Chemistry General: Chapter 20: Electrochemistry

Petrucci • Harwood • Herring • Madura
GENERAL
Ninth
Edition
CHEMISTRY
Principles and Modern Applications
Chapter 20: Electrochemistry
Philip Dutton
University of Windsor, Canada
Prentice-Hall © 2007
Slide 1 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

Contents
20-1 Electrode Potentials and Their Measurement
20-2 Standard Electrode Potentials
20-3 Ecell, ΔG, and Keq
20-4 Ecell as a Function of Concentration
20-5 Batteries: Producing Electricity Through
Chemical Reactions
20-6 Corrosion: Unwanted Voltaic Cells
20-7 Electrolysis: Causing Non-spontaneous Reactions
to Occur
20-8 Industrial Electrolysis Processes
 Focus On Membrane Potentials
20-1 Electrode Potentials and
Their Measurement
Cu(s) + 2Ag+(aq) Cu(s) + Zn2+(aq)
Cu2+(aq) + 2 Ag(s) No reaction

An Electrochemical Half Cell
Anode
Cathode

An Electrochemical Cell

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
(usually a salt bridge) shown by ||.

Terminology
Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)

Ecell = 1.103 V

Terminology
 Galvanic 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)

Standard Hydrogen Electrode
2 H+(a = 1) + 2 e- H2(g, 1 bar) E° = 0 V
Pt|H2(g, 1 bar)|H+(a = 1)

Standard Electrode Potential, E°
 E° defined by international agreement.

 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).

Reduction Couples
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

Standard Cell Potential
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

Measuring Standard Reduction Potential
anode cathode cathode anode

Standard Reduction Potentials

20-3 Ecell, ΔG, and Keq
 Cells do electrical work. elec = -nFE

 Moving electric charge.
Michael Faraday 1791-1867
 Faraday constant,
F = 96,485 C mol-1
ΔG = -nFE
ΔG° = -nFE°

Combining Half Reactions
Fe3+(aq) + 3e- → Fe(s) E°Fe3+/Fe = ?
Fe2+(aq) + 2e- → Fe(s) E°Fe2+/Fe = -0.440 V ΔG° = +0.880 J
Fe3+(aq) + e- → 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 V
ΔG° = +0.109 V = -nFE°
E°Fe3+/Fe = +0.109 V /(-3F) = -0.0363 V

Spontaneous Change
 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 = -nFE°cell
RT
E°cell = ln Keq
nF

Summary of Thermodynamic, Equilibrium
and Electrochemical Relationships.

20-4 Ecell as a Function of Concentration
ΔG = ΔG° -RT ln Q
-nFEcell = -nFEcell° -RT ln Q
RT
Ecell = Ecell° - ln Q
nF
Convert to log10 and calculate constants.
0.0592 V
The Nernst Equation: Ecell = Ecell° - log Q
n

EXAMPLE 20-8
Applying the Nernst Equation for Determining Ecell. What
is the value of Ecell for the voltaic cell pictured below and
diagrammed as follows?
Pt|Fe2+(0.10 M),Fe3+(0.20 M)||Ag+(1.0 M)|Ag(s)

EXAMPLE 20-8
0.0592 V
Ecell = Ecell° - log Q
n
0.0592 V [Fe3+]
Ecell = Ecell° - log
n [Fe2+] [Ag+]
Ecell = 0.029 V – 0.018 V = 0.011 V
Pt|Fe2+(0.10 M),Fe3+(0.20 M)||Ag+(1.0 M)|Ag(s)
Fe2+(aq) + Ag+(aq) → Fe3+(aq) + Ag (s)

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)

Concentration Cells
0.0592 V
Ecell = Ecell° - log Q 2 H+(1 M) → 2 H+(x M)
n
0.0592 V x2
Ecell = Ecell° - log 2
n 1
0.0592 V x2
Ecell = 0 - log
2 1
Ecell = - 0.0592 V log x
Ecell = (0.0592 V) pH

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)

EXAMPLE 20-10
Using a Voltaic Cell to Determine Ksp of a Slightly Soluble
Solute. With the date given for the reaction on the previous
slide, calculate Ksp for AgI.
AgI(s) → Ag+(aq) + I-(aq)
Let [Ag+] in a saturated Ag+ solution be x:

Ag+(0.100 M) → Ag+(sat’d M)
0.0592 V 0.0592 V [Ag+]sat’d AgI

Ecell = Ecell° - log Q = Ecell° - log
n n [Ag+]0.10 M soln

EXAMPLE 20-10
0.0592 V [Ag+]sat’d AgI
n [Ag+]0.10 M soln
0.0592 V x
n 0.100
0.0592 V
0.417 = 0 - (log x – log 0.100)
1
0.417
log x = log 0.100 - = -1 – 7.04 = -8.04
0.0592
x = 10-8.04 = 9.110-9 Ksp = x2 = 8.310-17

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.

The Leclanché (Dry) Cell

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)

Alkaline Dry 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-

Lead-Acid (Storage) Battery
 The most common secondary battery.

Lead-Acid Battery
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

The Nickel-Cadmium Cell
Cd(s) + 2 NiO(OH)(s) + 2 H2O(L) → 2 Ni(OH)2(s) + Cd(OH)2(s)

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
 = ΔG°/ ΔH° = 0.83

Air Batteries
4 Al(s) + 3 O2(g) + 6 H2O(l) + 4 OH- → 4 [Al(OH)4](aq)

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

Corrosion

Corrosion Protection

Corrosion Protection

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

Predicting Electrolysis Reaction
 An Electrolytic Cell
 e- is the reverse of the
voltaic cell.
 Battery must have a
voltage in excess of
1.103 V in order to force
the non-spontaneous
reaction.

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

Chlor-Alkali Process

Focus On Membrane Potentials

Nernst Potential, Δ

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.

Contoh Soal
 Arus listrik yang sama dialirkan melalui larutan
CuCl2 dan larutan CrCl3 (Ar Cu = 64, Ar Cr = 52).
Jika diperoleh 3,2 gram tembaga, berapa berat
logam krom yang diendapkan?
 Jawab:
 Cu2+ + 2e  Cu; Cr3+ + 3e  Cr
 mol Cr = 2/3 mol Cu = (2/3)(3,2/64)
= (2/3)(0,05) = 0,1/3
 mCr = (0,1/3)52 = 1,73 g

Contoh Soal
 Larutan garam platina dielektrolisis dengan arus
2,5 A selama 2 jam. Hasilnya berupa 18,18 gram
logam Pt yang mengendap pada katoda. Hitunglah
muatan ion (bilangan oksidasi) Pt dalam larutan
ini! (Ar Pt = 195; ℱ = 96.500 C)
 Jawab:
 Muatan = (2,5 A)(7200detik) = 18000C
 Mol electron = 18000/96500 = 0,18 mol
 Mol Pt = 18,18/195 = 0,09
 Muatan Pt = mol electron/mol Pt = 0,18/0,09 = 2

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Petrucci • Harwood • Herring • Madura

Chapter 20: Electrochemistry

Slide 1 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

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

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

Slide 3 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

Slide 4 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

Slide 5 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

 Electromotive force, Ecell.

Slide 6 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)

Slide 7 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

Slide 8 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

 Cell voltages, the potential differences between

The Standard Hydrogen Electrode (SHE)

Slide 9 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

Slide 10 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

 E° defined by international agreement.

Slide 11 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

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

Standard cell potential: the potential difference of a

E°cell = E°cathode - E°anode

Slide 12 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

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 V

Slide 13 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

anode cathode cathode anode

Slide 14 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

Slide 15 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

 Cells do electrical work. elec = -nFE

Slide 18 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

Fe2+(aq) + 2e- → Fe(s) E°Fe2+/Fe = -0.440 V ΔG° = +0.880 J

Fe3+(aq) + e- → 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 V

ΔG° = +0.109 V = -nFE°

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

Slide 19 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

 ΔG < 0 for spontaneous change.

Slide 20 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

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 21 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

ΔG° = -RT ln Keq = -nFE°cell

Slide 22 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

Slide 23 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

-nFEcell = -nFEcell° -RT ln Q

Convert to log10 and calculate constants.

Slide 24 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

Slide 25 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007

Ecell = 0.029 V – 0.018 V = 0.011 V

Pt|Fe2+(0.10 M),Fe3+(0.20 M)||Ag+(1.0 M)|Ag(s)

Fe2+(aq) + Ag+(aq) → Fe3+(aq) + Ag (s)

Slide 26 of 54 General Chemistry: Chapter 20 Prentice-Hall © 2007