Chapter 20 Petrucci

GENERAL CHEMISTRY
Principles and Modern Applications TENTH EDITION
PETRUCCI HERRING MADURA BISSONNETTE
Electrochemistry 20
PHILIP DUTTON
UNIVERSITY OF WINDSOR
DEPARTMENT OF CHEMISTRY AND
BIOCHEMISTRY
Slide 1 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

Spontaneous Change: CONTENTS
Entropy and Gibbs Energy 19-1 Electrode Potentials and Their
Measurement
19-2 Standard Electrode Potentials
19-3 Ecell, ΔG, and K
19-4 Ecell as a function of

Concentrations
19-5 Batteries: Producing Electricity
Through Chemical Reactions
19-6 Corrosion: Unwanted Voltaic

Cells
19-7 Electrolysis: Causing

Nonspontaneous Reactions to
Occur
19-8 Industrial Electrolysis Processes

20-1 Electrode Potentials and Their Measurement
Cu(s) + 2Ag+(aq) Cu(s) + Zn2+(aq)
Cu2+(aq) + 2 Ag(s) No reaction
FIGURE 20-1
Behaviour of Ag+(aq) and Zn+(aq) in the presence of copper
Anode
Cathode
FIGURE 20-2
An electrochemical half cell

FIGURE 20-3
Measurement of the electromotive force of an electrochemical cell

Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
Ecell = 1.103 V
FIGURE 20-4
The reaction Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) in an electrochemical cell

Cell Diagrams and Terminology
Electromotive force, Ecell
The cell voltage or cell potential.
Cell diagram
Shows the components of the cell in a symbolic way.
Anode (where oxidation occurs) on the left.
Cathode (where reduction occurs) on the right.
Boundary between phases shown by |.
Boundary between half cells
(commonly a salt bridge) shown by ||.

Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)
Ecell = 1.103 V
FIGURE 20-4
The reaction Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) in an electrochemical cell

Galvanic (or voltaic) cells
Produce electricity as a result of spontaneous reactions.
Electrolytic cells
Non-spontaneous chemical change driven by electricity.
Couple, M|Mn+
A pair of species related by a change in number of e-.

20-2 Standard Electrode Potentials
Cell voltages, the potential differences

between electrodes, are among the most
precise scientific measurements.
The potential of an individual electrode is
difficult to establish.
Arbitrary zero is chosen.
The Standard Hydrogen Electrode (SHE)

2 H+(a = 1) + 2 e- H2(g, 1 bar) E° = 0
V
Pt|H2(g, 1 bar)|H+(a = 1)
FIGURE 20-5
The standard hydrogen electrode (SHE)

Standard Electrode Potential, E°
E°cell = E°cathode (right) – E°anode,(left)
The tendency for a reduction process to occur at an electrode.
All ionic species present at a=1 (approximately 1 M).
All gases are at 1 bar (approximately 1 atm).
Where no metallic substance is indicated, the potential is

established on an inert metallic electrode (ex. Pt).

Cu2+(1M) + 2 e- → Cu(s) E°Cu2+/Cu = ?
Pt|H2(g, 1 bar)|H+(a = 1) || Cu2+(1 M)|Cu(s) E°cell = 0.340 V

anode cathode
Standard cell potential: the potential difference of a

cell formed from two standard electrodes.
E°cell = E°cathode - E°anode

Pt|H2(g, 1 bar)|H+(a = 1) || Cu2+(1 M)|Cu(s) E°cell = 0.340 V
E°cell = E°cathode - E°anode
E°cell = E°Cu2+/Cu - E°H+/H2
0.340 V = E°Cu2+/Cu - 0 V
E°Cu2+/Cu = +0.340 V
H2(g, 1 atm) + Cu2+(1 M) → H+(1 M) + Cu(s) E°cell = 0.340

V

anode cathode cathode anode
FIGURE 20-6
Measuring standard reduction potential

TABLE 20.1 Some Selected Standard Electrode (Reduction)
Potentials at 25°C
Reduction Half-Reaction E°, V
Acidic Solution

Potentials at 25°C (continued)
Acidic Solution

Potentials at 25°C (continued)
Acidic Solution
Basic Solution

20-3 Ecell, ΔG, and Keq
Michael Faraday 1791-1867
elec = -zFEcell
ΔG = -zFEcell
Faraday constant,
F = 96,485 C mol-1
When products are in their
standard states
ΔG° = -zFE°cell

Combining Reduction Half-Equations
Fe3+(aq) + 3e- → Fe(s) E°Fe3+/Fe = ?

can add ΔG°
Fe2+(aq) + 2e- → Fe(s) E°Fe2+/Fe = -0.440 V ΔG° = +0.880 J
Fe3+(aq) + 1e- → Fe2+(aq) E°Fe3+/Fe2+ = 0.771 V ΔG° = -0.771 J
Fe3+(aq) + 3e- → Fe(s) E°Fe3+/Fe = +0.331 V ΔG° = +0.109 J

but cannot simply add E°
ΔG° = +0.109 J = -nFE°
E°Fe3+/Fe = +0.109 J /(-3F) = -0.0363 V

Spontaneous Change in
Oxidation-Reduction Reactions
ΔG < 0 for spontaneous change.

Therefore E°cell > 0 because ΔGcell = -nFE°cell
E°cell > 0
Reaction proceeds spontaneously as written.
E°cell = 0
Reaction is at equilibrium.
E°cell < 0
Reaction proceeds in the reverse direction spontaneously.
The Behavior or Metals Toward Acids
M(s) → M2+(aq) + 2 e- E° = -E°M2+/M
2 H+(aq) + 2 e- → H2(g) E°H+/H2 = 0 V
2 H+(aq) + M(s) → H2(g) + M2+(aq)
E°cell = E°H+/H2 - E°M2+/M = -E°M2+/M
When E°M2+/M < 0, E°cell > 0. Therefore ΔG° < 0.

Metals with negative reduction potentials react with acids.

Relationship Between E°cell and Keq
ΔG° = -RT ln Keq = -zFE°cell
RT
E°cell = ln Keq
zF
0.25693 ln K
E°cell = eq
z

FIGURE 20-8
A summary of important thermodynamic, equilibrium and electrochemical
relationships under standard conditions.

20-4 Ecell as a Function of Concentration
ΔG = ΔG° - RT ln Q
-zFEcell = -zFEcell° - RT ln Q
RT
Ecell = Ecell° - ln Q
zF
FIGURE 20-9
Convert to log10 and calculate constants.
Variation of Ecell with ion concentrations
0.0592 V
Ecell = E°cell - log Q The Nernst Equation
z
Concentration Cells
Two half cells with identical electrodes but different ion concentrations.
Pt|H2 (1 atm)|H+(x M)||H+(1.0 M)|H2(1 atm)|Pt(s)
2 H+(1 M) + 2 e- → H2(g, 1 atm)
H2(g, 1 atm) → 2 H+(x M) + 2 e-
2 H+(1 M) → 2 H+(x M)
E°cell = E°H+/H2 - E°H+/H2 = 0

FIGURE 20-11
A concentration cell
2 H+(1 M) → 2 H+(x M) 0.0592 V
Ecell = Ecell° - log Q
z
E°cell = E°H+/H2 - E°H+/H2 = 0
0.0592 V x2
Ecell = Ecell° - log 2
z 1
but we can calculate 0.0592 V x2
using the Nernst Equation Ecell = 0 - log
2 1
Ecell = - 0.0592 V log x
Ecell = (0.0592 V) pH
Slide 35 of 54
53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.
Measurement of Ksp
Ag|Ag+(sat’d AgI)||Ag+(0.10 M)|Ag(s)
Ag+(0.100 M) + e- → Ag(s)
Ag(s) → Ag+(sat’d) + e-
Ag+(0.100 M) → Ag+(sat’d M)
Work Example 20-11 as an exercise to

understand the process.
FIGURE 20-12
A concentration cell for determining Ksp of AgI
Slide 38 of 54
0.22233 V
0.2680 V (sat’d KCl)

or
FIGURE 20-13 0.2412 V (1 M KCl)
Schematic diagrams of some common electrodes
Slide 40 of 54
The Glass Electrode and the Electrochemical
Measurement of pH
Ag|AgCl(s)|Cl-(1.0M),H+(1.0M)|glass membrane|H+(unknown)|| Cl-(1.0 M)|AgCl(s)|Ag(s)
Ag(s) + Cl- AgCl(s) + e-
H+(1.0 M) H+(unknown)
AgCl(s) + e- Ag(s) + Cl-(aq)
ΔG = G(unknown) – G(1.0M)
= G° + RTln[unknown] – G° - RTln(1.0)
=RTln[unknown]
E°cell = -RTln[unknown]/zF
pH = -log[unknown]=zFE°cell/RT
20-5 Batteries: Producing Electricity Through
Chemical Reactions
Primary Cells (or batteries).

Cell reaction is not reversible.
Secondary Cells.
Cell reaction can be reversed by passing
electricity through the cell (charging).
Flow Batteries and Fuel Cells.
Materials pass through the battery which converts
chemical energy to electric energy.

FIGURE 20-14
The Leclanché (dry) cell

The Leclanché Dry Cell
Oxidation: Zn(s) → Zn2+(aq) + 2 e-
Reduction: 2 MnO2(s) + H2O(l) + 2 e- → Mn2O3(s) + 2 OH-
Acid-base reaction: NH4+ + OH- → NH3(g) + H2O(l)
Precipitation reaction: NH3 + Zn2+(aq) + Cl- → [Zn(NH3)2]Cl2(s)

The alkaline cell
Reduction: 2 MnO2(s) + H2O(l) + 2 e- → Mn2O3(s) + 2 OH-
Oxidation reaction can be thought of in two steps:
Zn(s) → Zn2+(aq) + 2 e-
Zn2+(aq) + 2 OH- → Zn (OH)2(s)
Zn (s) + 2 OH- → Zn (OH)2(s) + 2 e-

The Lead-Acid (Storage) Battery
FIGURE 20
The lead-acid (storage) cell
Reduction:
PbO2(s) + 3 H+(aq) + HSO4-(aq) + 2 e- → PbSO4(s) + 2 H2O(l)
Oxidation:
Pb (s) + HSO4-(aq) → PbSO4(s) + H+(aq) + 2 e-
PbO2(s) + Pb(s) + 2 H+(aq) + HSO4-(aq) → 2 PbSO4(s) + 2 H2O(l)
E°cell = E°PbO2/PbSO4 - E°PbSO4/Pb = 1.74 V – (-0.28 V) =

2.02 V

The Silver-Zinc Cell: A Button Battery
Zn(s),ZnO(s)|KOH(sat’d)|Ag2O(s),Ag(s)
Zn(s) + Ag2O(s) → ZnO(s) + 2 Ag(s) Ecell = 1.8 V

FIGURE 20-16
The silver-zinc button (miniature) cell
The Nickel-Cadmium Cell: A Rechargeable
Battery
A rechargeable nickel-cadmium cell, or nicad battery
Cd(s) + 2 NiO(OH)(s) + 2 H2O(L) → 2 Ni(OH)2(s) + Cd(OH)2(s)

The Lithium-Ion Battery
FIGURE 20-17
The electrodes of a lithium-ion battery
The positive electrode consists of lithium cobalt(III) oxide, LiCoO2 , and the
negative electrode is highly crystallized graphite. To complete the battery an
electrolyte is needed, which can consist of an organic solvent and ions, such as
LiPF6 . The structure of LiCoO2 , and graphite electrode is illustrated in Figure 20-
17.
In the charging cycle at the positive electrode, lithium ions are released into
the electrolyte solution as electrons are removed from the electrode. To
maintain a charge balance, one cobalt(III) ion is oxidized to cobalt(IV) for
each lithium ion released.
LiCoO2(s)+Li(1-x) = 2CoO2(s) + xLi+(solvent) + x e-

C(s) + xLi+(solvent) + x e- = LixC(S)
The layered graphite electrode is shown with lithium ions (violet) intercalated. The
LiCoO2 is shown as a face-centered cubic lattice, with the oxygen atoms (red)
occupying the corners and the faces, the cobalt atoms (pink) occupying half of the
edges, and the lithium atoms occupying half of the edges and the central octahedral
hole. This arrangement leads to planes of oxygen, cobalt, oxygen, lithium, oxygen,
cobalt, and oxygen atoms, as indicated in the figure.
Fuel Cells
O2(g) + 2 H2O(l) + 4 e- → 4 OH-(aq)
2{H2(g) + 2 OH-(aq) → 2 H2O(l) + 2 e-}
2H2(g) + O2(g) → 2 H2O(l)
E°cell = E°O2/OH- - E°H2O/H2

= 0.401 V – (-0.828 V) = 1.229 V
FIGURE 20-18  = ΔG°/ ΔH° =

A hydrogen-oxygen fuel cell
0.83
Air Batteries
4 Al(s) + 3 O2(g) + 6 H2O(l) + 4 OH- → 4 [Al(OH)4](aq)
FIGURE 20-19
A simplified aluminum-air battery
20-6 Corrosion: Unwanted Voltaic Cells
In neutral solution:
O2(g) + 2 H2O(l) + 4 e- → 4 OH-(aq) EO2/OH- = 0.401 V
2 Fe(s) → 2 Fe2+(aq) + 4 e- EFe/Fe2+ = -0.440 V
2 Fe(s) + O2(g) + 2 H2O(l) → 2 Fe2+(aq) + 4 OH-(aq)

Ecell = 0.841 V
In acidic solution:
O2(g) + 4 H+(aq) + 4 e- → 4 H2O (aq) EO2/OH- = 1.229 V

• The pink color
results from the
indicator
phenolphthalein in
the presence of base.
• The dark blue color

Cu
results from the
formation of
Turnbull’s blue
KFe[Fe(CN)6].
Zn
FIGURE 20-20
Demonstration of corrosion and methods of corrosion protection

FIGURE 20-21
Protection of iron against electrolytic corrosion

Magnesium sacrificial anodes
The small cylindrical bars of magnesium attached to the steel ship
provide cathodic protection against corrosion.

20-7 Electrolysis: Causing Non-spontaneous
Reactions to Occur
Voltaic Cell:
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) EO2/OH- = 1.103 V
Electolytic Cell:
Cu(s) + Zn2+(aq) → Cu2+(aq) + Zn(s) EO2/OH- = -1.103 V

Predicting Electrolysis Reaction
An Electrolytic Cell
e- is the reverse of the
voltaic cell.
The battery must have a
voltage in excess of 1.103
V in order to force the
non-spontaneous reaction.
FIGURE 20-22
An electrolytic cell
Complications in Electrolytic Cells
Overpotential.
Competing reactions.
Non-standard states.
Nature of electrodes.

Quantitative Aspects of Electrolysis
1 mol e- = 96485 C
Charge (C) = current (C/s)  time (s)
It
ne- =
F

20-8 Industrial Electrolysis Processes
The refining of copper by electrolysis.

Electrorefining
Electroplating
Electrosynthesis
A rack of metal parts being lifted from

the electrolyte solution after
electroplating.

Chlor-Alkali Process
FIGURE 20-24 FIGURE 20-25

A diaphragm chlor-alkali cell The mercury-cell chlor-alkali process

End of Chapter Questions
Don’t just read examples, work them!!
If you write:
Information is going through your fingers,
Your muscles,
Your nerves,
Directly to your brain.
Physically experience the solution.
Your eyes and ears are not enough.

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GENERAL CHEMISTRY

Principles and Modern Applications TENTH EDITION

PETRUCCI HERRING MADURA BISSONNETTE

Slide 1 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

19-4 Ecell as a function of

19-6 Corrosion: Unwanted Voltaic

19-7 Electrolysis: Causing

Slide 2 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

Cu(s) + 2Ag+(aq) Cu(s) + Zn2+(aq)

Cu2+(aq) + 2 Ag(s) No reaction

Slide 4 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

Slide 5 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

Slide 6 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

Slide 7 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

Slide 8 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

Slide 9 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

Cell voltages, the potential differences

Slide 12 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

Slide 13 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

E°cell = E°cathode (right) – E°anode,(left)

The tendency for a reduction process to occur at an electrode.

All ionic species present at a=1 (approximately 1 M).

All gases are at 1 bar (approximately 1 atm).

Where no metallic substance is indicated, the potential is

Slide 14 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

Pt|H2(g, 1 bar)|H+(a = 1) || Cu2+(1 M)|Cu(s) E°cell = 0.340 V

Standard cell potential: the potential difference of a

E°cell = E°cathode - E°anode

Slide 15 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

E°cell = E°cathode - E°anode

E°cell = E°Cu2+/Cu - E°H+/H2

H2(g, 1 atm) + Cu2+(1 M) → H+(1 M) + Cu(s) E°cell = 0.340

Slide 16 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

Slide 17 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

Slide 18 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

Slide 19 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

Slide 20 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

Slide 23 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

Fe3+(aq) + 3e- → Fe(s) E°Fe3+/Fe = ?

Fe3+(aq) + 1e- → Fe2+(aq) E°Fe3+/Fe2+ = 0.771 V ΔG° = -0.771 J

Fe3+(aq) + 3e- → Fe(s) E°Fe3+/Fe = +0.331 V ΔG° = +0.109 J

ΔG° = +0.109 J = -nFE°

E°Fe3+/Fe = +0.109 J /(-3F) = -0.0363 V

Slide 24 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

ΔG < 0 for spontaneous change.

M(s) → M2+(aq) + 2 e- E° = -E°M2+/M

2 H+(aq) + 2 e- → H2(g) E°H+/H2 = 0 V

2 H+(aq) + M(s) → H2(g) + M2+(aq)

E°cell = E°H+/H2 - E°M2+/M = -E°M2+/M

When E°M2+/M < 0, E°cell > 0. Therefore ΔG° < 0.

Slide 28 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

ΔG° = -RT ln Keq = -zFE°cell

Slide 30 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

Slide 31 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

2 H+(1 M) + 2 e- → H2(g, 1 atm)

H2(g, 1 atm) → 2 H+(x M) + 2 e-

E°cell = E°H+/H2 - E°H+/H2 = 0

Work Example 20-11 as an exercise to

0.2680 V (sat’d KCl)

Ag(s) + Cl- AgCl(s) + e-

Primary Cells (or batteries).

Slide 42 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.

Slide 43 of 53 General Chemistry: Chapter 20 Copyright © 2011 Pearson Canada Inc.