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Marks
Rechargeable nickel-cadmium batteries normally operate (discharge) with the
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following oxidation and reduction half-cell reactions.
Cd(s) + 2OH(aq) Cd(OH)2(s) + 2e E = 0.82 V
NiO(OH)(s) + H2O(l) + e Ni(OH)2(s) + OH(aq) E = 0.60 V
Write out a balanced overall cell reaction.
Answer: +1.42 V
Using your balanced cell reaction, briefly explain why the cell potential does not
change as the battery discharges itself.
Write out the balanced overall reaction that occurs when this battery is being
recharged.
number of moles of e = It / F
= (2.75 A) (5.00 60.00 s) / (96485 C mol-1)
= 0.00855 mol
From the half-cell reaction, each mole of Cd(s) requires 2 mol of electrons. The
number of moles of Cd(s) redeposited is therefore:
Why are the cathode and anode not in separate compartments, as in the Cu/Zn
battery?
All the redox active species are solids so can be kept apart without needing
separate compartments.
How does H2SO4 serve as the salt bridge? Which ions flow in which direction to
maintain electroneutrality?
H2SO4 dissociates to give H+, HSO4 and SO42 ions which carries the current.
The H+ ions migrate to the cathode, whilst the HSO4 and SO42 ions migrate to
the anode.
What is the formula for the equilibrium constant for the discharge reaction above?
The cell potential for this battery is 2.05 V. If the concentration of the H2SO4 is
4.5 M, what is the standard potential of the cell at 25 C?
The Nernst equation, Ecell = E - lnQ, can be used to work out the standard
potential for this two electron process. As Ecell = 2.05 V when [H2SO4] = 4.5 M:
. ! ! ( )
2.05 V = E - ln(4.5)-2
( ! )
E = 2.01 V
Answer: +2.01 V
CHEM1001 2008-J-10 June 2008 22/01(a)
A solar powered light uses a nickel-cadmium battery to store electricity. Calculate the 3
standard voltage for the battery from the following:
NiO2(s) + Cd(s) + 2H2O(l) Ni(OH)2(s) + Cd(OH)2 Go = 251 kJ mol1
The reaction is a two electron process (as Cd is being oxidized to Cd(II) and Ni is
being reduced from Ni(IV) to Ni(II)). Hence, n = 2.
The standard electrode potential is linked to Gibbs free energy change by,
G = -nFE
E = 1.30 V
Answer: 1.30 V
CHEM1001 2007-J-8 June 2007 22/01(a)
Give the balanced half equation of the reaction that takes place at the cathode.
Why is it important that all redox active species are solids in this reaction?
As all redox active species are solids, their concentrations do not change during
the reaction. They therefore do not appear in the equilibrium expression or in the
Nernst equation.
Give the balanced half equation of the reaction that takes place at the anode.
Give the balanced half equation of the reaction that takes place at the cathode.
3
The half reactions describing the discharge of a silver-zinc cell are:
Zn(s) + 2OH(aq) ZnO(s) + H2O(l) + 2e
Ag2O(s) + H2O(l) + 2e 2Ag(s) + 2OH(aq)
List the chemical species that will be consumed as the battery discharges.
It acts like a salt bridge allowing the migration of ions away from and towards
the electrodes. OH(aq) ions are produced at the cathode and consumed at the
anode.
Marks
Explain the following features of the lead acid storage battery.
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It has a relatively constant voltage.
Both the anode and cathode are solids so can be placed in the same electrolyte.
It can be recharged.
The products are solids so remain trapped in the same electrode. External
voltage can reverse the reaction and regenerate the cathode and anode.
3
Consider the following cell reaction.
Pb(s) + Sn2+(aq) Pb2+(aq) + Sn(s)
Use the Nernst equation to calculate the ratio of cation concentrations for which the
cell potential, E = 0. (See the data sheet for a table of standard reduction potentials.)
The Nernst equation gives Ecell = E - 2.303 logQ. Ecell = 0 when:
E = 2.303 logQ = 2.303 logK
[Pb 2+ (aq)]
The ratio of cation concentrations is just Q = . The process involves
[Sn 2+ (aq)]
2e- so n = 2 and Q can be obtained using the E = 0.01 V:
Kc = /.= 0.5
Answer: 0.5
CHEM1001 2004-J-9 June 2004
Marks
The standard dry cell (battery) has the following shorthand notation:
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Zn(s) | Zn2+(aq) || MnO2(s), Mn2O3(s) | graphite(s)
Give the balanced half equation that takes place at the anode.
Zn(s) Zn2+(aq) + 2e
Give the balanced half equation that takes place at the cathode.
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What is meant by cathodic protection? Which of the following metals can provide
cathodic protection to iron and why?
Zn, Ni, Al, Sn
Efor oxidation of Fe to Fe2+ is 0.44 V. Zn and Al have more positive Eox values
than Fe and hence can provide cathodic protection of iron. Ni and Sn have less
positive Eox values so cannot protect the iron.