THE UNIVERSITY OF ZAMBIA

SCHOOL OF NATURAL SCIENCES

DEPARTMENT OF CHEMISTRY
ACADEMIC YEAR 2019/20
Solved questions on Electrochemistry

1. Calculate the standard electrode potential of the Na+/Na electrode given that when it was
joined to standard hydrogen electrode (SHE), the emf of the cell was -2.71 V.
Ecell = Eunknown – EStandard
-2.71 V = Eunknown – 0
Eunknown = - 2.71 V

2. Calculate the emf of the cell with standard silver- silver chloride electrode (E o= + 0.22 V)
as the left hand electrode and Fe2+ / Fe (Eo= - 0.44 V) as right hand electrode.

Ecell = ERHS – ELHS

= 0.22 – (-0.44) V =0.66 V

3. Which of the following disproprtionation reactions are spontaneous under standard

conditions? Give reasons.
(i) Cu+(aq) Cu2+ (aq) + Cu(s)
(ii) Fe2+(aq) Fe3+ (aq) + Fe(s)

i. E°cell = E°cathode - E°anode = 0.52 – (0.15) = + 0.37 V Spontaneous

Cell potential is +ve
ii. E°cell = E°cathode - E°anode= -0.44- 0.77 = - 1.21 V Nonspontaneous
Cell potential is - ve

4. Read Page 847 to 859 from text book, Chemistry by Zmdahl, Zumdahl, 8 th Edition and
answer the following questions:
(a) The electrolysis of BiO+ produces pure bismuth. How long will it take to produce
10.0 g of bismuth by the electrolysis of BiO+ solution using a current of 25.0 A?
𝟏𝟎.𝟎 𝒈
Moles of Bismuth = = 𝟎. 𝟎𝟒𝟕𝟖 𝒎𝒐𝒍
𝟐𝟎𝟗
𝟏
Moles of bismuth = (moles of electrons)
𝟑
Moles of electron = 3 x 0.0478 =0.1434 mol
Charge flowing through the cell = number of moles of electrons x Faraday = I. t
0.1434 mol x 96485 C = 25.0 A x t
t = 553.4 s

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 (b) An unknown metal M is electrolyzed. It took 74.1 s for the current of 2.00 A to plate
out 0.107 g of the metal from a solution containing M(NO 3)3. Identify the metal.

Charge = 2 A x 74.1 s = 148.2C

𝟏𝟒𝟖.𝟐𝑪
Moles of electron = / = 0.00153599mol
𝟗𝟔𝟒𝟖𝟓 𝐂/ 𝐦𝐨𝐥
𝟏
Moles of aluminium = ( moles of electrons)
𝟑
𝟏
= (0.00153599) = 0.000511996mol
𝟑
Molar Mass = 0.107 g / 0.00153599mol = 208.986 g /mol
Hence, the metal is Bismuth.

5. An iron bar is to be electroplated with zinc.

(a) Identify what will act as the two electrodes for the cell

The Iron bar and the zinc plate will act as electrodes.

(b) Identify each electrode as either the anode or cathode

Anode Zinc and Cathode iron

(c) Write the half-reactions occurring at each electrode

Reaction at anode Zn(s) Zn2+(aq) + 2e-

Reaction at Cathode Zn2+(aq) + 2e- Zn(s)

(d) Identify a solution that would make a suitable electrolyte for this cell

Zinc salt solution

(e) Identify which electrode will be attached to the negative post of the battery and
which will be attached to the positive post, and explain.

Anode to positive and cathode to the negative.

A fully labeled diagram may be a useful way to answer these questions.

6. Sketch the galvanic cells based on the following reactions. Clearly label the cells showing
direction of electron flow, ion migration through the salt bridge and identify cathode and
anode respectively. All concentrations are 1.0 M and partial pressure is 1.0 atm.

(a)IO (aq) + Fe (aq) ⇌ Fe (aq) + I (aq)

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 Split the equation into two half reactions

𝐈𝐎𝟑 (𝐚𝐪) + 𝟓𝒆 + 𝟔𝐇 (𝐚𝐪) ⇌ 𝟑𝑯𝟐 𝑶(𝐥) + 𝟏𝟐𝐈𝟐 (𝐚𝐪)ℇ𝒐 = 𝟏. 𝟐𝟎 𝑽

(𝐅𝐞𝟐 (𝐚𝐪) ⇌ 𝐅𝐞𝟑 (𝐚𝐪) + 𝒆 )x 5 to balance electronsℇ𝒐 = −𝟎. 𝟕𝟕 𝑽

Overall balanced reaction is
𝟏
𝐈𝐎𝟑 (𝐚𝐪)+ 𝟔𝐇 (𝐚𝐪) + 𝟓𝐅𝐞𝟐 (𝐚𝐪) ⇌ 𝟓𝐅𝐞𝟑 (𝐚𝐪) + 𝟑𝐇𝟐 𝐎(𝐥) + 𝟐𝐈𝟐 (𝐚𝐪)

The cell diagram is

(b) Zn(s) + Ag (aq) ⇌ Zn (aq) + Ag(s)

The half reactions are

𝐙𝐧(𝐬) ⇌ 𝐙𝐧𝟐 (𝐚𝐪) + 𝟐𝒆 )ℇ𝒐 = +𝟎. 𝟕𝟔 𝑽

𝐀𝐠 (𝐚𝐪) + 𝟏𝒆 ⇌ 𝐀𝐠(𝐬)ℇ𝒐 = +𝟎. 𝟖𝟎 𝑽 multiply by 2 to balance electrons

Overall equation is

𝐙𝐧(𝐬) + 𝟐𝐀𝐠 (𝐚𝐪) ⇌ 𝐙𝐧𝟐 (𝐚𝐪) + 𝟐𝐀𝐠(𝐬)

The cell diagram is

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 (c) Calculate ℇ for each galvanic in parts (a) and (b).

For (a) 𝓔𝒄𝒆𝒍𝒍 = 𝟏. 𝟐𝟎 + (−𝟎. 𝟕𝟕) = 𝟎. 𝟒𝟑 𝑽

For (b) 𝓔𝒄𝒆𝒍𝒍 = 𝟎. 𝟖𝟎 + 𝟎. 𝟕𝟔 = 𝟏. 𝟓𝟔 𝑽

7. The overall reaction in the lead storage battery is

Pb(s) + PbO (s) + 2H (aq) + 2HSO (aq) → 2PbSO (s) + 2H O (l)

If ℇ = 2.04 𝑉, calculate ℇ at 25 OC under the following conditions; [𝐻 𝑆𝑂 ] = 4.5 𝑀

clearly stating relevant thermodynamic conditions to be met for your calculation.

The overall reaction in the lead storage battery is

𝐏𝐛(𝐬) + 𝐏𝐛𝐎𝟐 (𝐬) + 𝟐𝐇 (𝐚𝐪) + 𝟐𝐇𝐒𝐎𝟒 (𝐚𝐪) → 𝟐𝐏𝐛𝐒𝐎𝟒 (𝐬) + 𝟐𝐇𝟐 𝐎 (𝐥)

Lead oxidises from the metallic form to the +2 state in leadsulfate hence n=2

𝟎. 𝟎𝟓𝟗𝟐 𝟎. 𝟎𝟓𝟗𝟐 [𝑷𝒃𝑺𝑶𝟒 ]𝟐 [𝑯𝟐 𝑶]𝟐

𝓔 = 𝓔𝒐 − 𝒍𝒐𝒈𝑸𝓔 = 𝟐. 𝟎𝟒 − 𝒍𝒐𝒈
𝒏 𝟐 [𝑷𝒃]𝟏 [𝑷𝒃𝑶𝟐 ]𝟏 [𝑯 ]𝟐 [𝑯𝑺𝑶𝟒 ]𝟐

𝟎. 𝟎𝟓𝟗𝟐 [𝟏]𝟐 [𝟏]𝟐 𝟎. 𝟎𝟓𝟗𝟐 𝟏

𝓔 = 𝟐. 𝟎𝟒 − 𝒍𝒐𝒈 𝟏 𝟏 𝟐 𝟐
= 𝟐. 𝟎𝟒 − 𝒍𝒐𝒈
𝟐 [𝟏] [𝟏] [𝟒. 𝟓] [𝟒. 𝟓] 𝟐 [𝟒. 𝟓] [𝟒. 𝟓]𝟐
𝟐

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 𝟎. 𝟎𝟓𝟗𝟐 𝟏
𝓔 = 𝟐. 𝟎𝟒 − 𝐥𝐨𝐠
𝟐 𝟐𝟎. 𝟐𝟓 × 𝟐𝟎. 𝟐𝟓
𝓔 = 𝟐. 𝟎𝟒 − (−𝟎. 𝟕𝟕) = 𝟐. 𝟏𝟏𝟕 𝐕 = 𝟐. 𝟏𝟐 𝐕

Thermodynamic conditions are that solids have a unit concentration and that
dissociation of sulfuric acid is 100%.

8. Given the following galvanic cell at 25OC.

Pt(s) | Cr2+ (0.3M),Cr3+(2.0M)|| Co2+ (0.20M) | Co(s)

Write a balanced overall cell reaction. Equilibrium constant, K, for this reaction is
2.79 X 107, calculate the cell potential ℇ and ∆G for this reaction at the given
temperature.

(Cr2+ → Cr3+ + e−) × 2

Co2+ + 2 e− → Co

Final balanced equation is

2Cr2+(aq) + Co2+(aq)→2Cr3+(aq)+ Co(s)

At equilibrium, 𝓔 = 𝟎 𝐚𝐧𝐝

𝟎. 𝟎𝟓𝟗𝟐 𝟎. 𝟎𝟓𝟗𝟐
𝓔𝐨 = 𝐥𝐨𝐠 𝐐 = 𝐥𝐨𝐠(𝟐. 𝟕𝟗 × 𝟏𝟎𝟕 ) = 𝟎. 𝟐𝟐𝐕
𝟐 𝟐

9. A CHE 1000 student constructs a concentration cell by dissolving 169.88 g of Silver

nitrate in water up to a volume of 1 L, in both compartments. He dips pure silver
electrodes in both solutions and connects them using a piece of wire.
(a) Calculate the concentration of silver nitrate in the compartments.

𝑚 169.88𝑔
𝑛= = = 1.00 𝑚𝑜𝑙
𝑀 169.88𝑔/𝑚𝑜𝑙

Concentration = 1.00 M

(b) Calculate the potential of this cell.

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 Realising his mistake, the student adds 16.988 g more of silver nitrate to one
compartment.

Cathode reaction: 𝐀𝐠 (𝐚𝐪) + 𝟏𝒆 ⇌ 𝐀𝐠(𝐬) ℇ𝒐 = +𝟎. 𝟖𝟎 𝑽

𝐀𝐧𝐨𝐝𝐞 𝐫𝐞𝐚𝐜𝐭𝐢𝐨𝐧: 𝐀𝐠(𝐬) ⇌ 𝐀𝐠 (𝐚𝐪) + 𝟏𝒆 ℇ𝒐 = −𝟎. 𝟖𝟎 𝑽

𝐸 = 0.80 − (0.80) = 0.00 𝑉

At 25 ºC

𝟎. 𝟎𝟓𝟗𝟏
𝑬 = 𝑬𝟎 − 𝒍𝒐𝒈 𝑸
𝒏
𝟎. 𝟎𝟓𝟗𝟏 𝟏
=𝟎− 𝒍𝒐𝒈
𝟏 𝟏
=𝟎𝑽
(c) Calculate the potential of the cell upon addition of the extra 16.988 g of silver nitrate.

𝟏𝟔.𝟗𝟖𝟖 𝐠
[Ag+] = = 0.100 mol
𝟏𝟔𝟗.𝟖𝟖 𝐠 𝐦𝐨𝐥 𝟏
In this experiment total number of moles are = 1.0 + 0.100 = 1.10 moles

𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒘𝒆 𝒄𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏

𝑬 = 𝑬𝟎 − 𝒍𝒐𝒈
𝒏 𝒉𝒊𝒈𝒉𝒆𝒓 𝒄𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏
𝟎. 𝟎𝟓𝟗𝟏 𝟏𝑴
𝑬=𝟎− 𝒍𝒐𝒈 = 𝟎. 𝟎𝟎𝟐𝟒𝟒 𝑽
𝟏 𝟏. 𝟏 𝑴

(d) Predict what happens to the cell potential if the student decides to add some sodium
chloride solution to the other compartment.
The Ag+ ion gets used up in the reaction with sodium chloride, therefore
concentration of Ag+ reduces, hence the cell potential increases.

10. A CHE 1000 student accidently drops her pure silver earrings in a 1 M acidified solution
of KMnO4 prepared by the technicians.
(a) Write the balanced full chemical equation for this reaction.
Oxidation half: Ag (s) ⇌ Ag+ (aq) + e-
Reduction half: 𝑴𝒏𝑶𝟒 (𝒂𝒒) + 𝟖𝑯 (𝒂𝒒) + 𝟓𝒆 ⇌ 𝑴𝒏𝟐 (𝒂𝒒) + 𝟒𝑯𝟐 𝑶(𝒍)

Overall reaction: 𝑴𝒏𝑶𝟒 (𝒂𝒒) + 𝟖𝑯 (𝒂𝒒) + 𝟓𝑨𝒈(𝒔) ⇌ 𝑴𝒏𝟐 (𝒂𝒒) + 𝟒𝑯𝟐 𝑶(𝒍) + 𝟓𝑨𝒈

(b) Calculate the ΔG° of this reaction

E°cell = E°cathode - E°anode = 1.51 – (0.80) = + 0.71 V

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 ∆𝐆𝟎 = 𝐧𝐅𝐄 𝟎
𝐜
= 𝟓 𝐦𝐨𝐥 𝐨𝐟 𝐞𝐥𝐞𝐜𝐭𝐫𝐨𝐧𝐬 × 𝟗𝟔𝟖𝟒𝟓 × 𝟎. 𝟕𝟏 𝐕
𝐦𝐨𝐥 𝐨𝐟 𝐞𝐥𝐞𝐜𝐭𝐫𝐨𝐧𝐬
= −𝟑𝟒𝟐𝟓𝟐𝟏. 𝟕𝟓 𝐉
Note: V = J/ C
(c) Predict whether the earrings will dissolve in this solution. Give a reason for your
answer.
Since ∆𝐆𝟎 is negative reaction will be spontaneous, therefore, earring will
dissolve in the soution.

12. (a) Define corrosion in electrochemical (redox) terms.

Corrosion is the slow oxidation of a metal

(b) Using E° values, arrange the following elements in increasing order of ease of
corrosion when exposed to air (assuming the air contains only oxygen).
Pb, Cu, Al, Ag, Au, Fe, Ni

Since corrosion involves oxidation, all metals with a reduction potential

lower than that of oxygen will easily be corroded. From the reduction
potentials, the least easily corroded is Auand the most easily corroded is Al.
Therefore, the order of corrosion in increasing order of ease shall be as
follows

Au (1.51V), Ag (0.80 V), Cu (0.52 V), Fe (-0.036 V), Pb (-0.13 V), Ni (-0.23 V), Al (-1.66 V)

(c) Briefly describe cathode protection.

Cathode protection is a method used to protect metals from corrosion. It

involves connecting an active metal, such as magnesium, through a wire to
the metal that needs to be protected. The active metal being a better reducing
agent than the metal being protected, furnishes the electrons keeping the
desired metal from being oxidised.