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Electrochemistry
Electrochemistry
Electrochemistry
1
Chapter Goals
1. Electrical Conduction
2. Electrodes
Electrolytic Cells
3. The Electrolysis of Molten Potassium Chloride
4. The Electrolysis of Aqueous Potassium Chloride
5. The Electrolysis of Aqueous Potassium Sulfate
6. Faraday’s Law of Electrolysis
7. Commercial Applications of Electrolytic Cells
2
Chapter Goals
Voltaic or Galvanic Cells
8. The Construction of Simple Voltaic Cells
9. The Zinc-Copper Cell
10. The Copper-Silver Cell
Standard Electrode Potentials
11. The Standard Hydrogen Electrode
12. The Zinc-SHE Cell
13. The Copper-SHE Cell
14. Standard Electrode Potentials
15. Uses of Standard Electrode Potentials
3
Chapter Goals
16. Standard Electrode Potentials for Other Half-
Reactions
17. Corrosion
18. Corrosion Protection
Effect of Concentrations (or Partial Pressures)
on Electrode Potentials
19. The Nernst Equation
20. Using Electrohemical Cells to Determine
Concentrations
21. The Relationship of Eocell to Go and K
4
Chapter Goals
Primary Voltaic Cells
22. Dry Cells
Secondary Voltaic Cells
23. The Lead Storage Battery
24. The Nickel-Cadmium (Nicad) Cell
25. The Hydrogen-Oxygen Fuel Cell
5
Electrochemistry
Electrochemical reactions are oxidation-reduction
reactions.
The two parts of the reaction are physically separated.
The oxidation reaction occurs in one cell.
The reduction reaction occurs in the other cell.
There are two kinds electrochemical cells.
1. Electrochemical cells containing in nonspontaneous
chemical reactions are called electrolytic cells.
2. Electrochemical cells containing spontaneous chemical
reactions are called voltaic or galvanic cells.
6
Electrical Conduction
Metals conduct electric currents well in a
process called metallic conduction.
In metallic conduction there is electron flow with
no atomic motion.
In ionic or electrolytic conduction ionic motion
transports the electrons.
Positively charged ions, cations, move toward the
negative electrode.
Negatively charged ions, anions, move toward the
positive electrode.
7
Electrodes
8
Electrodes
9
Electrolytic Cells
10
Electrolytic Cells
11
The Electrolysis of Molten
Potassium Chloride
Liquid potassium is produced at one
electrode.
Indicates that the reaction K+() + e- K() occurs
at this electrode.
Is this electrode the anode or cathode?
Gaseous chlorine is produced at the other
electrode.
Indicates that the reaction 2 Cl- Cl2(g) + 2 e-
occurs at this electrode.
Is this electrode the anode or cathode?
12
The Electrolysis of Molten
Potassium Chloride
Diagram of this electrolytic cell.
e-
e- Generator-source
of DC
- electrode + electrode
molten KCl
Cathode reaction 2 K e K -
Cell reaction 2 Cl - 2 K Cl 2 g 2 K
14
The Electrolysis of Molten
Potassium Chloride
In all electrolytic cells, electrons are forced
to flow from the positive electrode (anode)
to the negative electrode (cathode).
15
The Electrolysis of Aqueous
Potassium Chloride
In this electrolytic cell, hydrogen gas
- is produced at one electrode.
Anode reaction
The aqueous
Cl nearthis Cl
2basic
solution becomes 2(g) 2 e
electrode.
-
What reaction is occurring at this electrode? You do it!
Cathode reaction 2 H O 2 e H
-
Gaseous chlorine is produced at the other electrode.
2 2 g 2 OH -
What reaction is occurring at this electrode? You do it!
These experimental facts lead
- us to the following nonspontaneous
Cell reaction 2 Cl 2 H O H
electrode reactions: 2 2 g Cl
2 g 2 OH -
16
The Electrolysis of Aqueous
Potassium Chloride
- pole of battery + pole of battery
Cell diagram Battery, a source
e- flow of direct current e- flow
- electrode + electrode
aqueous KCl
2 H2O + 2e- H2 (g) + 2 OH- 2Cl- Cl2 (g) + 2e-
17
cathode reaction anode reaction
The Electrolysis of Aqueous
Potassium Sulfate
In this electrolysis, hydrogen gas is produced at one
electrode.
The solution becomes basic near this electrode.
What reaction is occurring at this electrode?
You do it!
Gaseous oxygen is produced at the other electrode
The solution becomes acidic near this electrode.
What reaction is occurring at this electrode?
You do it!
These experimental facts lead us to the following
electrode reactions:
18
The Electrolysis of Aqueous
Potassium Sulfate
Anode reaction 2 H 2 O O 2(g) 4 H 4 e -
Cathode reaction 2(2 H 2 O 2e- H 2(g) 2OH - )
Cell reaction 6 H 2 O 2 H 2(g) O 2(g) 4H 4 OH
-
4 H 2O
19
The Electrolysis of Aqueous
Potassium Sulfate
- pole of battery + pole of battery
Cell diagram Battery, a source
e- flow of direct current e- flow
- electrode + electrode
H2 gas O2 gas
aqueous K2SO4
2 H2O + 2e- H2 (g) + 2 OH- 2H2O O2 (g) + 4H+ + 4e-
20
cathode reaction anode reaction
Electrolytic Cells
21
Counting Electrons: Coulometry and
Faraday’s Law of Electrolysis
Faraday’s Law - The amount of substance undergoing chemical
reaction at each electrode during electrolysis is directly proportional
to the amount of electricity that passes through the electrolytic cell.
A faraday is the amount of electricity that reduces one equivalent of a
species at the cathode and oxidizes one equivalent of a species at
the anode.
22
Counting Electrons: Coulometry and
Faraday’s Law of Electrolysis
A coulomb is the amount of charge that passes a
given point when a current of one ampere (A) flows
for one second.
1 amp = 1 coulomb/second
23
Counting Electrons: Coulometry and
Faraday’s Law of Electrolysis
Faraday’s Law states that during electrolysis, one faraday
of electricity (96,487 coulombs) reduces and oxidizes,
respectively, one equivalent of the oxidizing agent and the
reducing agent.
This corresponds to the passage of one mole of electrons through
the electrolytic cell.
24
Counting Electrons: Coulometry and
Faraday’s Law of Electrolysis
Example 21-1: Calculate the mass of palladium produced by
the reduction of palladium (II) ions during the passage of 3.20
amperes of current through a solution of palladium (II) sulfate
for 30.0 minutes.
2+2 + -- 0
Cathode : Pd + 2e
Cathode: Pd + 2e Pd
11mol
mol 22molmol 11mol
mol
106
106gg 2(96,500)
2(96,500)106
106g g
3.20 amp = 3.20 C
s
60 s 3.20 C 106 g Pd
? g = 30.0 min 316
. g Pd
min s 2 96,500 C
25
Counting Electrons: Coulometry and
Faraday’s Law of Electrolysis
Example 21-2: Calculate the volume of oxygen
(measured at STP) produced by the oxidation of
water in example 21-1.
Anode
Anode::22 H O
H22O OO22 g g ++4H
4H+ +++4e4e- -
22 mol
mol 11mol
mol 44molmol 44mol
mol
22.4L
22.4 LSTP
STP
4496,500
96,500CC
60 s 3.20 C 22.4 LSTP O 2
? LSTP O 2 30.0 min
min s 4 96,500 C
0.334 LSTP O 2 or 334 mLSTP O 2
26
Commercial Applications of
Electrolytic Cells
Electrolytic Refining and Electroplating of Metals
Impure metallic copper can be purified
27
Commercial Applications of
Electrolytic Cells
The electrolytic solution is CuSO4 and H2SO4
The impure Cu dissolves to form Cu2+.
The Cu2+ ions are reduced to Cu at the cathode.
0 2
Anode impure Cu s Cu aq 2e
2+ 0
Cathode very pure Cu aq 2e Cu s
Net rxn. No net rxn.
28
Commercial Applications of
Electrolytic Cells
Any active metal impurities are oxidized to cations that are more difficult
to reduce than Cu2+.
This effectively removes them from the Cu metal.
2
Zn Zn 2e
0
2
Fe Fe 2e
0
Auto batteries
Flashlight batteries
Computer and calculator batteries
31
The Construction of Simple Voltaic
Cells
Voltaic cells consist of two half-cells which
contain the oxidized and reduced forms of an
element (or other chemical species) in contact
with each other.
A simple half-cell consists of:
A piece of metal immersed in a solution of its ions.
A wire to connect the two half-cells.
And a salt bridge to complete the circuit, maintain
neutrality, and prevent solution mixing.
32
The Construction of Simple Voltaic
Cells
33
The Zinc-Copper Cell
Cell components for the Zn-Cu cell are:
1. A metallic Cu strip immersed in 1.0 M copper (II) sulfate.
2. A metallic Zn strip immersed in 1.0 M zinc (II) sulfate.
3. A wire and a salt bridge to complete circuit
The cell’s initial voltage is 1.10 volts
34
The Zinc-Copper Cell
Anode reaction Zn 0 Zn 2+ 2e
Cathode reaction Cu 2+ 2e Cu 0
Overall cell reaction Zn 0 Cu 2+ Zn 2+ Cu 0
This is a spontaneous reaction with E 0cell 1.10V
In all voltaic cells, electrons flow spontaneously
from the negative electrode (anode) to the
positive electrode (cathode).
35
The Zinc-Copper Cell
There is a commonly used short hand notation for
voltaic cells.
The Zn-Cu cell provides a good example.
species (and concentrations)
in contact with electrode surfaces
salt bridge
electrode surfaces
36
The Copper - Silver Cell
Cell components:
1. A Cu strip immersed in 1.0 M copper (II) sulfate.
2. A Ag strip immersed in 1.0 M silver (I) nitrate.
3. A wire and a salt bridge to complete the circuit.
The initial cell voltage is 0.46 volts.
37
The Copper - Silver Cell
Anode reaction Cu 0 Cu 2 2e
Cathode reaction
2 Ag + + e - Ag 0
Overall cell reaction Cu 0 + 2 Ag + Cu 2+ + 2 Ag 0
This is a spontaneous reaction with E 0cell 0.46V
Compare the Zn-Cu cell to the Cu-Ag cell
The Cu electrode is the cathode in the Zn-Cu cell.
The Cu electrode is the anode in the Cu-Ag cell.
Whether a particular electrode behaves as an anode or as a
cathode depends on what the other electrode of the cell is.
38
The Copper - Silver Cell
These experimental facts demonstrate that Cu2+ is a stronger oxidizing agent
than Zn2+.
In other words Cu2+ oxidizes metallic Zn to Zn2+.
Similarly, Ag+ is is a stronger oxidizing agent than Cu2+.
Because Ag+ oxidizes metallic Cu to Cu 2+.
If we arrange these species in order of increasing strengths, we see that:
Zn 2+ < Cu 2+ < Ag +
strength as oxidizing agent
Zn 0 > Cu 0 > Ag 0
strength as reducing agent
39
Standard Electrode Potential
To measure relative electrode potentials, we must
establish an arbitrary standard.
That standard is the Standard Hydrogen Electrode
(SHE).
The SHE is assigned an arbitrary voltage of 0.000000… V
40
The Zinc-SHE Cell
For this cell the components are:
1. A Zn strip immersed in 1.0 M zinc (II) sulfate.
2. The other electrode is the Standard Hydrogen Electrode.
3. A wire and a salt bridge to complete the circuit.
The initial cell voltage is 0.763 volts.
41
The Zinc-SHE Cell
E0
Anode reaction Zn 0 Zn 2+ + 2 e - 0.763 V
Cathode reaction 2 H + + 2 e - H 2 g 0.000 V
Cell reaction Zn 0 + 2H + Zn 2+ + H 2 g E 0cell 0.763 V
42
The Copper-SHE Cell
The cell components are:
1. A Cu strip immersed in 1.0 M copper (II) sulfate.
2. The other electrode is a Standard Hydrogen Electrode.
3. A wire and a salt bridge to complete the circuit.
The initial cell voltage is 0.337 volts.
43
The Copper-SHE Cell
E0
Anode reaction H 2 g 2 H + + 2 e - 0.000 V
Cathode reaction Cu 2+ + 2e- Cu 0 0.337 V
Cell reaction H 2 g + Cu 2+ 2H + + Cu 0 E 0cell 0.337 V
44
Uses of Standard Electrode
Potentials
Electrodes that force the SHE to act as an anode are assigned
positive standard reduction potentials.
Electrodes that force the SHE to act as the cathode are assigned
negative standard reduction potentials.
Standard electrode (reduction) potentials tell us the tendencies of
half-reactions to occur as written.
For example, the half-reaction for the standard potassium electrode
is:
K e K 0 0
E = -2.925 V
The large negative value tells us that this reaction
will occur only under extreme conditions.
45
Uses of Standard Electrode
Potentials
Compare the potassium half-reaction to fluorine’s half-
reaction:
0 - - 0
F2 + 2e 2F E = +2.87 V
The large positive value denotes that this reaction occurs readily
as written.
Positive E0 values denote that the reaction tends to occur to the
right.
The larger the value, the greater the tendency to occur to the
right.
It is the opposite for negative values of E o.
46
Uses of Standard Electrode
Potentials
Use standard electrode potentials to predict
whether an electrochemical reaction at
standard state conditions will occur
spontaneously.
Example 21-3: Will silver ions, Ag+, oxidize
metallic zinc to Zn2+ ions, or will Zn2+ ions
oxidize metallic Ag to Ag+ ions?
Steps for obtaining the equation for the
spontaneous reaction.
47
Uses of Standard Electrode
Potentials
1.Choose the appropriate half-reactions from a table of standard
reduction potentials.
2. Write the equation for the half-reaction with the more positive E 0 value
first, along with its E0 value.
3. Write the equation for the other half-reaction as an oxidation with its
oxidation potential, i.e. reverse the tabulated reduction half-reaction
and change the sign of the tabulated E0.
4 Balance the electron transfer.
5 Add the reduction and oxidation half-reactions and their potentials.
This produces the equation for the reaction for which E0cell is positive,
which indicates that the forward reaction is spontaneous.
48
Uses of Standard Electrode Potentials
E0
Reduction 2(Ag + + e - Ag 0 ) + 0.7994 V
Oxidation 1(Zn Zn 2+ + 2 e - ) - (-0.7628 V)
Cell reaction 2Ag + + Zn 0 2Ag 0 + Zn 2+ E 0cell = +1.5662 V
49
Electrode Potentials for
Other Half-Reactions
Example 21-4: Will permanganate ions,
MnO4-, oxidize iron (II) ions to iron (III) ions,
or will iron (III) ions oxidize manganese(II)
ions to permanganate ions in acidic solution?
Follow the steps outlined in the previous
slides.
Note that E0 values are not multiplied by any
stoichiometric relationships in this procedure.
50
Electrode Potentials for
Other Half-Reactions
Example 21-4: Will permanganate ions, MnO 4-,
oxidize iron (II) ions to iron (III) ions, or will iron (III)
ions oxidize manganese(II) ions to permanganate
ions in acidic solution? 0
E
Reduction 1(MnO-4 8H + 5e- Mn 2 4H 2O) + 1.51 V
Oxdation 5(Fe2 Fe 3+ + e - ) - (0.771 V)
Cell reaction MnO -4 5Fe 2 8H Mn 2 4H 2O + 5Fe3+ E 0cell = +0.74 V
51
Electrode Potentials for
Other Half-Reactions
Example 21-5: Will nitric acid, HNO3, oxidize
arsenous acid, H3AsO3, in acidic solution? The
reduction product of HNO3 is NO in this reaction.
You do it!
E0
Reduction 2(NO 3- 4H + 3e - NO 2H 2 O) + 0.96 V
Oxidation 3(H 3AsO3 H 2 O H 3 AsO4 2H + 2e - ) - (0.58 V)
Cell reaction 2NO 3- 3H 3 AsO3 8H 3H 2 O 2NO 4H 2 O + 3H 3AsO4 6H
2NO 3- 3H 3 AsO3 2H 2NO H 2 O + 3H 3 AsO4 6H E 0cell = +0.38 V
52
Corrosion
Metallic corrosion is the oxidation-reduction
reactions of a metal with atmospheric components
such as CO2, O2, and H2O.
4 Fe 0 + 3 O 02 2 Fe 2 O 3 overall reaction
The reaction occurs rapidly at exposed points.
53
Corrosion Protection
Some examples of corrosion protection.
1 Plate a metal with a thin layer of a less active (less
easily oxidized) metal.
55
Corrosion Protection
56
Corrosion Protection
4 Galvanizing, the coating of steel with zinc, provides
a more active metal on the exterior.
57
Corrosion Protection
58
Effect of Concentrations (or Partial
Pressures) on Electrode Potentials
The Nernst Equation
Standard electrode potentials, those compiled
in appendices, are determined at
thermodynamic standard conditions.
Reminder of standard conditions.
1.00 M solution concentrations
1.00 atm of pressure for gases
All liquids and solids in their standard thermodynamic states.
Temperature of 250 C.
59
The Nernst Equation
The value of the cell potentials change if conditions
are nonstandard.
The Nernst equation describes the electrode
potentials at nonstandard conditions.
The Nernst equation is:
60
The Nernst Equation
0 2.303RT
E=E - log Q
nF
E = potential under condition of interest
E 0 potential under standard conditions
R = universal gas constant = 8.314 J
mol K
T = temperature in K
n = number of electrons transferred
F = the faraday = (96,487 C/mol e - ) 1 J .
CV
96,487 J/V mol e -
Q = reaction quotient
61
The Nernst Equation
Substitution of the values of the constants into the
Nernst equation at 25o C gives:
2.303 RT 2.303 8.314 J mol K 298 K
-
0.0592
F 96,487 J/V mol e
0 0.0592
Thus E = E - log Q
n
62
The Nernst Equation
For this half-reaction:
Cu 2+
e Cu
- 0
E = +0.153 V
The corresponding Nernst equation is:
E=E -
0.0592
0
log
Cu +
1 Cu 2
63
The Nernst Equation
Substituting E0 into the above expression gives:
E = 0.153 V -
0.0592
log
Cu +
1 Cu 2
If [Cu2+] and [Cu+] are both 1.0 M, i.e. at standard
conditions, then E = E0 because the concentration
term equals zero.
0.0592 1
E = 0.153 V - log
1 1
64
The Nernst Equation
65
The Nernst Equation
Example 21-6: Calculate the potential for the
Cu2+/ Cu+ electrode at 250C when the
concentration of Cu+ ions is three times that
of Cu2+ ions.
Cu 2+
+ e Cu
-
Cu
3 Cu
+
3
2+
Q=
Cu Cu 2+ 2+
66
The Nernst Equation
67
The Nernst Equation
Cu +
3
Cu
1 2+
0.333
Q=
Cu Cu
2+ 2+
You do it!
69
The Nernst Equation
Example 21-7: Calculate the potential for the
Cu2+/Cu+ electrode at 250C when the concentration
of Cu+ ions is 1/3 that of Cu2+ ions.
0 0.0592
E=E - log Q
1
0.0592
E = 0.153 V - log 1
1 3
70
The Nernst Equation
0 0.0592
E=E - log Q
1
0.0592
E = 0.153 V - log 1
1 3
E = 0.153V - 0.0592 - 0.477 V
E = 0.153 + 0.0282 V
E = 0.181 V
71
The Nernst Equation
Example 21-8: Calculate the electrode potential for a
hydrogen electrode in which the [H+] is 1.0 x 10-3 M and
the H2 pressure is 0.50 atmosphere.
+ H
2H +2e -
2
Q=
PH 2
0.50
H 1.0 10
+ 2 3 2
Q 5.0 10 5
72
The Nernst Equation
Example 21-8: Calculate the electrode potential for a
hydrogen electrode in which the [H+] is 1.0 x 10-3 M and
the H2 pressure is 0.50 atmosphere.
E=E -
0.0592
0
2
log 5.0 10
5
0.0592
E 0 5.699
2
E 0.168 V
73
The Nernst Equation
The Nernst equation can also be used to calculate
the potential for a cell that consists of two
nonstandard electrodes.
Example 21-9: Calculate the initial potential of a cell
that consists of an Fe3+/Fe2+ electrode in which
[Fe3+]=1.0 x 10-2 M and [Fe2+]=0.1 M connected to a
Sn4+/Sn2+ electrode in which [Sn4+]=1.0 M and
[Sn2+]=0.10 M . A wire and salt bridge complete the
circuit.
74
The Nernst Equation
75
The Nernst Equation
Substitute the ion concentrations into Q to calculate
Ecell.
0.0592
E cell = E 0cell - log Q
2
= 0.62 V -
0.0592
log
Fe
2 2
Sn4
Sn
2
2 Fe3 2
E cell = 0.62 V -
0.0592
log
. 10
010 .
2
2
2 2
. 10 010
10 .
76
The Nernst Equation
E cell = 0.62 V -
0.0592
log
0.10 1.0
2
0.0592
E cell 0.62 V - 3.00
2
E cell 0.62 0.09 V
E cell = 0.53 V
77
Relationship of E0cell to G0 and K
From previous chapters we know the relationship of
G0 and K for a reaction.
G -RT lnK
0
or
G 2.303 RT log K
0
78
Relationship of E0cell to G0 and K
G -n F E
0 0
cell
n number of e -
79
Relationship of E0cell to G0 and K
-n FE 0
cell - RT lnK
or
0
n FE
ln K cell
RT
80
Relationship of E0cell to G0 and K
81
Relationship of E0cell to G0 and K
GG nnFFEE
00 00
cell
cell
00
GG 22mol
mole e 9696 ,500J J
,500
VV mol
mol e e - .463
- 0 VV
0.463
G 0 -89.4 kJ
83
Relationship of E0cell to G0 and K
Example 21-11: Calculate the thermodynamic
equilibrium constant for the reaction in
example 21-10 at 250C.
G RT ln K
0
G 0 8.94 10 4 J
mol
ln K
RT - 8.314 J
mol K
298 K
ln K 36.1 K 5 10 15
Pb
2
Cu
2
84
Relationship of E0cell to G0 and K
Zn 2 Ag 0.30 M 2Ag Zn
2
0.50 M
85
Relationship of E0cell to G0 and K
86
Relationship of E0cell to G0 and K
Q=
Zn 2+
0.50
5.6
Ag 0.30
+ 2 2
87
Relationship of E0cell to G0 and K
Q=
Zn 0.50
2+
5. 6
Ag 0.30
+ 2 2
Q=
Zn 0.50
2+
5.6
Ag 0.30
+ 2 2
90
Relationship of E0cell to G0 and K
Equilibrium constants do not change with reactant
concentration.
We can use the value of E0cell at 250C to get K.
- n F E 0cell 2.303 RT log K
- n F E 0cell
log K =
2.303 RT
2 96,500 1.562
log K
2.303 8.314 298
log K 52.8
K = 6 10 52
Zn
2+
Ag
+ 2
91
Primary Voltaic Cells
92
The Dry Cell
One example of a dry cell is flashlight, and radio, batteries.
The cell’s container is made of zinc which acts as an
electrode.
A graphite rod is in the center of the cell which acts as the
other electrode.
The space between the electrodes is filled with a mixture
of:
1. ammonium chloride, NH4Cl
2. manganese (IV) oxide, MnO2
3. zinc chloride, ZnCl2
4. and a porous inactive solid.
93
The Dry Cell
As electric current is produced, Zn dissolves and
goes into solution as Zn2+ ions.
The Zn electrode is negative and acts as the anode.
94
The Dry Cell
The anode reaction is:
0 2+ -
Zn Zn +2 e
The graphite rod is the positive electrode (cathode).
Ammonium ions from the NH4Cl are reduced at the cathode.
+ -
2 NH 4 2 e 2 NH 3 g H 2 g
95
The Dry Cell
The cell reaction is:
96
The Dry Cell
The other components in the cell are included to remove the
byproducts of the reaction.
MnO2 prevents H2 from collecting on graphite rod.
H 2 g 2 MnO2 s 2 MnO(OH) s
At the anode, NH3 combines with Zn2+ to form a soluble
complex and removing the Zn2+ ions from the reaction.
4 NH 3 Zn
2+ 2
Zn NH 3 4
97
The Dry Cell
98
The Dry Cell
Alkaline dry cells are similar to ordinary dry cells
except that KOH, an alkaline substance, is added to
the mixture.
Half reactions for an alkaline cell are:
Anode reaction Zn 0s + 2 OH - Zn OH 2 s 2 e
Cathode reaction 2 MnO 2 s 2 H 2 O + 2 e - 2 MnO(OH) s + 2 OH -
Cell reaction Zn 0s + 2 MnO 2 s 2 H 2 O Zn OH 2 s 2 MnO(OH) s
E 0cell 1.5 V
99
The Dry Cell
Alkaline dry cells are similar to ordinary dry cells
except that KOH, an alkaline substance, is added to
the mixture.
Half reactions for an alkaline cell are:
100
Secondary Voltaic Cells
Secondary cells are reversible, rechargeable.
The electrodes in a secondary cell can be regenerated by the
addition of electricity.
These cells can be switched from voltaic to electrolytic cells.
One example of a secondary voltaic cell is the lead storage or car
battery.
101
The Lead Storage Battery
In the lead storage battery the electrodes are two sets of lead
alloy grids (plates).
Holes in one of the grids are filled with lead (IV) oxide, PbO 2.
The other holes are filled with spongy lead.
The electrolyte is dilute sulfuric acid.
102
The Lead Storage Battery
Diagram of the lead storage battery.
103
The Lead Storage Battery
As the battery discharges, spongy lead is oxidized to
lead ions and the plate becomes negatively charged.
Pb 0s Pb 2+ 2 e -
This is the anode reaction.
The anode is the negative battery post during discharge.
The Pb2+ ions that are formed combine with SO42- from
sulfuric acid to form solid lead sulfate on the Pb
electrode.
2+ 2-
Pb SO 4 PbSO 4 s
104
The Lead Storage Battery
The net reaction at the anode during discharge is:
0 2- -
Pb s SO4 PbSO4 s + 2 e
Electrons are produced at the Pb electrode.
These electrons flow through an external circuit
(the wire and starter) to the PbO2 electrode.
PbO2 is reduced to Pb2+ ions, in the acidic solution.
The Pb2+ ions combine with SO42- to form PbSO4 and
coat the PbO2 electrode.
PbO2 electrode is the positive electrode (cathode).
105
The Lead Storage Battery
PbO2 s + 4 H + + SO2-
4 + 2 e -
PbSO4 s + 2 H 2 O
The cell reaction for a discharging lead storage battery is:
106
The Lead Storage Battery
PbO2 s + 4 H + + SO2-
4 + 2 e -
PbSO4 s + 2 H 2 O
The cell reaction for a discharging lead storage battery is:
107
The Lead Storage Battery
What happens at each electrode during recharging?
At the lead (IV) oxide, PbO2, electrode, lead ions are oxidized
to lead (IV) oxide.
+ 4H + 2SO
PbSO 2H O
discharge
Pb s PbO 2 s + 2-
4
charge 4 s 2
108
The Lead Storage Battery
What happens at each electrode during recharging?
At the lead (IV) oxide, PbO2, electrode, lead ions are oxidized
to lead (IV) oxide.
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The Nickel-Cadmium (Nicad) Cell
110
The Hydrogen-Oxygen Fuel Cell
111
The Hydrogen-Oxygen Fuel Cell
Anode reaction 2 H 2 g 2 OH -(aq) 2 H 2 O ( ) 2 e -
Cathode reaction O 2 H O
2 g 2 ( ) 4 e -
4 OH -
(aq)
Cell reaction 2 H 2 g O 2 g 2 H 2 O
Notice that the overall reaction is the combination of
hydrogen and oxygen to form water.
The cell provides a drinking water supply for the astronauts
as well as the electricity for the lights, computers, etc. on
board.
Fuel cells are very efficient.
Energy conversion rates of 60-70% are common!
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Synthesis Question
113
Synthesis Question
114
Group Question
115
End of Chapter 21
116