Tutorial 20: Electrochemistry Suggested Solutions

1(a)(1)
(i)

Cr2O72 (aq) + 14H+ (aq) + 6e 2Cr3+ (aq) + 7H2O (l)

E = +1.33 V

Cu2+(aq) + 2e- Cu (s)

E = +0.34 V

Cathode: Pt electrode in Cr2O72 (aq) / Cr3+ (aq) halfcell

Red:
Cr2O72 (aq) + 14H+ (aq) + 6e 2Cr3+ (aq) + 7H2O (l)
Anode:

Copper electrode in Cu2+ (aq) / Cu (s) halfcell

Oxid:

Cu (s) Cu2+ (aq) + 2e

[1]

(ii)

Cr2O72 (aq) + 14H+(aq) + 3Cu(s) 2Cr3+ (aq) + 7H2O(l) + 3Cu2+(aq)

(iii)

Ecell

=
=

+1.33 (+0.34)
+0.99 V

(iv)

[1]

[1]

[1]
Correct drawing & labeling
Correct conditions
Correct e direction

e
V
T = 298 K

[1]
[1]
[1]

Cu
salt bridge
Pt
[Cr2O72 (aq)]
= [Cr3+(aq)]
= [H+(aq)]
= 1 mol dm3

2+

[Cu (aq)]
= 1 mol dm3

1(a)(2)
(i)

H2O2 (aq) + 2H+ (aq) + 2e 2H2O (l)

E = +1.77 V

O2 (g) + 2H+ (aq) + 2e H2O2 (aq)

E = +0.68 V

Cathode: Pt electrode in H2O2 (aq) / H2O (l) halfcell

Red:
H2O2 (aq) + 2H+ (aq) + 2e 2H2O (l)

[1]

Anode:
Oxid:

[1]

Pt electrode in O2 (g) / H2O2 (aq) halfcell

H2O2 (aq) O2 (g) + 2H+ (aq) + 2e

(ii)

2H2O2 (aq) 2H2O (l) + O2 (g)

(iii)

Ecell

=
=

[1]

+1.77 (+0.68)
+1.09 V
e

(iv)

[1]
Correct drawing & labeling
Correct conditions
Correct e direction

V
T = 298 K

O2
(1 atm)

[H2O2(aq)]
= [H+(aq)]
= 1 mol dm3

salt bridge
Pt

Pt

[H2O2(aq)]
= [H+(aq)]
= 1 mol dm3

[1]
[1]
[1]

1(b)(i)

CO32- precipitates out Cu2+ so that [Cu2+(aq)] decreases.

[1]

This shifts the position of equilibrium in Cu2+(aq) + 2e Cu(s) to the left so that EL
decreases. Hence Ecell = ER EL increases (i.e. Ecell > Ecell).
[1]
(ii)

Br reduces Cr2O72 to Cr3+.

This decreases [Cr2O72 (aq)] but increases [Cr3+ (aq)] [1] so that the position of
equilibrium in Cr2O72(aq) + 14H+(aq) + 6e 2Cr3+(aq) + 7H2O(l) shifts to the left and so
ER decreases.
Hence Ecell = ER EL decreases (i.e. Ecell < Ecell).
[1]

1(c)(i)

To decrease Ecell, either decrease ER or increase EL.

(1) ER can be decreased by using H2O2 or H+ of a lower concentration in the H2O2/H2O
halfcell.
[1]
+
(2) EL can be increased by using O2 of a higher pressure, H of a higher concentration
or H2O2 of a lower concentration in the O2 / H2O2 halfcell.
[1]

(ii)

Hydrogen peroxide can spontaneously undergo oxidation and reduction under standard
conditions:
2H2O2 (aq) 2H2O(l) + O2 (g),
Ecell = +1.77 (+0.68)V = +1.09V > O
[1]
reaction is energetically feasible and spontaneous under standard conditions.
Hence bubbles of oxygen are given off by a solution of hydrogen peroxide on standing.
Disproportionation. [1] (In general, substances disproportionate if their ER > EL.)

2(a)

I2 (aq) + 2e 2I (aq)

E = +0.54 V

Fe2+ (aq) + 2e Fe (s)

E = 0.44 V

Ecell = 0.44 (+0.54)

= 0.98 V < 0
reaction is not likely to occur.
(b)

[1]

H2O2 (aq) + 2H+ (aq) + 2e 2H2O (l)

E = +1.77 V

I2 (aq) + 2e 2I (aq)

E = +0.54 V

Ecell =
=

+1.77 (+0.54)
+1.23 V > 0

[1]

reaction is energetically feasible and spontaneous under standard conditions.

H2O2 (aq) + 2H+ (aq) + 2I (aq) 2H2O (l) + I2 (aq)

A brown solution is formed.
(c)

[1]
[1]

Cr2O72 (aq) + 14H+ (aq) + 6e 2Cr3+ (aq) + 7H2O (l)

E = +1.33 V

SO42 (aq) + 4H+ (aq) + 2e- SO2 (aq) + 2H2O (l)

E = +0.17 V

Ecell = +1.33 (+0.17)

= +1.16 V > 0
[1]
reaction is energetically feasible and spontaneous under standard conditions.
Cr2O72(aq) + 2H+ (aq) + 3SO2 (aq) 2Cr3+ (aq) + H2O (l) + 3SO42 (aq)
Orange solution turns green.
2

[1]
[1]

2(d)

O2 (g) + 2H2O (l) + 4e 4OH (aq)

E = +0.40 V

Cr3+ (aq) + e Cr2+ (aq)

E = 0.41 V

Ecell = +0.40 (0.41)

= +0.81 V > 0
[1]
reaction is energetically feasible and spontaneous under standard conditions.
O2 (g) + 2H2O (l) + 4Cr2+ (aq) 4Cr3+(aq) + 4OH (aq)

[1]

and Cr (aq) + 3OH (aq) Cr(OH)3 (s)

Blue solution decolourises and a greyishgreen ppt is formed in a green solution.
3+

[1]
[1]

3(a)

O2 (g) + 4H+ (aq) + 4e 2H2O (l)

[1]

(b)

CH4 (g) + 2H2O (l) CO2 (g) + 8H+ (aq) + 8e

[1]

(c)

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l)

[1]

(d)

So long as the two reactants i.e. O2(g) and CH4(g) are not in direct contact [1], there is
no need to have two separate fuel cells. (These two reactants are in fact, separated by a
common electrolyte i.e. aqueous dilute H2SO4.)

(e)

Direction of e flow
Labelling of electrodes
Labelling of electrolyte and gases

V
CH4 (g)

O2 (g)

(anode)

(cathode)

Pt

Pt

[1]
[1]
[1]

dilute
sulphuric
acid

(f)

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g)

[1]

(g)

They are the same except for the state of water.

[1]

(h)

More efficient conversion of chemical energy into electrical energy.

Also the products formed are much less polluting.

[1]

4(a)

MnO4(aq) + 8H+(aq) + 5e Mn2+(aq) + 4H2O (l)

E = +1.52 V

Cl2(g) + 2e 2Cl (aq)

E = +1.36 V

Cr2O7(aq) + 14 H+(aq) + 6e 2Cr3+(aq) + 7H2O(l)

E = +1.33 V

From the E values,

it can be seen that, under standard conditions, MnO4 can oxidise Cl to Cl
i.e. Ecell
= +1.52 (+1.36)
= +0.16 V > 0

[1]

In the titration determination of iron(II) ions (e.g. using aqueous FeCl2), the amount of
Fe2+ present is determined by the amount of oxidant it reacts with.
3

If MnO4 were used, some MnO4 will be consumed by Cl instead of reacting solely with
Fe2+. [1] This would result in a larger amt of MnO4 used than required i.e. the results
would be inaccurate.
On the other hand, under standard conditions, Cr2O72 cannot oxidise Cl to Cl2
i.e. Ecell
= +1.33 (+1.36)
= -0.03 V < 0

[1]

Hence all Cr2O72 will be used to react with Fe2+ and thus K2Cr2O7 (aq) can be used for
the titration determination of iron(II) ions in the presence of chloride ions

4(b)

Al3+ + 3e Al

E = 1.66 V

Pb2+ + 2e Pb

E = 0.13 V

Aluminium has a very low reduction potential and so its ion is not easily reduced to the
metal.
[1]
Its ore (e.g. Al2O3) cannot be reduced by C and requires electrolysis.
[1]
(Note: the Al2O3 ore is not soluble in water and even if it were dissolved in acid to make up an
aqueous solution, the latter would generate H2 (from water) at the cathode. Hence molten ore is
needed.)

Lead has a less negative reduction potential and so it is relatively easier for its ion to
be reduced to the metal.
[1]
Hence its oxide can be reduced by C.
(Note: carbon is a much cheaper raw material compared to the expensive electrical power needed
for electrolysis.)

(c)

At the cathode:
2H2O(l) + 2e H2(g) + 2OH(aq)
[1]
+

H2 (E = 0.83 V) is preferentially discharged [1] since Na (E = 2.71 V) is less

readily reduced.
At the anode,
gas B contains 80% C by mass high C content; other element present could be H.
Assuming B is CxHy, then for 1.0 g of B,
mole ratio of C:H

0.80 0.20
= 1:3 i.e. empirical formula = CH3
:
12.0 1.0

B is likely C2H6.

[1]

The oxidation of CH3CO2(aq) could likely produce CO2 as the other gas A.
Hence at anode, the balanced halfequation is:
2CH3CO2(aq) CH3CH3(g) + 2CO2(g) + 2e

[1]
[1]

From the halfequation, it can be seen that the amt of CO2 is twice that of CH3CH3.
At the same temperature and pressure, the volume ratio of CO2: CH3CH3 is 2:1.
[1]

5(a)(i) amt of Ag deposited

(ii)

Ag+(aq) + e Ag
amt of e
quantity of charge passed
current passed

(iii)

Cr3+(aq) + 3e Cr (s)
amt of Cr deposited
mass of Cr deposited

(b)

= 0.100 / 108
= 9.26 x 104 mol

= amt of Ag deposited
= 9.26 x 104 mol
= 96 500 x 9.26 x 104
= 89.35 C
= 89.35 / (30 x 60)
= 0.0496 A
0.05 A

= 1/3 x amt of e passed

= 3.086 x 104 mol
= 3.086 x 104 x 52.0
= 0.0160 g

volume of Al2O3 to be deposited

mass of Al2O3
amt of Al2O3

= 500 x 1 x 103
= 0.5 cm3
= 4.0 x 0.5
= 2.0 g
= 2.0 / (27.0 x 2 + 16.0 x 3)
= 0.0196 mol

At the anode: 2H2O(l) O2(g) + 4H+(aq) + 4e

then
4Al(s) + 3O2(g) 2Al2O3 (s)
amt of e

[1]

[1]

[1]

[1]
[1]

[1]

[1]

= 4 x amt of O2 produced
=4x(

3
x amt of Al2O3)
2

= 0.1176 mol
quantity of charge needed

(c)

= 96 500 x 0.1176
= 11 348 C

Ni2+ (aq) + 2e Ni (s)

2Ag+ (aq) + 2e 2Ag (s)
For the same current passed,
amt of Ag: amt of Ni deposited
hence mass of Ag: mass of Ni deposited

=2:1
= 2 x 108 : 1 x 58.7
= 3.68 : 1

[1]

[1]
[1]

5(d)

2Cu2+ (aq) + 4e 2Cu (s)

2H2O(l) O2(g) + 4H+(aq) + 4e

cathode:
anode:

amt of O2 produced

= x amt of Cu deposited
= x (0.635 / 63.5)
= 0.005 mol

vol. of O2 produced at r.t.p.

= 0.005 x 24.0
= 0.12 dm3

[1]
[1]

[1]

Addtional Questions (Optional)

A1(i)

Ecell

(ii)

Fe3+ (aq) + e Fe2+ (aq)

Cu (s) Cu2+ (aq) + 2e
2Fe3+ (aq) + Cu (s) 2Fe2+ (aq) + Cu2+ (aq)

(iii)

Ecell of the reaction is +0.43V >>0. Hence even though the conditions in a testtube may
not be under standard conditions, Ecell is still > 0 such that reaction can proceed in a test
tube.
[1]

(iv)

(Any suitable halfcell with E > +0.77 V) e.g.

Cl2 / Cl halfcell: E = + 1.36V
Electrode: Pt, with chlorine gas and sodium chloride solution.

A2(i)

= +0.77(+0.34)

= +0.43 V

O2 (g) + 2H2O (l) + 4e 4OH (aq)

[1]
[1]
[1]
[1]

[1]
[1]

E = +0.40 V

Zn2+ (aq) + 2e Zn (s)

E = 0.76 V
O2(g) + 2H2O (l) + 2Zn (s) 2Zn(OH)2 (s)

[1]

Ecell

[1]

= +0.40(+0.76)

(ii)

= +1.16 V

O2 (g)

Zn

()

(+)

electrolyte (aq)

(iii)

aqueous KCl. [1]

(Note: choice of electrolyte requires careful consideration i.e. it must not oxidise Zn or C.
e.g.
dilute acids cannot be used since H+ reacts with Zn.
solutions containing ions of metals less reactive than Zn (e.g. CuSO4) cannot be
used as it undergoes displacement reaction with Zn.)

SelfCheck
1(i) The standard electrode potential of a halfcell is the electromotive force, measured at 298K
and 1 atm, between the halfcell and the standard hydrogen electrode, in which the reacting
species in solution are at molar concentrations.
(ii) Ecell is the potential difference between two halfcells under standard conditions. It gives a
measure of the e.m.f. (electromotive force) which pumps the electrons around the circuit.
2(i)

V
T = 298 K
H2
(1 atm)

Cu
salt bridge
Pt
Cu2+
H+

[H+(aq)] = 1 mol dm3

[Cu2+(aq)] = 1 mol dm3

(ii)

V
T = 298 K
H2
(1 atm)
salt bridge
Pt

Pt
2+

Fe

Fe3+

[H+(aq)] = 1 mol dm3

[Fe2+(aq)] = [Fe3+(aq)]
= 1 mol dm3

3(i)
E of Co2+ / Co = - 0.28V (oxid) Co is negative electrode
E of Cl2 / Cl = + 1.36V (red) Pt is positive electrode
(ii) Cl2 (g) + Co(s) 2Cl(aq) + Co2+(aq)
(iii) Ecell = 1.36 (-0.28) = +1.64V