

86
Chapter 18 Notes

Experimental Systems:

Aluminum-Air Battery
An aluminum anode is oxidized and oxygen from flowing moist air is reduced
at an inactive porous graphite cathode. An aqueous NaOH electrolyte
circulates through the cell.
Anode: 4[Al(s) + 4OH-(aq) → Al(OH)4-(aq) + 3e-]
Cathode: 3[O2(g) + 2H2O(l) + 4e- → 4OH-(aq)
Ecell = 2.7 V

Sodium-Sulfur Battery
Molten Na is the anode, and
molten S8 is the cathode.
Anode: 2Na(l) → 2Na+(l) + 2e-
Cathode: n/8S8(l) + 2e- → nS2-(l)
Ecell = 2.1 V

87

88
Chapter 18 Notes

Corrosion

89

The Corrosion of Iron

• Corrosion is the oxidative deterioration of a metal,
such as the rusting of iron.
• Iron does not rust because of a simple reaction
between iron metal and oxygen gas:
4Fe + 3O2(g) → 2Fe2O3(s)
– Water must be present for rusting to occur; in
oxygen-free water or dry air, iron does not rust.
– Rusting is accelerated by electrolytes and acids.
– Rusting also involves pitting of the metal surface,
but the rust is deposited at a different location
from the pits.
– Iron is oxidized in one region, and oxygen is
reduced in another region. 90
Chapter 18 Notes

The Corrosion of Iron

Figure 18.27

• The surface of the iron and the droplet of water form

a tiny galvanic cell.
– Portions of the iron surface act as an anode,
where iron is oxidized. Other portions act as
cathodes, where oxygen is reduced to water.
– The water droplet itself acts as an electrolyte.
91

The Corrosion of Iron

anode: 2Fe(s) → 2Fe2+(aq) + 4e-; E° = 0.45 V
cathode: O2(g) + 4H+(aq) + 4e- → 2H2O(l); E° = 1.23 V

• When Fe2+ ions migrate away from the pitted anode

region, they come in contact with O2 dissolved in the
water droplet and are oxidized to Fe3+ ions:
4Fe2+(aq) + O2(g) + 4H+(aq) → 4Fe3+(s) + 2H2O

• The Fe3+ ions form a very insoluble hydrated oxide,

which is deposited as red-brown rust:
2Fe3+(aq) + 4H2O(g) → 4Fe2O3•H2O(s) + 6H+(aq)
92
ACT: Corrosion Activity
Chapter 18 Notes

The Corrosion of Iron

• Ionic compounds dissolved in the water accelerate
the rusting process by increasing the conductivity of
the electrolyte solution; this is a problem in areas
where salt is used to melt ice on the roads, and is a
big problem in ocean-going vessels.
• Rusting also occurs faster at lower pH.
• Many other metals, such as Al, Mg, Cr, Ti, and Zn,
form hard, impenetrable metal oxide coatings when
they oxidize, which prevent any further corrosion.
Iron(III) oxide is too porous to shield the underlying
metal from further oxidation.

93

Preventing Corrosion
• The corrosion of iron can be prevented or minimized
by shielding the metal surface from oxygen and
moisture with paint, or by coating the iron with a
more durable metal such as Cr, Sn, or Zn.
• Galvanized iron is produced by dipping iron into
molten zinc. When oxidation occurs, Zn is oxidized
instead of Fe, since Zn has a lower reduction
potential. (Zn also reduces Fe2+ back to Fe.)
– The zinc oxide does not flake off the metal
surface, and forms a protective coating.

Fe2+ + 2e- h Fe(s); E° = -0.44

Zn2+ + 2e- h Zn(s); E° = -0.76

94
Chapter 18 Notes

Preventing Corrosion
• Protecting a metal from corrosion by connecting it to
a more easily oxidized metal is called cathodic
protection.
– It is not always necessary to coat the entire metal
surface, as long as there is electrical contact with
the second metal.
– Underground iron pipelines or propellers on boats
can be protected by placing them in contact with
Mg, which is more easily oxidized, and acts as a
sacrificial anode.

95

Preventing Corrosion
• If iron is in contact with a less active metal, such as
copper, the iron anodic action is improved, and will
corrode more rapidly (since Fe2+ is lost only at the
anode).
– When iron plumbing is connected directly to
copper plumbing with no electrical insulation
between them, the iron pipe corrodes rapidly.

Figure 21.16 96
Chapter 18 Notes

Electrolytic Cells

97

Galvanic vs. Electrolytic Cells

• Galvanic cells use spontaneous redox reactions (E >
0; ΔG < 0) to generate electricity.
– Chemical energy is converted to electrical energy
as the reaction proceeds toward equilibrium.
• Electrolytic cells use electric current from an
external source to drive a nonspontaneous redox
reaction (E < 0; ΔG > 0).
– Electrical energy in converted to chemical energy
as the reaction proceeds away from equilibrium.

Reaction Type Ecell ΔG Cell Type

Spontaneous + - Galvanic
Nonspontaneous - + Electrolytic
Equilibrium 0 0 Dead Battery 98
Chapter 18 Notes

Galvanic vs. Electrolytic Cells

99
Figure 18.22

Electrolytic Cells and Electrolysis

• The process of using an electric current to bring
about chemical change is called electrolysis.
Electrolysis can be performed on pure substances
(molten salts, water), mixtures of molten salts, or
aqueous solutions of salts.
– In an electrolytic cell, oxidation occurs at the
anode, and reduction occurs at the cathode.
– The cathode is negative and the anode is positive.
(Current is supplied to the cathode by the battery,
and electrons are pulled out of the anode by the
battery).
• A rechargeable battery functions as a galvanic cell
when it is operating (i.e., supplying current), but as
an electrolytic cell when it is being recharged.
100
Chapter 18 Notes

Electrolysis of Molten Salts

• If a pure molten salt is subjected to electrolysis, the
cation will be reduced at the cathode and the anion
will be oxidized at the anode.

Anode: 2Cl-(l) → Cl2(g) + 2e-

Cathode: Na+(l) + e- → Na(s)
Overall: 2Na+(l) + 2Cl-(l) → 2Na(s) + Cl2(g)

• The electrolyte is the molten salt itself.

– Na+ is attracted to the negative electrode, and Cl-
is attracted to the positive electrode.
– The moving charges allow current to flow
through the molten salt, completing the circuit.
101

Electrolysis of Molten Salts

102
Figure 18.23
Chapter 18 Notes

Electrolysis of Mixed Molten Salts

• When there are two or more molten salts present in
an electrolytic cell:
– the more easily oxidized species (stronger
reducing agent) reacts at the anode (oxidation).
– the more easily reduced species (stronger
oxidizing agent) reacts at the cathode (reduction).
• In determining which potential oxidations and
reductions take place, we cannot use the table of
reduction potentials, since these are determined for
aqueous ions. Instead, we have to rely on our
knowledge of periodic atomic trends to predict
which species will gain or lose electrons more
easily.

103

Examples: Electrolysis of Molten Salts

18. In the electrolysis of molten MgBr2, what products
form at the anode and cathode?

104
Chapter 18 Notes

Examples: Electrolysis of Molten Salts

19. A chemical engineer melts a naturally occurring
mixture of NaBr and MgCl2 and decomposes it in
an electrolytic cell. Predict the substance formed at
each electrode, and write balanced half-reactions
and the overall cell reaction. (sim. to Ex. 18.9a)

105

Examples: Electrolysis of Molten Salts

20. Metallic potassium was first prepared in 1807 by
Humphrey Davy by the electrolysis of molten
potassium hydroxide. For this cell, label the anode
and cathode, and show the direction of ion flow,
and write balanced equations for the anode,
cathode, and overall cell reactions.

106
Chapter 18 Notes

Electrolysis of Water
• The electrolysis of water is usually carried out in the
presence of a nonreacting salt, such as Na2SO4, since
pure water does not carry electrical currents well.
Anode (oxidation):
2H2O(l) → O2(g) + 4H+(aq) + 4e- -E = -0.82 V
Cathode (reduction):
2H2O(l) + 2e- → H2(g) + 2OH-(aq) E = -0.41 V
Overall:
2H2O(l) → 2H2(g) + O2(g) E = -1.23 V
• Since the cell is not at standard conditions, the
potentials are calculated from the Nernst equation.

107

Electrolysis of Water

108
Figure 18.20
Chapter 18 Notes

Electrolysis of Aqueous Salt Solutions

• When predicting the electrolysis products of an
aqueous ionic solution, it is necessary to consider
that water is also present, and may be reduced or
oxidized instead of the ionic compound.
• For example, in an ionic solution of NaI, there are
two processes that can potentially take place at the
anode and cathode:
Anode:
Oxidation of I-:
2I-(aq) → I2(s) + 2e- -E° = -0.54 V
Oxidation of water:
2H2O(l) → O2(g) + 4H+(aq) + 4e- -E = -0.82 V
Oxidation of I- takes place. 109

Electrolysis of Aqueous Salt Solutions

Cathode:
Reduction of Na+:
Na+(aq) + e- → Na(s) E° = -2.71 V
Reduction of water:
2H2O(l) + 2e- → H2(g) + 2OH-(aq) E = -0.41 V
Reduction of water takes place.

Overall Reaction:
2I-(aq) + 2H2O(l) → I2(s) + H2(g) + 2OH-(aq)

110
Chapter 18 Notes

Electrolysis of Aqueous Salt Solutions

111
Figure 18.24

Electrolysis of Aqueous Salt Solutions

• If electrolysis were performed on aqueous KNO3:
Anode:
Oxidation of NO3-: can’t be done
Oxidation of water:
2H2O(l) → O2(g) + 4H+(aq) + 4e- -E = -0.82 V
Oxidation of H2O takes place.
Cathode:
Reduction of K+:
K+(aq) + e- → K(s) E° = -2.93 V
Reduction of water:
2H2O(l) + 2e- → H2(g) + 2OH-(aq) E = -0.41 V
Reduction of water takes place.
Overall Reaction:
2H2O(l) → 2H2(g) + O2(g) 112
Chapter 18 Notes

Electrolysis of Aqueous Salt Solutions

113

Electrolysis of Aqueous Salt Solutions

• Sometimes unexpected products are obtained,
however. When gases are produced at electrodes, an
additional voltage called the overvoltage is required
to overcome the kinetic factors (such as high Eact).
– E.g., in the electrolysis of NaCl, H2 forms at the
cathode and Cl2 forms at the anode, even through
a comparison of electrode potentials would seem
to indicate that O2 should form:
Oxidation of water:
2H2O(l) → O2(g) + 4H+(aq) + 4e- -E = -0.82 V
(~ -1.4 V with overvoltage)
Oxidation of Cl-:
2Cl-(aq) → Cl2(g) + 2e- -E° = -1.36 V
114
Chapter 18 Notes

Electrolysis of Aqueous Salt Solutions

• In general, cations of less active metals are reduced
to the neutral metal, such as Au, Ag, Cu, Cr, Pt, and
Cd.
• More active metals are not reduced, such as those of
Group I, Group II, and Al. Water is reduced to H2
and OH- instead.
• Anions that are oxidized include the halides (except
F-.)
• Anions that are not oxidized include F-, SO42-, NO3-,
and PO43-. Water is oxidized to O2 and H+ instead.

115

Examples: Predicting Electrolysis Products

21. Predict the half-cell reactions that occur when
aqueous solutions of the following salts are
electrolyzed in a cell with inert electrodes. What is
the overall cell reaction in each case? (sim. to Ex.
18.9a)
a. KBr
b. AgNO3
c. MgSO4
d. CuSO4

116
Chapter 18 Notes

The Stoichiometry of Electrolysis

• Faraday’s law of electrolysis — the amount of
substance produced at each electrode is directly
proportional to the quantity of charge flowing
through the cell. (Michael Faraday, 1830s)
• In order to calculate how much charge is needed to
produce a given amount of material:
– Balance the half-reaction to find the number of
moles of electrons needed per mole of product.
– Use the Faraday constant (F = 9.65 × 104 C/mol
e-) to find the corresponding charge.
– Use the molar mass the find the charge needed for
a given mass of product.

117

The Stoichiometry of Electrolysis

• The amount of charge flowing through the cell is
determined from the current, measured in amperes
(A):
1A = 1C/s
• Thus, current multiplied by time gives the charge:
A × s = C/s × s = C

118
Chapter 18 Notes

Examples: Stoichiometry and Electrolysis

22. How many minutes will it take for a current of 10.0
A to deposit 3.00 g of gold from a solution of
AuCl3?

119

Examples: Stoichiometry and Electrolysis

23. How many grams of copper are deposited on the
cathode of an electrolytic cell if an electric current
of 2.00 A is run through a solution of CuSO4 for a
period of 20.0 min? (sim. to Ex. 18.10)

120
Chapter 18 Notes

Examples: Stoichiometry and Electrolysis

24. What current must be supplied to deposit 3.00 g of
gold from a solution of AuCl3 in 20.0 min?

121

122
Chapter 18 Notes

Industrial
Applications of
Electrolysis

123

Manufacture of Sodium

Sodium metal is produced in a Downs cell from a mixture of

sodium chloride and calcium chloride; the cell is designed to
keep the sodium metal separate from the chlorine gas, or they
will recombine (violently!). 124
Chapter 18 Notes

Manufacture of Chlorine and Sodium Hydroxide

The production of Cl2 gas and NaOH by electrolysis is the basis

of the chlor-alkali industry, which generates sales of about $4
billion in the US alone. Saturated NaCl(aq) is oxidized in the
anode compartment to produce Cl2; water is reduced in the
cathode compartment to OH-; Na+ from the anode compartment
moves by osmosis through a cation-permeable membrane to the
cathode compartment, maintaining neutrality and thereby
producing sodium hydroxide. 125

Manufacture of Aluminum

Aluminum is the third most abundant element in the crust

(8.3%), usually in the form of the ore bauxite (Al2O3). Al used
to be extremely valuable because of the difficulty in extracting
Al metal from the ore. Now, Al is produced using the Hall-
Héroult process by dissolving bauxite in molten cryolite
(Na3AlF6), and subjecting it to electrolysis. Al3+ is reduced to
Al, and the liquid metal is drained off, cooled, and rolled into
plates, sheets, or foil. This process made the production of Al
much more cost-effective, but still requires large amounts of
126
electricity (n=3: 1 mol e- produces 9.0 g Al).
Chapter 18 Notes

Electroplating
In electroplating, a 0.03 to 0.05
mm coating of one metal is
deposited on another metal. In
this illustration, silver dissolves
from a solid Ag bar (the anode)
and is deposited as solid silver on
a fork (the cathode).
Electroplating can be used to
provide a variety of protective or
decorative metal surfaces, such as
chrome (Cr), galvanized metal
(Zn), gold, silver, etc.

127

Refining of Copper

Copper can be obtained from ore in 99% purity, but this is not
good enough to use in wire. Impure copper is used as the anode,
and a sheet of very pure copper is used as the cathode; Cu
dissolves at the anode, and plates out as pure copper at the
cathode. Other easily oxidized metal ions, such as Zn2+ and Fe2+
remain in solution, and less easily oxidized metals fall to the
bottom of the cell as anode mud. The anode mud contains such
“impurities” as silver, gold, and platinum. 128
Chapter 18 Notes

Equation Summary
• Cell Potentials:
E°cell = E°red + (-E°ox)
• Thermodynamics:
0.0592 V
ΔG° = - nFE°cell o
Ecell = log K
n

129

Equation Summary
• The Nernst equation:
0.0592 V
Ecell = Ecell
o
- log Q (at 25o C)
n

• Electrolysis:
1A=1C/s 1V=1J/C
1 mol e- = 9.65×104 C (F, Faraday constant)

130