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2. Electrolytic Cell
It is a cell that does work by absorbing free energy from a
source of electricity to drive a nonspontaneous reaction,
i.e., it uses electrical energy to drive a nonspontaneous
reaction (G > 0).
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REDOX REACTIONS AND ELECTROCHEMICAL CELLS ions will not react with other ions in the cell or with the
Whether an electrochemical process releases or absorbs electrode materials. As oxidation and reduction proceed at
free energy, it always involves the movement of electrons the electrodes, ions from the salt bridge migrate to
from one chemical species to another in an oxidation- neutralize charge in the cell compartments. Anions
reduction (redox) reaction. migrate toward the anode, and cations toward the
cathode.
In electrochemical reactions, as in any redox process,
oxidation is the loss of electrons, and reduction is NOTE
the gain of electrons. An oxidizing agent is the species No measurable electron flow will occur through the external
that does the oxidizing, taking electrons from the substance circuit unless a means is provided for ions to migrate
being oxidized. A reducing agent is the species that does through the solution from one electrode compartment to
the reducing, giving electrons to the substance being another, thereby completing the circuit.
reduced.
After the reaction, the oxidized substance has a higher Because the negatively charged electrons flow from the
(more positive or less negative) oxidation number, and the anode to the cathode, the anode in a voltaic cell is labeled
reduced substance has a lower (less positive or more with a negative sign and the cathode with a positive
negative) oxidation number. sign. We can envision the electrons as being attracted to
Keep in mind three key points: the positive cathode from the negative anode through the
Oxidation (electron loss) always accompanies re.duction external circuit.
(electron gain).
The oxidizing agent is reduced, and the reducing agent is NOTE
oxidized. Although the anode and cathode are labeled with (-) and
The total number of electrons gained by the atoms/ions (+) signs respectively, you should not interpret the labels
of the oxidizing agent always equals the total number lost as charges on the electrodes. The labels simply tell us the
by the atoms/ions of the reducing agent. electrode at which the electrons are released to the
external circuit, the anode, and received from the external
Consider the spontaneous reaction that occurs when Zn is circuit, the cathode. The actual charges on the electrodes
added to HCl. are essentially zero.
Zn(s) + 2H+(aq) Zn2+(aq) + H2(g) Example : consider a Zn Cu electrochemical cell
Electrical neutrality in the solution is maintained by the As the voltaic cell operates, oxidation of Zn introduces
migration of ions between the two compartments through a additional Zn2+ ions into the anode compartment. Unless a
device such as a salt bridge. means is provided to neutralize this positive charge, no
further oxidation can take place. Similarly, the reduction of
A salt bridge consists of a U-shaped tube that contains an Cu2+ at the cathode leaves an excess of negative charge in
electrolyte solution, such as KCl(aq) or NaNO 3(aq), whose solution in that compartment.
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NOTE Standard Reduction Potentials
The flow of electrons from the anode to the cathode is The cell potential of a voltaic cell depends on the particular
possible only if ions are transferred through the salt bridge cathode and anode half cells involved. The cell potential
in order to maintain overall charge balance for each of the is the difference between two electrode potentials, one
two compartments. associated with the cathode and the other associated with
the anode.
To balance charges the cation in the salt bridge migrate
toward the cathode and the anions migrate toward the By convention, the potential associated with each electrode
anode. is chosen to be the potential for reduction to occur at that
electrode.
Illustration
Thus, standard electrode potentials are tabulated for
reduction half reactions and are called standard
reduction potentials, E red.
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Standard Reduction Potentials in Water at 25C occur. The more positive the value of E red the
greater the driving force for reduction.
Standard Reduction Half - Reaction
Potential (V) In any voltaic cell the reaction at the cathode has a more
positive value of Ered than does the reaction at the anode.
+ 2.87 F2 (g) + 2 e- 2 F- (aq) The greater driving force of the cathode half reaction is
+ 1.51 MnO4- (aq) + 8 H+ (aq) + 5 e - Mn2+ (aq) + used to force the anode reaction to occur in reverse , as
4 H2O (l) an oxidation.
+ 1.36 Cl2 (g) + 2 e- 2 Cl- (aq)
+ 1.33 Cr2O72- (aq) + 14 H+ (aq) + 6 e- 2 Cr3+ (aq) Ecell is the net driving force that pushes the electrons
+ 7 H2O (l) through an external circuit.
+ 1.23 O2 (g) + 4 H+ (aq) + 4 e- 2 H2O (l)
+ 1.06 Br2 (l) + 2 e- 2 Br-(aq) Sample Exercise
+ 0.96 NO3 - (aq) + 4 H+ (aq) + 3 e - NO (g) + H2O 3. A voltaic cell is based on the following standard half
(l) reactions:
+ 0.80 Ag+ (aq) + e- Ag (s) Cd2+(aq) + 2e- Cd(s) Ered = - 0.403 V
+ 0.77 Fe3+ (aq) + e- Fe2+ (aq) Sn2+(aq) + 2e- Sn(s) Ered = - 0.136 V
+ 0.68 O2 (g) + 2 H+ (aq) + 2 e- H2O2 (aq) Determine the half reactions that occur at the cathode
+ 0.59 MnO4 - (aq) + 2 H2O (l) + 3 e - MnO2 (s) + and the anode. Determine the standard cell potential.
4 OH- (aq) (0.267 V)
+ 0.54 I2 (s) + 2 e- 2 I- (aq)
+ 0.40 O2 (g) + 2 H2O (l) + 4 e- 4 OH- (aq) Practice Exercise
+ 0.34 Cu2+ (aq) + 2 e- Cu (s) 3. A voltaic cell is based on a Co2+/Co half cell (Ered =
0.00 2H+ (aq) + 2 e- H2 (g) - 0.277) and a AgCl/Ag half cell (E red = +0.222V).
- 0.28 Ni2+ (aq) + 2 e- Ni (s) What reactions occur at the anode and cathode? What
- 0.44 Fe2+ (aq) + 2 e- Fe (s) is the standard cell potential?
- 0.76 Zn2+ (aq) + 2 e- Zn (s) (+0.499 V)
- 0.83 2 H2O (l) + 2 e- H2 (g) + 2 OH- (aq)
- 1.66 Al3+ (aq) + 3e- Al (s) The more positive the E red, the greater is the
- 2.71 Na+ (aq) + e- Na (s) tendency for reduction (gain of e-) to occur and the
- 3.05 Li+ (aq) + e- Li (s) electrode has greater tendency to be a cathode. The
more negative the E red, the greater is the tendency
These standard reduction potentials, often called half for oxidation (loss of e-) to occur and the electrode
cell potentials, can be combined to calculate the emfs of has greater tendency to be an anode.
a large variety of voltaic cells. Oxidizing and Reducing Agents
The more positive the E red value for a half
Standard reduction potentials are intensive properties reaction, the greater the tendency for the reactant
because electrical potential measures potential energy per of the half reaction to be reduced, and, therefore,
electrical charge. Thus, changing the stoichiometric to oxidize another species.
coefficient in a half reaction does not affect the Examination of the standard cell potentials shows that F2
value of the standard reduction potential. with the highest positive voltage (+ 2.87 V) is the most
easily reduced species and is consequently the strongest
e.g. Zn2+(aq, 1 M) + 2e- Zn(s) Ered = - 0.76 V oxidizing agent listed.
2 Zn2+(aq, 1 M) + 4e- 2Zn(s) Ered = - 0.76 V F2(g) + 2e- 2F-(aq) Ered = + 2.87 V
Sample Exercise Among the most frequently used oxidizing agents are the
1. For the Zn – Cu2+ voltaic cell, Ecell = 1.10 V and the Zn halogens, O2, and oxyanions such as MnO 4-, Cr2O72-, and
electrode is the anode. Given that the standard NO3-, whose central atoms have high positive oxidation
reduction potential of Zn2+ is – 0.76 V, calculate the states. All of these species undergo reduction with large
Ered for the reduction of Cu2+ to Cu: positive values of Ered.
Cu2+(aq, 1 M) + 2e- Cu(s)
(1.10 V) Lithium ion, Li+, with the highest negative voltage
(- 3.05 V) is the most difficult species to reduce and is
2. Using standard reduction potentials, calculate the therefore the poorest oxidizing agent.
standard emf for the cell reaction
Cr2O72-(aq) + 14H+(aq) + 6I-(aq) 2Cr3+(aq) + 3I2(s) Li+(aq) + e- Li(s) Ered = - 3.05 V
+ 7H2O(l)
(0.79 V) The fact that Li+ is so difficult to reduce tells us that the
reverse reaction, the oxidation of Li(s) to Li+(aq), is a
Practice Exercises highly favorable reaction. Lithium metal has a great
1. A voltaic cell is based on the following half reactions: tendency to transfer electrons to other species; in water it
In+(aq) In3+(aq) + 2e- is the strongest reducing agent among the substances
Br2(l) + 2e- 2Br-(aq) listed.
The standard emf for this cell is 1.46 V. Calculate
Ered for the reduction of In3+ to In+. Commonly used reducing agents include H 2 and the active
(- 0.40 V) metals such as the alkali metals and the alkaline earth
metals. Zn and Fe are also used as reducing agents.
2. Calculate the standard emf for a cell that employs the Solutions of reducing agents are difficult to store for
following overall cell reaction: extended periods because of the ubiquitous presence of O 2,
2Al(s) + 3I2(s) 2Al3+(aq) + 6I-(aq) a good oxidizing agent.
(+ 2.20 V) e.g. Developer solutions used in photography are mild
reducing agents; they have only a limited shelf life because
For each of the half cells, the standard reduction potential they are readily oxidized by O2 from the air.
provides a measure of the driving force for reduction to
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The standard reduction potentials, Ered are related to the n represents the number of electrons transferred in the
ability of substances to serve as oxidizing or reducing reaction
agents. Species on the left side of the half reactions can F is the Faradays constant the quantity of electrical
act as oxidizing agents, and those on the right side can charge on 1 mol of electrons
serve as reducing agents. As Ered becomes more positive, - named after Michael Faraday
the oxidizing strength of the species on the left increases.
As Ered becomes more negative, the reducing strength of This quantity of charge is called a faraday, F:
the species on the right increases.
1 F = 96,500 C/mol = 96,500 J/V-mol
Most positive values of Ered NOTE
Per mole unit means per mole of reaction as written .
F2(g) + 2e- 2F (aq)
-
A positive value of E and a negative value of G both
indicate that a reaction is spontaneous.
2H+(aq) + 2e- H2(g)
At standard conditions, i.e., when the reactants and
products are all in their standard states
Li+(aq) + e- Li(s) G = - nFE
Most negative values of Ered Sample Exercise
Sample Exercise 6. Use the standard reduction potentials to calculate the
4. Which of the following species is the strongest standard free-energy change, G, for the following
oxidizing agent: NO3-(aq), Ag+(aq), Cr2O72-? reaction:
4Ag(s) + O2(g) + 4H+(aq) 4Ag+(aq) + 2H2O(l)
Practice Exercise
4. Which of the following species is the strongest reducing Suppose the above reaction was written as
agent: I-(aq), Fe(s), Mn2+(aq)?
2Ag(s) + ½O2(g) + 2H+(aq) 2Ag+(aq) + H2O(l)
The reduced form of any element will reduce the oxidized what are the values of E and G?
form of any element above it in the table. ( -170 kJ/mol ; +0.43 V ; -83 kJ/mol)
The oxidized form of any element will oxidize the reduced
form of any element below it in the table. Practice Exercise
6. Consider the following reaction:
SPONTANEITY OF REDOX REACTIONS 3 Ni2+(aq) + 2 Cr(OH)3(s) + 10 OH-(aq) 3 Ni(s) + 2
Voltaic cells use redox reactions that proceed CrO42-(aq) + 8 H2O(l)
spontaneously. Any reaction that can occur in a voltaic cell
to produce a positive emf must be spontaneous. What is the value of n for this reaction? Calculate G
for this reaction given that Ered = - 0.13 V for the half-
For a general redox reaction, cell reaction:
CrO42-(aq) + 4H2O(l) + 3e- Cr(OH)3(s) + 5OH-(aq)
E = E red (reduction process) - E red (oxidation process)
(6 ; +87 kJ/mol)
In general,
EFFECT OF CONCENTRATION ON CELL EMF
A positive value of E indicates a spontaneous As a voltaic cell is discharged, the reactants of the reaction
process, and a negative value of E indicates a are consumed and the products are generated, so the
nonspontaneous process. concentrations of these substances change. The emf
progressively drops until E = 0, at which point we say the
NOTE cell is dead.
E represents the emf under nonstandard conditions
E represents the standard emf At that point the concentrations of the reactants and
products cease to change; they are at equilibrium.
Sample Exercise
5. Using the standard reduction potentials, determine Under nonstandard conditions the emf generated by a cell
whether the following reactions are spontaneous under can be calculated using the Nernst equation that was first
standard conditions: derived by Walther Nernst, a German chemist who
(a) Cu(s) + 2H+(aq) Cu2+(aq) + H2(g) established many of the theoretical foundations of
(b) Cl2(g) + 2I-(aq) 2Cl-(aq) + I2(s) electrochemistry.
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When [Zn2+] = 1.00 M and [Cu2+] = 0.100 M Therefore, the compartment with the more dilute solution
will be the anode compartment; oxidation of Ni(s) at the
E = 1.0704 V anode increases [Ni2+] in the more dilute solution. The
When [Zn2+] = 0.100 M and [Cu2+] = 1.00 M compartment with the more concentrated solution will be
the cathode compartment, for the reduction of Ni 2+(aq) at
E = 1.1296 V the cathode decreases [Ni2+] in that compartment.
Concentration Cells
A concentration cell is a cell based solely on the emf Cell EMF and Chemical Equilibrium
generated because of a difference in concentration. It is The emf of a voltaic cell drops as it is discharged. As
constructed using the same species in both the anode and reactants are converted to products, the value of Q
cathode compartments but with different concentrations. increases, so the value of E decreases. Eventually the cell
emf reaches E = 0. When E = 0 , G = 0 and the cell
e.g. consider a Ni2+ - Ni concentration cell reaction has reached equilibrium; no net reaction is
One compartment consists of a strip of nickel metal occurring in the voltaic cell.
immersed in a 1.00 M solution of Ni 2+(aq). The other
compartment also has a Ni(s) electrode, but immersed in a At equilibrium, E = 0 and Q = K, thus at 298 K
1.00 x 10-3 M solution of Ni2+(aq). The two compartments E = E - (0.0592 / n) log Q
are connected by a salt bridge and by an external wire with
a voltmeter. The half cell reactions are the reverse of 0 = E - (0.0592 / n) log K
one another:
or
Anode : Ni(s) Ni2+(aq) + 2e- Ered = -0.28 V
Cathode : Ni2+(aq) + 2e- Ni(s) Ered = -0.28 V log K = (n E / 0.0592)
Sample Exercise
The standard emf for this cell is 10. Using the standard reduction potentials, calculate the
Ecell = Ered (cathode) - Ered (anode) = 0 V equilibrium constant for the oxidation of Fe 2+ by O2 in
acidic solution. The reaction is
This cell operates under nonstandard conditions because of O2(g) + 4H+(aq) + 4Fe2+(aq) 4Fe3+(aq) + 2H2O(l)
the difference in concentration of Ni 2+(aq) in the two (1.2 x 1031)
compartments. The driving force for the cell is provided by Practice Exercise
the difference in concentration. Operation of the cell tends 10. Using standard reduction potentials, calculate the
to equalize the concentrations of Ni 2+ in both equilibrium constant at 25C for the reaction
compartments. Br2(l) + 2Cl-(aq) Cl2(g) + 2Br-(aq)
(7.3 x 10-11)
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Preventing the Corrosion of Iron
C5ell Notation Iron is often covered with a coat of paint or another metal
Cell notation is a shorthand method of constructing a such as tin or zinc to protect its surface against corrosion.
galvanic cell without taking the trouble to draw the actual Covering the surface with paint or tin is a means of
picture of the cell. preventing O2(g) and H2O(l) from reaching the iron surface.
Conventions: If the coating is broken and the iron is exposed to O 2(g)
a salt bridge is represented by a // and H2O(l) , corrosion will begin.
boundaries between different phases are represented
by a / e.g. galvanized iron - iron coated with a thin layer of Zn
boundaries between 2 different species in the same
phase are indicated by a , From the standard reduction potentials, the Ered for the
to represent the complete cell, anode is written first reduction of Fe2+ is less (-) than the reduction of Zn 2+, so
before the cathode using a salt bridge to separate Fe2+ is easier to reduce than Zn2+ and Zn(s) is easier to
them oxidize than Fe(s). Thus, even if the zinc coating is broken
to represent the anode, oxidation, write the solid first and the galvanized iron is exposed to O 2(g) and H2O(l), the
then the ion, electrolyte, separated by a single bar zinc serves as the anode and is corroded instead of the
e.g. anode of Zn metal in a solution of Zn 2+ : Zn / Zn2+ iron. The iron serves as the cathode at which O 2(g) is
e.g. anode consisting of solid Pt in contact with H 2 reduced.
immersed in an aqueous solution of an acid solution like
HCl or H2SO4 : Pt / H2 / H+ cathodic protection - protection of a metal by making it
to represent the cathode, write the electrolyte first then the cathode in an electrochemical cell
the solid last sacrificial anode - the metal that is oxidized while
e.g. cathode of Zn metal immersed in a solution containing protecting the cathode
Zn2+ : Zn2+ / Zn
e.g. solid Pt with Cl2 adsorbed in the Pt surface immersed in Sample Exercise
another solution containing Cl- ions : 12. Predict the nature of the corrosion that would take
Cl- / Cl2 / Pt place if an iron gutter were nailed to a house using
aluminum nails.
Sample Exercise
11. Write the cell notation for the Daniell cell Practice Exercise
12. Using the standard reduction potential, indicate which
Practice Exercise of the following metals could provide cathodic
11. Write the half - cell reactions and the cell notations for protection to iron: Al, Cu, Ni, Zn
the following reactions: (Al ; Zn)
(a) Ni(s) + Cu2+(aq) Ni2+(aq) + Cu(s)
(b) Zn(s) + 2Fe3+(aq) Zn2+(aq) + 2Fe2+(aq)
(c) Cl2(g) + 2I-(aq) 2Cl-(aq) + I2(g)
CORROSION
Corrosion reactions are spontaneous undesirable redox
reactions in which a metal is attacked by some substance in
its environment and converted to an unwanted compound.
Corrosion of Iron
- rusting of iron
- requires O2(g) and H2O(l)
- the pH of the solution, the presence of salts,
contact with metals more difficult to oxidize
than iron, and stress on iron can accelerate
rusting
electrode reactions:
anode : Fe(s) Fe2+(aq) + 2e-
cathode : O2(g) + 4H+(aq) + 4e- 2H2O(l)
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