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Module 7:
Oxidation-reduction reactions and
transformation of chemical energy
Oxidation-reduction reactions (oxidation-reduction
reactions, redox pair, balancing redox reactions,
oxidation-reduction potential).
Transformation of chemical energy into electric energy
(electrolysis, battery, galvanic corrosion and
preventing galvanic corrosion).
Exercise
Write each of the following formula unit equations as a net ionic
equation if the two differ. Which ones are redox reactions? For
the redox reactions, identify the oxidizing agent, the reducing
agent, the species oxidized, and the species reduced.
Ans
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Balancing half-reactions
Each half-reaction can be balanced independently. This is done
in four steps, which must be done in the order listed:
a. Balance all elements except oxygen and hydrogen by adjusting
stoichiometric coefficients.
b. Balance oxygen by adding H2O to the side that is deficient in
oxygen.
c. Balance hydrogen without unbalancing oxygen, as follows:
Unless the solution is basic, add H3O+ cations to the side that is
deficient in hydrogen and an equal number of H2O molecules to
the other side. If the solution is basic, add H2O to the side that is
deficient in hydrogen and an equal number of OH- anions to the
other side.
d. Balance net charge by adding electrons to the side that has the
more positive (less negative) netcharge.
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Exercise
Ans:
Iron half-reaction: Fe2+ Fe3+
Steps a, b, c: Iron is already balanced, and neither
oxygen nor hydrogen is present.
Step d: The net charge on the left is +2, and on the right
it is +3. The charge on the right needs to be made less
positive: To balance the charges, add one electron on the
right: Fe2+ Fe3+ + 1e-
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Exercise
Now for the chromium half-reaction: Cr2O72- Cr3+
Step a: to balance chromium, give Cr3+ a coefficient of 2:
Cr2O72- 2Cr3+
Step b: there are seven oxygen atoms on the left, so add seven
water molecules on the right
Cr2O72- 2Cr3+ + 7 H2O
Step c: the solution is identified as a aqueous, so it is not basic.
There are 14 hydrogen atoms on the right, requiring 14 H3O+ ion
on the left and 14 addition H2O molecules on the right:
14 H3O+ + Cr2O72- 2Cr3+ + 21 H2O
Step d: the left-hand side has 14 (+1) + 1 (-2) = +12 charge. The
right-hand side has 2 (+3) = +6 charge. Charge balance requires
six electrons on the left.
14 H3O+ + Cr2O72- + 6e- 2Cr3+ + 21 H2O
13
O+
+ Cr2O7
2-
Electrochemistry
Electrolytic cells
The chemical reaction involved in an electrolytic cell is
nonspontaneous.
Electric current is used to drive the reaction.
This process is called electrolysis and hence the name,
electrolytic cell.
The reaction involves the transfer of electrons and thus it is a
redox reaction.
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Exercise
Calculate the mass of copper metal produced during the
passage of 2.5 amperes of current through a solution of
copper(II) sulfate for 50 minutes.
Ans:
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13
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14
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To maintain electroneutrality and complete the circuit, two Clions from the salt bridge migrate into the anode solution for
every Zn2+ ion formed. Two K+ ions migrate into the cathode
solution to replace every Cu2+ ion reduced.
As the reaction proceeds, the cell voltage decreases. When the
cell voltage reaches zero, the reaction has reached equilibrium,
and no further net reaction occurs.
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2.
3.
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Corrosion
Ordinary corrosion is the redox process
by which metals are oxidized by oxygen,
O2, in the presence of moisture.
Corrosion is responsible for the loss of
billions of dollars annually in metal
products.
The oxidation of metals occurs most
readily at points of strain. Thus, a steel
nail, which is mostly iron, first corrodes
at the tip and head. A bent nail corrodes
most readily at the bend.
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Corrosion
The Fe2+ ions can migrate from the anode through the solution
toward the cathode region, where they combine with OH- ions
to form iron(II) hydroxide. Iron is further oxidized by O2 to the
+3 oxidation state. It can be represented as Fe2O3.xH2O. 52
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Corrosion protection
There are several methods for protecting metals against
corrosion. The most widely used are:
1. Plating the metal with a thin layer of a less easily oxidized
metal.
2. Connecting the metal directly to a sacrificial anode, a piece
of another metal that is more active and therefore
preferentially oxidized.
3. Allowing a protective film, such as a metal oxide, to form
naturally on the surface of the metal.
4. Galvanizing, or coating steel with zinc, a more active metal
5. Applying a protective coating, such as paint.
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Corrosion protection
An iron pipe connected to a strip of magnesium, a more active
metal, to protect the iron from oxidation. The magnesium is
preferentially oxidized. It is called a sacrificial anode.
Similar methods are used to protect bridges and the hulls of
ships from corrosion. Other active metals, such as zinc, are
also used as sacrificial anodes.
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Corrosion protection
Cathodic protection of a ships hull.
The small yellow horizontal strips
are blocks of titanium (coated with
platinum) that are attached to the
ships hull. The hull is steel (mostly
iron).
When the ship is in salt water, the
titanium blocks become the anode,
and the hull the cathode, in a voltaic
cell.
Because oxidation always occurs at
the anode, the ships hull (the
cathode) is protected from oxidation
(corrosion).
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Corrosion protection
Galvanizing is another method of corrosion protection. Even if
the zinc coating is broken, it is still oxidized in preference to the
less reactive iron as long as the two metals remain in contact.
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E = Eo where:
2.303 RT
log Q
nF
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E = Eo -
0.0592
log Q
n
E0 = -0.763 V
E = Eo -
0.0592
1
log
[Zn 2+ ]
2
E = 0.763 -
0.0592
1
log
[Zn 2+ ]
2
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Exercise
Calculate the potential, E, for the Fe3+/Fe2+ electrode when
the concentration of Fe2+ is exactly five times that of Fe3+.
Ans
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0.522
? M HCl
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E0cell = +0.763 V
[Zn ] PH
0.0592
0.0592
logQ = E ocell log
n
n
[H + ]2
2+
E cell = E
o
cell
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o
cell
G o
=
nF
o
Ecell
=
RT ln K
nF
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Exercise
Calculate the standard Gibbs free energy change, G0, in J/mol
at 25C for the following reaction from standard electrode
potentials.
3Sn4+ + 2Cr 3Sn2+ + 2Cr3+
Ans:
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Summary
After you have studied this module 7, you should be able to
Assign oxidation numbers to elements when they are free, in
compounds, or in ions.
Recognize oxidationreduction reactions and identify which
species are oxidized, reduced, oxidizing agents, and reducing
agent.
Use the terminology of electrochemistry (terms such as
cell, electrode, cathode, anode).
Describe the differences between electrolytic cells and
voltaic (galvanic) cells.
Recognize oxidation and reduction half-reactions, and know
at which electrode each occurs.
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Summary
Write half-reactions and overall cell reactions for electrolysis
processes.
Use Faradays Law of Electrolysis to calculate amounts of
products formed, amounts of current passed, time elapsed,
and oxidation state.
Describe the construction of simple voltaic cells from halfcells and a salt bridge, and understand the function of each
component.
Write half-reactions and overall cell reactions for voltaic cells
Interpret standard reduction potentials.
Use standard reduction potentials, E0, to calculate the
potential of a standard voltaic cell, E0 cell.
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Summary
Use standard reduction potentials to identify the cathode and
the anode in a standard cell.
Use standard reduction potentials to predict the spontaneity of a
redox reaction.
Use standard reduction potentials to identify oxidizing and
reducing agents in a cell or in a redox reaction.
Describe some corrosion processes and some methods for
preventing corrosion.
Use the Nernst equation to relate electrode potentials and cell
potentials to different concentrations and partial pressures.
Relate the standard cell potential (E0 cell ) to the standard Gibbs
free energy change (G0) and the equilibrium constant (K).
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