5 Electrochemistry

Chapter 18
Electrochemistry
Chapter 18
Table of Contents
18.1 Balancing Oxidation–Reduction Equations
18.2 Galvanic Cells
18.3 Standard Reduction Potentials
18.4 Cell Potential, Electrical Work, and Free Energy
18.5 Dependence of Cell Potential on Concentration
18.6 Batteries
18.7 Corrosion
18.8 Electrolysis
18.9 Commercial Eletrolytic Processes
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Section 18.1
Balancing Oxidation–Reduction Equations
Review of Terms
• 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
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Section 18.1
Half–Reactions
• The overall reaction is split into two half–

reactions, one involving oxidation and one
reduction.
8H+ + MnO4– + 5Fe2+ → Mn2+ + 5Fe3+ + 4H2O
Reduction: 8H+ + MnO4– + 5e– → Mn2+ + 4H2O

Oxidation: 5Fe2+ → 5Fe3+ + 5e–
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Section 18.1
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.
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Section 18.1
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.
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Section 18.1
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Section 18.1
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.
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Section 18.1
Method of Half Reactions

• Cr2O72-(aq) → 2Cr3+(aq)
• SO32-(aq) → SO42-(aq)
• How many electrons are involved in each
half reaction?
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Section 18.1
Method of Half Reactions (continued)

• 6e- + Cr2O72-(aq) → 2Cr3+(aq)
• SO32-(aq) → + SO42-(aq) + 2e-
• How can we balance the oxygen atoms?
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Section 18.1

• 6e- + Cr2O72-(aq) → Cr3+(aq) + 7H2O
• H2O +SO32-(aq) → + SO42-(aq) + 2e-
• How can we balance the hydrogen
atoms?
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Section 18.1

• This reaction occurs in an acidic solution.
• 14H+ + 6e- + Cr2O72- → 2Cr3+ + 7H2O
• H2O +SO32- → SO42- + 2e- + 2H+
• How can we balance the electrons?
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Section 18.1

• 14H+ + 6e- + Cr2O72- → 2Cr3+ + 7H2O
• 3[H2O +SO32- → SO42- + 2e- + 2H+]
• Final Balanced Equation:
Cr2O72- + 3SO32- + 8H+ → 2Cr3+ + 3SO42- + 4H2O
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Section 18.1
Exercise
Balance the following oxidation–reduction

reaction that occurs in acidic solution.
Br–(aq) + MnO4–(aq) → Br2(l)+ Mn2+(aq)
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Section 18.1
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, add a
number of OH– ions that is equal to the
number of H+ ions. (We want to eliminate
H+ by forming H2O.)
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Section 18.1
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.
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Section 18.1
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Section 18.2
Atomic Masses
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.
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Section 18.2
Atomic Masses
Galvanic Cells
A Galvanic Cell
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Section 18.2
Atomic Masses
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.
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Section 18.2
Atomic Masses
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.
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Section 18.3
The Mole Reduction Potentials
Standard
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.
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Section 18.3
Standard
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 Return to TOC

Section 18.3
Standard
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
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Section 18.3
Standard
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
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Section 18.3
Standard
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.
• 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)
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Section 18.3
Standard
Description of a Galvanic Cell
• The cell potential is 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.
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Section 18.3
Standard
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.
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Section 18.3
Standard
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)
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Section 18.3
Standard
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)
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Section 18.3
Standard
Concept Check
Consider the cell from part b.
What would happen to the potential if you

increase the [Cu2+]?
Explain.
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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.
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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–
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Section 18.5
Dependence of Cell Potential on Concentration
A Concentration Cell
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Section 18.5
Nernst Equation
• At 25°C:
0.0591
E = E − log (Q )
n
or
0.0591
E= log ( K )
n
(at equilibrium)
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Section 18.5
Concept Check
Explain the difference between E and E °.

When is E equal to zero?
When is E ° equal to zero?
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Section 18.5
Exercise
A concentration cell is constructed using two

nickel electrodes with Ni2+ concentrations of
1.0 M and 1.00 x 10-4 M in the two half-cells.
Calculate the potential of this cell at 25°C.
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Section 18.5
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.
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Section 18.6
Batteries
One of the Six Cells in a

12–V Lead Storage
Battery
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Section 18.6
Batteries
A Common Dry Cell Battery
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Section 18.6
Batteries
A Mercury Battery
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Section 18.6
Batteries
Schematic of the
Hydrogen-Oxygen Fuel
Cell
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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.
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Section 18.7
Corrosion
The Electrochemical Corrosion of Iron
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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.
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Section 18.7
Corrosion
Cathodic Protection
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Section 18.8
Electrolysis
• Forcing a current through a cell to produce a

chemical change for which the cell potential is
negative.
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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
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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
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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?
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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.
Do the metals form on the cathode or the anode?

Explain.
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Section 18.9
Commercial Electrolytic Processes
• Production of aluminum
• Purification of metals
• Metal plating
• Electrolysis of sodium chloride
• Production of chlorine and sodium hydroxide
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Section 18.9
Producing Aluminum by the Hall-Heroult Process
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Section 18.9
Electroplating a Spoon
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Section 18.9
The Downs Cell for the Electrolysis of Molten Sodium Chloride
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Section 18.9
The Mercury Cell for Production of Chlorine and Sodium
Hydroxide
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5 Electrochemistry

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Chapter 18

Copyright © Cengage Learning. All rights reserved 2

• Oxidation–reduction (redox) reaction – involves

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• The overall reaction is split into two half–

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

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

• How can we balance this equation?

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Method of Half Reactions

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Method of Half Reactions (continued)

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Method of Half Reactions (continued)

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Method of Half Reactions (continued)

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Method of Half Reactions (continued)

• Final Balanced Equation:

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

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Balance the following oxidation–reduction

Br–(aq) + MnO4–(aq) → Br2(l)+ Mn2+(aq)

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• Device in which chemical energy is changed to

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• Oxidation occurs at the anode.

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• A galvanic cell consists of an oxidizing agent in

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• All half-reactions are given as reduction

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

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Overall Balanced Cell Reaction

2Fe3+ + 2e– → 2Fe2+ E ° = 0.77 V (cathode)

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Order the following from strongest to weakest

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• Used to describe electrochemical cells.

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Description of a Galvanic Cell

• The cell potential is always positive for a

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Description of a Galvanic Cell

• Designation of the anode and cathode.

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Sketch a cell using the following solutions and

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

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Sketch a cell using the following solutions and

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

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Consider the cell from part b.

What would happen to the potential if you