Topic 3 - Electrochemistry

I Electrochemical Cell

Spontaneous Reactions:

Use the data below to determine whether the following reactions will occur under standard conditions:

Half-equation Eo/V
Pb2+(aq) + 2e ⇌ Pb(s) -0.14
2H+(aq) + 2e ⇌ H 2 (g) 0.00
Cu2+(aq) + e ⇌ Cu+(aq) +0.15
Cu2+(aq) + 2e ⇌ Cu(s) +0.34
Cu+(aq) + e ⇌ Cu(s) +0.52
I 2 (aq) + 2e ⇌ 2I-(aq) +0.54
2H+(aq) + O 2 (g) + 2e ⇌H 2 O 2 (aq) +0.68
Fe3+(aq) + e ⇌ Fe2+(aq) +0.77
Ag+(aq) + e ⇌ Ag(s) +0.80
NO 3 -(aq) + 2H+(aq) + e ⇌ NO 2 (g) + H 2 O(l) +0.81
Br 2 (aq) + 2e ⇌ 2Br-(aq) +1.09
Cr 2 O 7 2-(aq) + 14H+(aq) + 6e ⇌ 2Cr3+(aq) + 7H 2 O(l) +1.33
H 2 O 2 (aq) + 2H+(aq) + 2e ⇌ 2H 2 O(l) +1.77
Ag2+(aq) + e ⇌ Ag+(aq) +1.98

a) Ag+(aq) + Fe2+(aq)  Ag(s) + Fe3+(aq)

b) Cr 2 O 7 2-(aq) + 14H+(aq) + 6I-(aq)  2Cr3+(aq) + 7H 2 O(l) + 3I 2 (aq)

c) Cu(s) + Pb2+(aq)  Cu2+(aq) + Pb(s)

d) 2Fe3+(aq) + 2Br-(aq)  2Fe2+(aq) + Br 2 (aq)

e) 2Cu+(aq)  Cu2+(aq) + Cu(s)

Electrochemical Cell:

1. Use the data below, where appropriate, to answer the questions which follow.

Standard electrode potentials E /V

Br 2 (aq) + 2e → 2Br–(aq) +1.09
2BrO 3 -(aq) + 12H+(aq) + 10e → Br 2 (aq) + 6H 2 O(l) +1.52

Each of the above can be reversed under suitable conditions.

a) State the hydrogen ion concentration and the hydrogen gas pressure when, at 298 K, the potential of
the hydrogen electrode is 0.00 V.

Hydrogen ion concentration:

Hydrogen gas pressure:

[2]

b) The electrode potential of a hydrogen electrode changes when the hydrogen ion concentration is
reduced. Explain, using Le Chatelier’s principle, why this change occurs and state how the electrode
potential of the hydrogen electrode changes.

Explanation of change:

Change in electrode potential:

[3]

c) A diagram of a cell using platinum electrodes X and Y is shown below.

V
X Y
Salt Bridge

Solution containing Solution containing BrO –3 (aq),

Br 2 (aq) and Br – (aq) H +(aq) and Br 2 (aq)

i. Use the data above to calculate the e.m.f. of the above cell under standard conditions.
ii. Write a half-equation for the reaction occurring at electrode X and an overall equation for the
cell reaction which occurs when electrodes X and Y are connected.

Half-equation:

Overall equation:

[4]

Total: 9 marks
2. Use the data given below, where appropriate, to answer the questions which follow.

Standard electrode potentials in acid solution E /V

Mg2+ (aq) + 2e → Mg(s) –2.37
Zn2+ (aq) + 2e → Zn(s) –0.76
Sn4+(aq) + 2e → Sn2+(aq) +0.15
VO2+(aq) + 2H+(aq) + e → V3+(aq) + H 2 O(l) +0.34
VO 2 +(aq) + 2H+(aq) + e → VO2+(aq) + H 2 O(l) +1.02
Ce4+(aq) + e → Ce3+(aq) +1.70

a) Give the components of the standard reference electrode used in determining the standard electrode
potentials above. State the conditions under which this standard reference electrode has a potential
of 0.00 V.

Components:

Conditions:

[6]

b) A diagram of a cell is shown below.

V
Zinc Magnesium
Salt bridge

1.0 M Zn2+ (aq) 1.0 M Mg 2+(aq)

i. Calculate the overall standard potential of this cell.

ii. State the polarity of the zinc electrode.

[2]
c) A diagram of a cell is shown below.

V
Inert electrode Inert electrode
Salt bridge

Solution 1.0 M with Solution 1.0 M with

respect to VO 2+ (aq), respect to Ce4+ (aq),
V 3+(aq) and H + (aq) Ce 3+ (aq) and H +(aq)

i. Calculate the overall standard potential of the cell.

ii. Deduce the direction of electron flow in the external circuit when the inert electrodes are
connected.

[2]

d) Using data from the table on page 6, derive an equation for the overall redox process which occurs
when a solution containing Ce4+(aq) is added to a solution containing V3+(aq).

[3]

e) Which, if any, of the four vanadium-containing species, V2+(aq), V3+(aq), VO2+(aq) and VO2+(aq),
will convert Sn2+(aq) into Sn4+(aq) in acid solution?

[2]

Total: 15 marks
3. Where appropriate, use the standard electrode potential data in the table below to answer the questions
which follow.
Eο/V
Zn2+(aq) + 2e → Zn(s) –0.76
V3+(aq) + e → V2+(aq) –0.26
SO 4 (aq) + 2H (aq) + 2e → SO 3 (aq) + H 2 O(l)
2- + 2 − +0.17
2+ +
VO (aq) + 2H (aq) + e → V (aq)
3+
+ H 2 O(l) +0.34
3+
Fe (aq) + e → Fe (aq)
2+
+0.77
VO 2 +(aq) + 2H+(aq) + e → VO2+(aq) + H 2 O(l) +1.00
C l2 (aq) + 2e → 2Cl–(aq) +1.36

a) From the table above select the species which is the most powerful reducing agent.

[1]

b) From the table above select

i. a species which, in acidic solution, will reduce VO 2 +(aq) to VO2+(aq) but will not reduce
VO2+(aq) to V3+(aq),

ii. a species which, in acidic solution, will oxidise VO2+(aq) to VO 2 +(aq).

[2]

c) The cell represented below was set up under standard conditions.

Pt|Fe2+(aq), Fe3+(aq)||Tl3+(aq),Tl+(aq)|Pt Cell e.m.f. = + 0.48 V

1. Deduce the standard electrode potential for the following half-reaction.

Tl3+(aq) + 2e– → Tl+(aq)

2. Write an equation for the spontaneous cell reaction.

[3]

Total: 6 marks
II Electrolysis

Extraction of Aluminium:

1. Explain why aluminium is not extracted by reaction of its oxide with carbon

2. Explain why aluminium oxide is dissolved in molten cryolite.

3. Write half-equations for the reactions at each electrode, and write an overall equation for the reaction.

4. State what each electrode is made of.

5. Explain why the anodes need to be regularly replaced.

6. Explain why the elctrolysis of aluminium oxide is expensive.

Faraday:

1. Calculate the quantity of electricity, Q, obtained when a current of 25 amps runs for 1 minute.

2. Calculate the current needed to provide 30,000 coulombs of electricity in 5 minutes.

3. Calculate the time required to produce 12,000 C of electricity using a current of 10 A.

4. Calculate the quantity of electricity obtained from 2 moles of electrons

5. Calculate the moles of electrons obtained from 250 C of electricity

6. Calculate the time required to deposit 56g of silver from a silver nitrate solution using a current of 4.5 A.

Ag+ + e → Ag(s)

7. What mass of copper could be deposited from a copper (II) sulphate solution using a current of 0.50 A
over 10 seconds?
Cu2+ + 2e → Cu(s)