Corrosion: Unwanted Voltaic Cell
Corrosion reactions are spontaneous redox reactions in which a metal is attacked by some
substance in its environment and converted to an unwanted compound.
About 25% of steel produced in the US each year is used to replace steel in which the iron has
corroded
Corrosion: Unwanted Voltaic Cell
For nearly all metals, oxidation is thermodynamically favorable in air at room temperature.
Rusting of Iron
Corrosion
Preventing Corrosion
Objects made of iron are often covered with a coat of paint or another metal to protect against
corrosion. Covering the surface with paint prevents oxygen and water from reaching the iron
surface. If the coating is broken, however, and the iron exposed to oxygen and water, corrosion
begins as the iron is oxidized.
Preventing Corrosion
Preventing Corrosion: Cathodic Protection
Preventing Corrosion: Cathodic Protection
Corrosion
Electrolysis
Electrolytic cell uses electricity to produce a nonspontaneous reaction
Voltaic vs. Electrolytic Cell
Voltaic vs. Electrolytic Cell
Electrolysis of Molten Salt
In an electrolytic cell,
the more easily reduced species (stronger oxidizing agent, more positive electrode
potential) reacts at the cathode.
the more easily oxidized species (stronger reducing agent, less positive electrode
potential) reacts at the anode.
cations tend to undergo reduction, anions oxidation
Example 25
The most ionic and least ionic of the common alkali halides are, respectively, CsF and LiI. A
solid mixture of these compounds is melted and electrolyzed. Determine which metal and
nonmetal form at the electrodes, and write the overall cell reaction.
Electrolysis of Water
Electrolysis of Aqueous Solutions
In an electrolytic cell,
the more easily reduced species (stronger oxidizing agent, more positive electrode
potential) reacts at the cathode.
the more easily oxidized species (stronger reducing agent, less positive electrode
potential) reacts at the anode.
Electrolysis of KI(aq)
Possible Reduction Reactions:
Possible Oxidation Reactions:
Overvoltage
The products predicted from a comparison of electrode potentials are not always the actual
products. For gases to be produced at metal electrodes, additional voltage (overvoltage) is
required.
Consider the electrolysis of NaCl(aq)
Possible Reduction Reactions:
Possible Oxidation Reactions:
Example 27
Use half-reactions to show which product forms at each electrode during the electrolysis of
aqueous solutions of the following salts:
(a) KBr
(b) AgNO3
(c) MgSO4
Electroplating
Faraday’s law of electrolysis: the amount of substance produced at each electrode is directly
proportional to the quantity of charge flowing through the electrolytic cell.
Example 28
Using a current of 4.75 A, how many minutes does it take to plate a sculpture with 1.50 g of Cu
from a CuSO4 solution?
Example 29
Calculate the number of grams of aluminum produced in 1.00 h by the electrolysis of molten
AlCl3 if the electrical current is 10.0 A.
Integrative Example 1
The Ksp at 298 K for iron(II) fluoride is 2.4×10–6. (a) Write a half-reaction that gives the
likely products of the two-electron reduction of FeF2(s) in water. (b) Use the Ksp value and
the standard electrode potential of Fe2+(aq) to calculate the standard electrode potential for
the half-reaction in part (a). (c) Rationalize the difference between the electrode potential in
part (a) and the electrode potential for Fe2+(aq).
Integrative Example 2
In a galvanic cell the cathode is an Ag+ (1.00 M)/Ag(s) half-cell. The anode is a hydrogen
electrode immersed in a buffer solution containing 0.10 M HA and 0.050 M NaA. The
measured cell voltage is 1.030 V. What is the pKa of HA?
