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Voltaic Cell
Stored chemical energy is converted by a spontaneous reaction to
electrical energy; for example, a battery.
Electrolytic Cell
A chemical reaction is made to occur by passage of an electric
current.
Electrical energy is converted to chemical energy, for example,
electroplating.
Recall that a voltaic cell is one in which the redox reaction occurs
spontaneously and electrical energy is produced.
Consider the following reaction:
Zn (s)
Cu
2+
(aq)
Zn
2+
(aq)
Cu (s)
Electrical energy can only be produced if the two half reactions are
actually separated in space.....
What does this look like ?
What actually happens when the cell is operating ??
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Zn metal in
Zn2+(aq) solution
Cu metal in
Cu (aq) solution
2+
A voltaic cell consists of two half cells; in this cell there is a zinc
half cell and a copper half cell
The Zn metal and the Cu metal are acting as the electrodes.
Recall that oxidation occurs at the anode, which has a negative
charge; reduction occurs at the cathode, which has a positive
charge.
The electrons must pass through an external circuit which connects
the two half cells (electrons flow from anode to cathode).
A salt bridge connects the solutions and prevents mixing; it allows
for ions to flow between the two solutions.
If the salt concentrations are 1 M, and a current is allowed to flow
by completing the external circuit, a potential difference of 1.10 V
(at 25EC) will be established; this is the Standard Cell Potential.
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at Zn electrode:
at Cu electrode:
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H2 (g)
The reduction potential for this cell has been defined as: 0.00 V
Overall:
EEcell =
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EXAMPLE:
AR (s) / AR
3+
(aq) // Fe
2+
(aq) , Fe
3+
(aq) / Pt (s)
Overall:
EE cell =
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Once EE values have been measured relative to the H+/H2 halfreaction, a table of standard reduction potentials may be drawn up
(see tutorial problems, p. 17-18 or MH5; page 481) from which EEcell
for any overall redox reaction may be calculated........
A redox reaction and overall EEcell value can only be made up by
reversing one half-reaction (and its EE value) and adding
them................
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EXAMPLE:
a) Will the reaction Ce3+ (aq) + Fe3+ (aq) ! Ce 4+ (aq) + Fe2+ (aq)
proceed spontaneously ?
b) Write the cell diagram for this reaction.
Write the two half reactions... Look up Eo values
Remember:
Half-reactions with large +ve values occur readily.
EXAMPLE:
Which of the metals Ag, Cu, Sn and Fe will dissolve in aqueous acid ?
(Recall that acid means H+)....
At the anode:
At the cathode:
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Quantitative Electrolysis
Faradays Law defines the relationship between the amount of
electricity passed in an electrochemical cell and the amount of
reactants used or products formed in the corresponding redox
reaction.................
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EXAMPLES:
Half Reactions
Electrons
React / Prod
Ag+(aq) + e- ! Ag(s)
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The link between the charge and the number of moles of electrons is
known as the Faraday Constant.
This constant tells us that each mole of electrons that are passed
carries a charge of 96490 Coulombs.
EXAMPLE 1:
What mass, in g, of silver, Ag, can be plated out from a solution of
AgNO3 if a current of 0.750 amperes flows for 1 hour ?
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EXAMPLE 2:
We wish to electroplate 6.50 g of copper, Cu, from a solution of CuCR2.
How long will the electrolysis take if we use a current of 3.50 Amperes?
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EXAMPLE 3:
Electroplating is the deposition of a thin layer of metal on a
conducting surface.
The object to be electroplated is used as the cathode; the anode is
the electroplating metal.
Chromium metal has been used for chrome plating; suppose we wish
At the anode
At the cathode
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EXAMPLE 4:
Two electrolysis cells were connected in series as follows:
Cu*Cu2+*CuCCCAg*Ag+*Ag
Cell 1
Cell 2
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Electrolysis of Water
While we know that pure water does not conduct electricity very
well; it can participate in a redox reaction if there are some ions
present..............
2 H2O
(l)
! 2 H2
(g)
+ O2
(g)
(g)
Eocell =
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There are also two possibilities for the reaction occurring at the
anode:
1) The anion may be oxidized to the corresponding non metal....
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EXAMPLE 1:
At the anode:
2 CR
! CR2 (g)
2 e
E o = - 2.714 V
E o = - 1.36 V
Overall:
2 CR
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At the cathode:
2 H2O + 2 e ! H2 (g) + 2 OH
At the anode:
2 CR
! CR2 (g)
2 e
Eo = - 0.83 V
E o = - 1.36 V
Batteries
Batteries are voltaic, or galvanic cells; they undergo spontaneous
reactions.
These reactions are exothermic (heat producing); but when reaction
happens in a cell, the energy is released in the form of electricity.
There are two main types of batteries: dry cells (or primary
batteries) and rechargeable (secondary batteries).
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At the cathode:
2 MnO2 (aq) + 2 NH4+ (aq) + 2 e ! Mn2O3 (s) + H2O (R) + 2NH3(aq)
Overall:
(aq) !
ZnO (s)
At the cathode:
2 MnO2 (s) + H2O (R) + 2 e
Overall:
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H2O (R) + 2 e
Mn2O3 (s)
2 OH
(aq)
The mercury cell is a very small primary cell used in watches, hearing
aids, cameras and some calculators.
The anode is a zinc - mercury amalgam, with the reacting species
being zinc.
The cathode is mercury (II) oxide, HgO.
At the anode:
Zn (s) + 2 OH
(aq)
Zn(OH)2 (s)
2e
At the cathode:
HgO (s) + H2O + 2 e ! Hg (R) + 2 OH (aq)
Overall:
currents to flow for short periods of time (like when starting the
car).
The electrolyte is sulfuric acid, H2SO4.
2 H2O !
Pb (s) +
(cathode)
SO4 2 (aq)
PbSO4 (s)
2 e
E o = + 0.36 V
Cathode:
PbO2 (s) + 4 H +(aq) + SO4 2 (aq) + 2 e ! PbSO4 (s) + 2 H2O (R)
E o = + 1.68 V
Overall:
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CdO (s)
H2O (R) + 2 e
NiO (s)
2 OH
(aq)
Overall:
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EXAMPLE 1:
Consider the mercury cell described on p. 274. Suppose
this battery contains 0.030 g of Zn and 0.150 g of HgO. If the
battery can deliver a current of 0.00100 milliamps, how long, in hours,
will it take for the battery to completely discharge (go dead) ?
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-278-
Fuel Cells
In a fuel cell, a fuel (usually hydrogen) is oxidized at the anode.
In the reduction reaction at the cathode, oxygen is reduced.
In fuel cells currently in use, the reaction takes place in alkaline
solution.
Anode:
Cathode:
Overall:
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When these metals have higher oxidation numbers, (+4, +5, +6, +7),
they are only found in covalent compounds or complex ions.
EXAMPLE:
EXAMPLES:
Cr3+
- 0.41 V
!
Mn3+
1.56 V
!
3+
Fe
0.77 V
!
Cr2+
- 0.91 V
!
Cr(s)
Mn2+
- 1.18 V
!
Mn(s)
2+
Fe
- 0.41 V
!
1.95 V
Co3+
Cu
2+
Au
3+
0.16 V
!
1.40 V
!
Fe(s)
- 0.28 V
Co2+
Cu
Au
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Co(s)
0.52 V
!
Cu(s)
1.70 V
!
Au(s)
Now lets look at some questions that can be answered using the
information on the previous page.............
1)
2)
3)
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4)
Given: O2 + 4 H+ + 4 e
!
Which ions should oxidize water ?
5)
6)
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H2 O
EE = + 1.23 V