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Chapter 13
Chapter 13
Tom Holme
www.cengage.com/chemistry/brown
Chapter 13
Electrochemistry
2
Chapter Objectives
• Use standard reduction potentials to predict the spontaneous
direction of a redox reaction.
4
Corrosion
• Different metals corrode differently.
5
Corrosion
7
Oxidation-Reduction and Half-Reactions
8
Oxidation-Reduction and Half-Reactions
10
Oxidation-Reduction and Half-Reactions
• For the reaction between silver cation and copper metal, two
half-reactions are written.
• One for the oxidation of copper and one for the reduction
of silver.
• Neither half-reaction can occur without the other.
Cu 2+ (aq) + 2e
Cu(s)
2Ag + (aq) + 2e
2Ag(s)
11
Oxidation-Reduction and Half-Reactions
Cu 2+ (aq) + 2e
Cu(s)
2Ag + (aq) + 2e
2Ag(s)
Cu(s) + 2Ag + (aq)
Cu 2+ (aq) + 2Ag(s)
12
Oxidation-Reduction and Half-Reactions
13
Building a Galvanic Cell
• A galvanic cell is any electrochemical cell in which a
spontaneous chemical reaction can be used to generate an
electric current.
• The name electrochemistry comes from the observation of
electric currents in galvanic cells.
14
Building a Galvanic Cell
• Current flows by the migration of ions in solution.
15
Building a Galvanic Cell
• For a salt bridge composed of NH4Cl:
• NH4+ will flow into the Ag+ beaker to offset the removal of
Ag+ from solution.
• Cl– will flow into the Cu2+ beaker to offset the production of
Cu2+ in solution.
16
Building a Galvanic Cell
18
Terminology for Galvanic Cells
• General form of cell notation
anode | anode electrolyte || cathode electrolyte | cathode
• For the previous example of copper and silver
19
Atomic Perspective on Galvanic Cells
20
Atomic Perspective on Galvanic Cells
22
Galvanic Corrosion and Uniform Corrosion
25
Cell Potentials
• The relative corrosivities of various plated steels can be
expressed as cell potential.
26
Measuring Cell Potential
• When a voltmeter is connected to the previously described
copper/silver cell, a potential of 0.462 V is measured.
• Connecting the copper half-cell to a reducing iron(III)/iron(II)
half-cell, a cell potential of 0.434 V is measured.
• Connecting the iron(III)/iron(II) half-cell to the silver half-cell
results in a cell potential of 0.028.
• For the three cell potentials measured, the fact that 0.462 V =
0.434 V + 0.028 V suggests two things:
• The behavior of cell potentials is akin to state functions.
• If a specific standard electrode is chosen, comparison to
all other electrodes will result in a practical system for
determining cell potential.
27
Measuring Cell Potential
30
Measuring Cell Potential
• For some galvanic cells, the SHE acts as the anode and for
other galvanic cells, the SHE acts as the cathode.
31
Measuring Cell Potential
• When the SHE is always connected to the positive terminal,
the sign of the potential tells us the direction of the redox
reaction.
32
Measuring Cell Potential
34
Standard Reduction Potentials
36
Standard Reduction Potentials
• All potentials are measured with a SHE connected to the
negative terminal.
37
Standard Reduction Potentials
• The tendency for the chemicals involved in a half-reaction to
be an oxidation or reduction depends on the value of the
reduction potential.
38
Standard Reduction Potentials
• For a galvanic cell, the half-reaction with the more positive
reduction potential will be the cathode.
• The half-reaction with the more negative reduction
potential will be the anode.
E o
cell Eo
red E o
ox
39
Standard Reduction Potentials
40
Example Problem 13.1
• Using standard reduction potentials, identify the anode and
the cathode and determine the cell potential for a galvanic cell
composed of copper and iron. Assume standard conditions.
41
Nonstandard Conditions
• The cell potential at nonstandard conditions is calculated
using the Nernst equation.
RT
EE o
ln Q
nF
42
Example Problem 13.2
• Assume that you have a cell that has an iron(II) concentration
of 0.015 M and an H+ concentration of 1.0 10-3 M. The cell
temperature is 38ºC, and the pressure of hydrogen gas is
maintained at 0.04 atm. What would the cell potential be
under these conditions?
43
Cell Potentials and Free Energy
• Corrosion is a spontaneous process and has a negative
Gibbs free energy change.
Go nFE o
• n is the number of electrons transferred and F is Faraday’s
constant.
• The minus sign in required because a galvanic cell has a
positive cell potential, spontaneously generates electrical
work, and thus must have a negative G value.
44
Example Problem 13.3
• Suppose that we wish to study the possible galvanic corrosion
between zinc and chromium, so we set up the following cell:
• What is the chemical reaction that takes place and what is the
standard free energy change for that reaction?
45
Equilibrium Constants
• The cell potential can be used to calculate the equilibrium
constant for an electrochemical reaction.
RT
E
o
ln K
nF
• n is the number of electrons transferred, R is the universal
gas law constant, and F is Faraday’s constant.
46
Equilibrium Constants
• The relationship between the cell potential and the equilibrium
constant can be re-written in terms of the common (base 10)
log.
2.303RT
E
o
log K
nF
0.0592 V
E
o
log K
n
47
Equilibrium Constants
• The equilibrium
constant increases
as the cell potential
and number of
electrons transferred
increases.
48
Batteries
• A battery is a cell or series of cells that generate an electrical
current.
49
Primary Cells
• Single-use batteries that cannot be recharged are primary
cells, or primary batteries.
• The most prevalent type of primary cell is the alkaline
battery.
• The chemistry of an
alkaline dry cell battery.
The net reaction is shown
above.
51
Primary Cells
• Mercury batteries are another type of primary cell and are quite
small. They are used for medical devices like pacemakers.
• Zinc is the anode.
Zn(s) + 2OH (aq)
Zn(OH)2 (s) + 2e
NiO(OH)(s) + H2O(l ) + e
Ni(OH)2 (s) + OH (aq)
54
Secondary Cells
NiO(OH)(s) + H2O(l ) + e
Ni(OH)2 (s) + OH (aq)
57
Secondary Cells
• The lead-acid storage battery found in cars is a secondary
cell.
• The anode for a lead-acid battery is lead metal.
Pb(s) + HSO4 (aq)
PbSO4 (s) + H+ (aq) + 2e
• The cathode for a lead-acid battery is lead oxide.
PbO2 (s) + 3H+ (aq) + HSO4 (aq) + 2e
PbSO4 (s) + 2H2O(l )
58
Fuel Cells
• A fuel cell is a voltaic cell in which the reactants can be
supplied continuously and the products of the cell reaction are
continuously removed.
• Most common type is based on the reaction of hydrogen and
oxygen to produce water.
2H2 O2 2H2O
• Oxygen is reduced at the cathode.
O2 4H 4e 2H2O
• Hydrogen is oxidized at the anode.
H2 2H 2e
59
Limitations of Batteries
• Corrosion is a major cause for the loss of performance in
batteries.
60
Electrolysis
• Electrolysis is the process of passing an electric current
through an ionic solution or molten salt to produce a chemical
reaction.
63
Active Electrolysis and Electroplating
64
Active Electrolysis and Electroplating
• Anode
Ag(s) + 2CN (aq)
Ag(CN)2 (aq) + e
• Cathode
Ag(CN)2 (aq) + e
Ag(s) + 2CN (aq)
• Opposite reactions at the anode and cathode are common for
electroplating operations.
• Silver is transferred from the anode to the cathode, coating the
cathode in a thin layer of silver.
• The zero cell potential is not critical since an external current
drives electrolysis.
65
Active Electrolysis and Electroplating
66
Electrolysis and Stoichiometry
• For electroplating, it can be vitally important to use carefully
controlled amounts of materials.
67
Current and Charge
• When current is measured in an electric circuit, the
observation is the flow of charge for a period of time.
68
Current and Charge
• Using Faraday’s constant, F = 96,485 C mol-1 and the
calculated charge, the number of moles of electrons that pass
through the circuit can be calculated.
69
Example Problem 13.4
• In a process called flash electroplating, a current of
2.5 x 103 A passes through an electrolytic cell for
5.00 minutes. How many moles of electrons are
driven through the cell?
70
Example Problem 13.5
• Suppose that a batch of parts is plated with copper in an
electrolytic bath running at 0.15 V and 15.0 A for exactly 2
hours. What is the energy cost of this process if the electric
utility charges the company $0.0500 per kWh?
71
Calculations Using Masses of Substances in Electrolysis
72
Example Problem 13.6
• An electrolysis cell that deposits gold (from Au+(aq)) operates
for 15.0 minutes at a current of 2.30 A. What mass of gold is
deposited?
73
Example Problem 13.7
• Suppose that you have a part that requires tin coating. You’ve
calculated that you need to deposit 3.60 g of tin to achieve an
adequate coating. If your electrolysis cell (using Sn2+) runs at
2.00 A, how long must you operate the cell to obtain the
desired coating?
74
Corrosion Prevention
• The following observations can be used to reduce corrosion in
a number of ways.
76
Coatings
• Rust inhibitors can be added to paint to further inhibit
corrosion.
77
Cathodic Protection
• Some materials are more easily oxidized than iron, which
provides a way to construct galvanic corrosion conditions
intended to protect the iron.
• Mg has a reduction potential more negative than Fe.
• When combined, Mg will oxidize and Fe will be reduced.
80