Tutorial 9 - Level 2 Worked Solutions
Tutorial 9 - Level 2 Worked Solutions
Note: If Ecell is greater than 0 V, you should check if the vanadium product
can undergo further redox!
Note: There two other reactions that are also energetically feasible (i.e. H2O2 with
Cl and H+ with Sn2+). However, we would usually give the one that is the
most energetically feasible as the answer.
salt bridge
The copper electrode is oxidised by oxygen in the air to generate copper(I) oxide.
During discharge, copper(I) oxide will be reduced to copper solid at the cathode.
Similarly, during discharge, lithium will be oxidised to give lithium ions at the
anode and pass through the separator into the aqueous alkaline electrolyte.
(a) (i) Write half–equations for the reaction occurring at each electrode when
the battery discharges.
anode (or Li) : Li Li+ + e (use ‘’)
cathode (or Cu) : Cu2O + H2O + 2e 2Cu + 2OH (use ‘’)
(not Cu+ + e Cu !)
Note:
For half–equation that cannot be obtained from the Data Booklet, read the
information given in the question and apply ‘KOHe’ to form the half–equation
on your own!
(i) Draw a fully labelled diagram of the electrochemical cell you would set
up in order to measure the relative oxidising powers of chlorine and
iodine under standard conditions.
Note: Qn stated that “I3 reacts as if it were a solution of I2 in water”.
E(I3/ I) = +0.54 V ---[O] (more –ve)
E(Cl2/Cl) = +1.36 V ---[R] (more +ve)
anode e e cathode
V
(negative) (positive)
Cl2(g), 1 bar,
298 K
salt bridge
3
1 mol dm I3(aq), 1 mol dm3
3
1 mol dm I (aq), Cl(aq), 298 K
298 K
platinised
Pt(s)
Pt(s)
Examiners’ Report:
Despite the question asking for only one electrochemical cell, many
candidates chose to draw two cells, each with a standard hydrogen electrode
on one side.
Although most candidates could describe the chlorine electrode, few
described correctly the iodine electrode (a Pt electrode dipped in a mixture of
1 mol dm3 I(aq) and I2(s) or I3(aq)).
Many suggested a solid electrode made of (nonconducting) iodine or
suggested passing I2(g) over a Pt electrode.
Other incorrect answers were the omission of salt bridge or the inclusion of a
battery in the circuit.
(ii) Describe the measurements you would make, and explain their
significance.
Note the Ecell value on the voltmeter at first instance of cell
being connected.
The X2 in the half–cell connected to positive electrode has a
greater tendency to be reduced and is a stronger oxidising agent.
Hence, the positive electrode is the half–cell with the more positive
E.
Examiners’ Report:
Candidates were expected to suggest measuring the E of the cell and to
explain that the more positive of the two electrodes would contain the
stronger oxidising agent. Candidates should be aware of the difference
between ‘more positive’ and ‘larger or bigger’.
(b) When solutions of I(aq) and Fe3+(aq) are mixed, an equilibrium is set up.
(i) Write a balanced equation for this equilibrium.
2Fe3+(aq) + 2I–(aq) 2Fe2+(aq) + I2(aq) (use ‘’)
Examiners’ Report:
Some candidates suggested incorrectly the Ksplike equilibrium: 3I(aq) +
Fe3+(aq) FeI3(s) whilst other suggested that I(aq) could reduce Fe3+ to Fe
metal. Overall, most showed the correct redox reaction.
(ii) Use the Data Booklet to suggest how the position of equilibrium,
involving I(aq) and Fe3+(aq), would change in the presence of CN
ions. Explain your answer.
[Hint: Consider which Fe(III)/Fe(II) electrode potential you should use.]
When CN‒(aq) is added, both Fe2+(aq) and Fe3+(aq) forms the
complex ions Fe(CN)64‒(aq) and Fe(CN)63‒(aq) respectively.
Hence, the position of equilibrium in (b)(i) will lie more to the left.
Examiners’ Report:
The majority of candidates gave answers written in terms of CN ions causing
[Fe3+] to decrease and thus moving the equilibrium to the left. These
candidates did not appreciate that the CN forms complexes with both Fe3+
and Fe2+ and therefore, adding CN to a solution containing Fe3+ and Fe2+ will
cause the concentrations of both cations to decrease.
Only a minority of candidates made use of the E value for the
[Fe(CN)6]3/[Fe(CN)6]4 electrode (+0.36 V) in the Data Booklet to correctly
explain that this indicates that the Fe(III) is less oxidising than I2 (+0.54 V)
under standard condition.
(ii) Use E values from the Data Booklet to explain your answer to (c)(i).
Species present: Fe2+ and Cl2
Fe3+(aq) + e– Fe2+(aq) E = +0.77 V ---[O]
Cl2(g) + 2e– 2Cl–(aq) E = +1.36 V ---[R]
(iii) Use E values to explain why there is no change when I2(aq) is added
to Fe2+(aq). Hence, comment on the relative reactivity of Cl2 and I2
with Fe2+.
Species present: Fe2+ and I2
Fe3+(aq) + e– Fe2+(aq) E = +0.77 V ---[O]
I2(aq) + 2e– 2I–(aq) E = +0.54 V ---[R]
(iii) What substance causes the purple colour when hexane is added?
Note: from Topic 2 – Chemical Bonding
Hexane (C6H14) is a non-polar molecule with weak id-id between the molecules.
Thus, I2 (which is also a non-polar molecule with weak id-id between molecules)
will dissolve preferentially in hexane compared to water.
Hexane is normally added to confirm the identity of the halogen present as the
colour of the halogen in organic solvents are more distinct than in aqueous
solvents such as water.
Colour tends to brown
(from Data Booklet)
with increasing conc.
Note: For new syllabus (9729), the colours of the halogens in their elemental state,
aqueous phase and in hexane are given in the Data Booklet!
(iv) Hence write an ionic equation, with state symbols, for the reaction of
copper(II) sulfate with potassium iodide.
2Cu2+(aq) + 4I–(aq) 2CuI(s) + I2(aq)
Note: “Cu2+(aq) + 3I–(aq) CuI(s) + I2(aq)” is incorrect as the charges on both sides
of equation are not balanced.
Examiners’ Report:
Even though they knew the identities of the reactants and products, most candidates
struggled with this equation, giving equations that were not balanced, contained the
wrong species or were not ionic. From earlier parts of the question, candidates had
established that a redox reaction occurs between Cu2+ ions and I ions with the
formation of CuI and I2.
Examiners’ Report:
This part was less well answered. Candidates were again required to extract
relevant E data from the Data Booklet. The most common mistake was to
use data for Cu/Cu+ despite the fact that the reaction involves the formation
of Cu+ from Cu2+. Those candidates who chose the correct E values were
usually able to show that the reaction is unlikely to occur – as stated in the
question.
(ii) By using your answers to (d)(iii) and (d)(iv), explain why this reaction
does, in fact, occur.
Cu2+ + e– Cu+ ---(1)
Cu+ formed reacts with I to give CuI ppt which reduces [Cu+(aq)].
This causes the position of equilibrium of (1) to shift right, making
E(Cu2+/Cu+) more positive than +0.15 V
Examiners’ Report:
This was the most poorly answered part of any question but it was meant to
test candidates’ understanding of some difficult concepts. The question states
that the reaction does in fact occur despite the E data. Examiners gave
credit for straightforward explanation such as how the formation of CuI(s),
which is extremely insoluble, will drive the reaction.
(i) Construct equations for the reactions occurring at the cathode and
anode.
cathode : O2 + 4H+ + 4e– 2H2O ---(1)
anode : CH3OH + H2O CO2 + 6H+ + 6e– ---(2)
(ii) Hence, construct the equation for the overall reaction, showing your
working.
(1) 3 + (2) 2:
2CH3OH + 2H2O + 3O2 + 12H+ + 12e– 2CO2 + 12H+ + 6H2O + 12e–
Overall: 2CH3OH + 3O2 2CO2 + 4H2O
(Working for the derivation of the overall equation is required as stated
in the question.)
Examiners’ Report:
Part (i) to (iii) were generally well answered: the equation of the cathode
reaction of the fuel cell was correctly identified, and hence for the overall
reaction. Some candidates did not show the working as was requested in the
wording of the question.
For (iii): The value for the E of the CO2/CH3OH electrode reaction was
determined, some candidates however gave a negative sign for the answer.
Extension:
Suggest a disadvantage of using the methanol fuel cell compared to
the hydrogen–oxygen fuel cell.
(ii) Using the equations in (a)(i) and (b)(i), and the data given in (a)(iii),
determine the standard enthalpy change of combustion of liquid
methanol, given that the standard entropy change of combustion of
liquid methanol is 107 J mol1 K1.
Using Gr (in J mol1) = zFEcell and z = 12,
Gr = 12 96500 (+1.18) = 1.37 106 J mol1
= 1370 kJ mol1 (for 2 mol CH3OH)