Electrochemistry

I lift, you grab…… was that concept

just a little too complex, Ibrahim?

Ibrahim Suba Kamara

MSc. Analytical Chemistry 1
Electrochemistry is the branch of physical chemistry that studies chemical
processes that cause electrons to move. This movement of electrons is called
electricity, which can be generated by movements of electrons from one element
to another in a reaction known as an oxidation-reduction (redox) reaction.

2
 Topic Outline
• Redox Reactions
 Brief consideration of the types of reactions: combinations,
Decomposition, Double Decomposition, Precipitations & Neutralizations.
• Oxidation – Reduction Reactions: Initial concepts: Meaning of oxidation and
reduction in terms of Loss and gain of oxygen; Loss and gain of hydrogen;
Electron transfer
• Concept of oxidation number. Rules of assigning oxidation numbers.
Oxidation and reduction in terms of oxidation numbers.
• Complementary nature of oxidation and reduction. Oxidation and reduction
half reactions. Separation of simple Redox Reactions into ion-electron half
equations and the combination to obtain the overall redox equation.

3
 Electrolysis
• Initial concept: Electrolytes, Non-electrolytes, Strong and Weak Electrolytes;
Acids, Bases & Salts as Electrolytes; Electrodes: Anode and Cathode.
Definitions and examples of the above. Diagram of simple electrolytic cell:
Definition of Electrolysis.
• Electrolytes Dissociation & mechanism of Electrolytes. Exchange of
electrons between electrodes and ions.
• Selective discharge of ions. Factors governing selective discharge.
• Electrolysis of simple compounds e.g. acidified water (pt electrodes),
𝑁𝑎𝐶𝑙(𝑎𝑞) (dilute and concentrated), Pt. electrodes and Hg cathode, 𝐶𝑢𝑆𝑂4
using Pt and Cu electrodes to illustrate the principles of electrolysis.
• Quantitative Aspects of electrolysis. Sketch graphs of mass vs time at
constant current; mass vs. current at constant time; mass vs. Quantity of
electricity leading to Faraday’s first law of electrolysis. 4
The Faraday constant calculation. Faraday’s 2nd law of electrolysis
• Applications of electrolysis
 Purification of Cu
 Extraction of Al
 Electroplating
 Calibration of Ammeter

Reference books:
• Physical Chemistry (10th Edition) by Pater Atkins
• General Chemistry (3rd Edition) by Raymond Chang
• Fundamental University Physical Chemistry by Olajire A.

5
 Redox Reactions
Oxidation-Reduction in terms of gain or loss of Oxygen & Hydrogen
Oxidation reaction occurs when oxygen is chemically added to an element or
compound. Or when hydrogen is chemically removed from an element of
compound
4𝐹𝑒(𝑠) + 3𝑂2 → 2𝐹𝑒2 𝑂3(𝑠)
2𝐶𝑂(𝑔) + 𝑂2(𝑔) → 2𝐶𝑂2(𝑔)
2𝑀𝑔(𝑠) + 𝑂2(𝑔) → 2𝑀𝑔𝑂(𝑠)
𝐶𝑙2(𝑔) + 𝐻2 𝑆(𝑔) → 𝑆(𝑔) + 2𝐻𝐶𝑙(𝑔)
Reduction reaction occurs when oxygen is chemically removed from an element or
compound. Or when hydrogen is chemically added to an element or compound
𝑍𝑛𝑂(𝑠) + 𝐶(𝑠) → 𝑍𝑛(𝑠) + 𝐶𝑂(𝑔)
∆
2𝑀𝑔𝑂(𝑠) → 2𝑀𝑔(𝑠) + 𝑂2(𝑔)
2𝑁𝑎(𝑠) + 𝐻2(𝑔) → 2𝑁𝑎𝐻(𝑠)
6
Oxidation-Reduction in terms of gain or loss of electrons
Oxidation reactions occur when an element or compound looses one or more
electrons
𝑀𝑔(𝑠) − 2𝑒 − → 𝑀𝑔2+ (𝑎𝑞)
Reduction reactions occur when an element or compound gains one or more
electrons
𝑀𝑔2+ 𝑎𝑞 + 2𝑒 − → 𝑀𝑔(𝑠)
Oxidizing and Reducing agents
• Any substance which helps oxidation to occur is called the oxidizing agent. Since
oxidation involves the loss of electrons, the substance that accepts the lost
electrons is called the oxidizing agent. That’s, an oxidizing agent is a substance
which accepts electrons.
• Similarly, a reducing agent occurs when an element or compound gains
electrons. The substance that donates the electrons is called the reducing
agent. 7
 Examples of Oxidation-Reduction Reactions
Chemical Equation Oxidizing agent Reducing agent
2𝑀𝑔(𝑠) + 𝑂2(𝑔) → 2𝑀𝑔𝑂(𝑠) Oxygen Magnesium

𝐶(𝑠) + 2𝑍𝑛𝑂(𝑠) → 𝐶𝑂2(𝑔) + 2𝑍𝑛(𝑠) Zinc Oxide Carbon

2𝑃𝑏𝑂(𝑔) + 𝑐(𝑠) → 2𝑃𝑏(𝑠) + 𝐶𝑂(𝑔) Lead(II) Oxide Carbon

𝐻2 𝑆(𝑔) + 2𝐹𝑒𝐶𝑙3(𝑎𝑞) → 𝑆(𝑠) + 2𝐻𝐶𝑙(𝑎𝑞) + 2𝐹𝑒𝐶𝑙2(𝑎𝑞) Iron(III) Chloride Hydrogen Sulphide

2𝐻2 𝑆(𝑔) + 𝑆𝑂2(𝑔) → 𝐻2 𝑂(𝑙) + 3𝑆(𝑠) Sulphur (IV) Oxide Hydrogen Sulphide

𝐶𝑢𝑂(𝑠) + 𝐻2(𝑔) → 𝐶𝑢(𝑠) + 𝐻2 𝑂(𝑙) Cupper(II) Oxide Hydrogen

4𝐻𝐶𝑙(𝑔) + 𝑂2(𝑔) → 2𝐶𝑙2(𝑔) + 𝐻2 𝑂(𝑙) Oxygen Hydrogen Chloride

8
Note: Oxidizing agents does not always contain oxygen atom or atoms. A reducing
agent does not always also does not always contain hydrogen atom or atoms.
Consider the following equation:
Oxidation
2+ 2+
𝑀𝑔(𝑠) + 𝐶𝑢(𝑎𝑞) → 𝑀𝑔(𝑎𝑞) + 𝐶𝑢(𝑠)
reducing agent oxidizing agent

Reduction
From the equation above:
• Magnesium atom looses electrons; it is therefore oxidized to 𝑀𝑔2+
• Cupper ions gain electrons; and were reduced to Cu metal.
• Magnesium atoms donate electrons to Cu ions; they are the reducing agents
• Cupper ions accepts electrons from Mg atoms; they are the oxidizing agents
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 Half equations
A half-equation is a separate equation showing which substance gains or looses
electrons in a redox reaction
• An oxidation half-equation is the separate equation showing the substance that
becomes oxidized by loosing one or more electrons
• A reduction half-equation is the separate equation showing the substance that
becomes reduced by gaining one or more electrons
Consider the equation:
2+ 2+
𝑀𝑔(𝑠) + 𝐶𝑢𝑎𝑞) → 𝑀𝑔(𝑎𝑞) + 𝐶𝑢(𝑠)
2+
Oxidation-half equation: 𝑀𝑔(𝑠) → 𝑀𝑔(𝑎𝑞)
2+
Reduction-half equation: 𝐶𝑢𝑎𝑞) → 𝐶𝑢(𝑠)
2+
The oxidation-half equation means Mg has been oxidized to 𝑀𝑔(𝑎𝑞)
2+
The reduction-half equation means 𝐶𝑢𝑎𝑞) has been reduced to Cu
10
 Oxidation number
• Oxidation number (also called oxidation state) refers to the number of charges
an atom would have in a molecule (or an ionic compound) if electrons were
transferred completely.
• A substance is said to be oxidized when its oxidation number increases
• A substance is reduced when its oxidation number decreases.
• If the oxidation number of a substance reduces, it has acted as an oxidizing
agent
• If the oxidation number of a substance increases, it has acted as a reducing
agent. +5 +4

𝐶𝑢(𝑠) + 4𝐻𝑁𝑂3(𝑙) → 𝐶𝑢(𝑁𝑂)2(𝑎𝑞) + 2𝑁𝑂2(𝑔) + 2𝐻2 0(𝑙)

0 +2 11
 +1 +1
+ 2−
2𝐶𝑟𝑂42+ 𝑎𝑞 + 2𝐻(𝑎𝑞) → 𝐶𝑟𝑂7(𝑎𝑞) + 𝐻2 𝑂(𝑙)

+6 +6
• Any reaction that shows no change in oxidation number of any of its elements is
not a redox reaction .
Rules for assigning oxidation numbers
1. In free elements (that is, in the uncombined state), each atom has an oxidation
number of zero. Thus, each atom of 𝐻2 , 𝐵𝑟2 , 𝑁𝑎, 𝐵𝑒, 𝐾, 𝑂2 𝑎𝑛𝑑 𝑃4 has the same
oxidation number: zero.
2. For ions composed of only one atom, the oxidation number is equal to the
charge on the ion. Thus 𝐿𝑖 + has an oxidation number of +1; 𝐵𝑎2+ ion, +2; 𝐹𝑒 3+
ion, +3; 𝐼 − ion, -1; 𝑂2− , -2 and so on. All alkali metals have an oxidation
number of +1, and all alkali earth metals have an oxidation number of +2 in
their compounds. Al has an oxidation number of +3 in all its compounds.
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3. The oxidation number of oxygen in most compounds is -2 except in peroxide
ion and hydrogen peroxides where it is -1.
4. The oxidation number of hydrogen is +1 in most compounds except in metal
hydrides where it is -1.
5. Fluorine has an oxidation number of -1 in all its compound. Other halogens (Cl,
Br and I) have negative oxidation numbers when they occur as halide ions in
their compounds.
6. In a neutral compound, the sum of the oxidation numbers of all the atoms must
be equal to zero. In a polyatomic ion, the sum of the oxidation numbers of all
the elements in the ion must be equal to the charge f the ion.
Example: Assign oxidation numbers to all the elements in the compounds.
𝐿𝑖2 𝑂
𝐻𝑁𝑂3
𝐶𝑟2 𝑂7−
𝑀𝑛𝑂4−
𝐾2 𝐶𝑟2 𝑂7 13
 Disproportionation
In some reactions, some atoms or ions are oxidized, whilst others, identical, atoms
or ions are reduced. Such a reaction is called disproportionation.
+3 +5

3𝐻𝑁𝑂2(𝑎𝑞) → 𝐻𝑁𝑂3(𝑎𝑞) + 2𝑁𝑂(𝑔) + 𝐻2 𝑂(𝑙)

+3 +2
+1 0

+ 2+
2𝐶𝑢(𝑎𝑞) → 𝐶𝑢(𝑠) + 𝐶𝑢(𝑎𝑞)

+1 +2
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Reading assignment: Test for redox reactions
Balancing Redox reaction
The following rules are applicable in balancing REDOX reactions in acidic medium:
1. Write the unbalanced equation for the reaction in ionic form.
2. Separate the equation into two half-equations: Oxidation half equation and
reduction half equation.
3. Balance the atoms other than H and O in each half-reaction separately.
4. Add 𝐻2 𝑂 to balance the O atoms and 𝐻 + to balance the H atoms on the sides
that are less in oxygen and hydrogen respectively.
5. Add electrons to one side of each half-reaction to balance the charges. If
necessary, equalize the number of electrons in the two-reactions by multiplying
one or both half-reactions by appropriate coefficients.
6. Add the two half-reactions together and balance the final equation by
inspection. The electrons on both sides must cancel. 15
6. Add the half equations together, and do cancellation where necessary.
Note: if there is no differences in the number of oxygen atoms on both the left and
right hand sides of the half equations, then proceed to the next step.
Exercises
Balance the following redox reactions in acidic medium
1. 𝐶2 𝑂42− + 𝑀𝑛𝑂4− → 𝑀𝑛2+ + 𝐶𝑂2
2. 𝐾𝑀𝑛𝑂4 + 𝐹𝑒𝑆𝑂4 → 𝑀𝑛𝑆𝑂4 + 𝐹𝑒2 (𝑆𝑂4 )3 + 𝐾2 𝑆𝑂4
Solution
𝐶2 𝑂42− + 𝑀𝑛𝑂4− → 𝑀𝑛2+ + 𝐶𝑂2
Half equations are:
𝐶2 𝑂42− → 𝐶𝑂2 (Oxidation)
𝑀𝑛𝑂4− → 𝑀𝑛2+ (Reduction)
Balanced half-equations are:
𝐶2 𝑂42− → 2𝐶𝑂2 + 2𝑒 − (i)
𝑀𝑛𝑂4− + 8𝐻 + + 5𝑒 − → 𝑀𝑛2+ 4𝐻2 𝑂 (ii) 16
Multiply equation (I) by 5 and equation (II) by 2 and cancel the electrons
5𝐶2 𝑂42− → 10𝐶𝑂2 + 10𝑒 − (iii)
2𝑀𝑛𝑂4− + 16𝐻+ + 10𝑒 − → 2𝑀𝑛2+ 8𝐻2 𝑂 (iv)
5𝑪𝟐 𝑶𝟐−
𝟒 + 𝟐𝑴𝒏𝑶 −
𝟒 + 𝟏𝟔𝑯 + → 𝟏𝟎𝑪𝑶 + 𝟐𝑴𝒏𝟐+ 𝟖𝑯 𝑶(Balanced)
𝟐 𝟐
Exercises
Balance the following redox reactions:
1. 𝐶2 𝑂42− + 𝑀𝑛𝑂4− → 𝑀𝑛2+ + 𝐶𝑂2 (Basic medium)
2. 𝐾𝑀𝑛𝑂4 + 𝐹𝑒𝑆𝑂4 → 𝑀𝑛𝑆𝑂4 + 𝐹𝑒2 (𝑆𝑂4 )3 + 𝐾2 𝑆𝑂4 (acidic medium)
Basic Medium: the following rules are applicable in balancing redox reactions in
basic medium
I. Rules (1), (2), (3), (5) and (6) used in balancing redox reactions in acidic
medium are also applicable for balancing redox reactions in basic medium.
Whilst rule (4) of acidic medium should be modified as follows:
II. We would add 𝑂𝐻− to both sides of the equation for every 𝐻 + . Where 𝐻 + and
𝑂𝐻 − appear on the same side of the equation, we should combine the ions to
give us 𝐻2 𝑂. 17
 Exercise
Balance the following redox reaction in basic medium.
• The unbalanced equation is: 𝑀𝑛𝑂4− + 𝐼 − → 𝑀𝑛𝑂2 + 𝐼2
• The two half-reactions are:
Oxidation: 𝐼 − → 𝐼2
Reduction: 𝑀𝑛𝑂4− → 𝑀𝑛𝑂2
• To balance the I atoms in the oxidation half-reaction, we write
2𝐼 − → 𝐼2
• In the reduction half-reaction, we add two 𝐻2 𝑂 molecules on the right to
balance the O atoms
𝑀𝑛𝑂4− → 𝑀𝑛𝑂2 + 2𝐻2 𝑂
To balance the H atoms, we add four 𝐻 + ions on the left:
𝑀𝑛𝑂4− + 4𝐻 + → 𝑀𝑛𝑂2 + 2𝐻2 𝑂
Because the reaction occurs in a basic medium and there are four 𝐻 + ions, we add
four 𝑂𝐻 − ions to both sides of the equation: 18
 𝑀𝑛𝑂4− + 4𝐻 + + 4𝑂𝐻 − → 𝑀𝑛𝑂2 + 2𝐻2 𝑂 + 4𝑂𝐻 −
Combining 𝑡ℎ𝑒 𝐻 + 𝑎𝑛𝑑 𝑂𝐻 − ions to form 𝐻2 𝑂 and cancelling two 𝐻2 𝑂 molecules
from both sides, we have: 𝑀𝑛𝑂4− + 4𝐻2 𝑂 → 𝑀𝑛𝑂2 + 2𝐻2 𝑂 + 4𝑂𝐻 −
𝑀𝑛𝑂4− + 2𝐻2 𝑂 → 𝑀𝑛𝑂2 + 4𝑂𝐻 −
• Next step is to balance the charges of the two half-reactions:
2𝐼 − → 𝐼2 + 2𝑒 −
𝑀𝑛𝑂4− + 2𝐻2 𝑂 + 3𝑒 − → 𝑀𝑛𝑂2 + 4𝑂𝐻 −
To balance the charges, we multiply the oxidation half-reaction by 3 and the
reduction half-reaction by 2.
6𝐼 − → 3𝐼2 + 6𝑒 −
2𝑀𝑛𝑂4− + 4𝐻2 𝑂 + 6𝑒 − → 2𝑀𝑛𝑂2 + 8𝑂𝐻 −
• The two half-reactions are added together to give:
𝟔𝑰− + 𝟐𝑴𝒏𝑶𝟒− + 𝟒𝑯𝟐 𝑶 → 𝟑𝑰𝟐 + 𝟐𝑴𝒏𝑶𝟐 + 𝟖𝑶𝑯− (Balanced).

19
 Homework
Balance the following redox reactions in basic medium.
− − −
𝑁2 𝑂4(𝑔) + 𝐵𝑟(𝑎𝑞) → 𝑁𝑂2(𝑎𝑞) + 𝐵𝑟𝑂3(𝑎𝑞)
− − −
𝐶𝑁(𝑎𝑞) + 𝑀𝑛𝑂4(𝑎𝑞) → 𝐶𝑁𝑂(𝑎𝑞) + 𝑀𝑛𝑂2(𝑠)
𝐴𝑙(𝑠) + 𝑁𝑂3− → 𝐴𝑙(𝑂𝐻)− 4 + 𝑁𝐻3(𝑔)
Calculations
Ammonium Iron (II) tetraoxosulphate (VI) crystals have the formula:
(𝑁𝐻4 )2 𝑆𝑂4 𝐹𝑒𝑆𝑂4 . 𝑛𝐻2 𝑂. In an experiment to determine ‘n’8.492g of the salt
were dissolved and made up to 250 𝑐𝑚3 of solution with distilled water and dilute
tetraoxosulphate (VI) acid. A 25.0 𝑐𝑚3 portion of the solution was further acidified
and titrated against 𝐾𝑀𝑛𝑂4 solution of concentration 0.0150 mol 𝑑𝑚−3 . A volume
of 22.5 𝑐𝑚3 was required. From the above experimental data, determine the value
of ‘n’ in the formula of the salt.
𝑵 = 𝟏𝟒. 𝟎; 𝑯 = 𝟏. 𝟎; 𝑺 = 𝟑𝟐. 𝟎; 𝑭𝒆 = 𝟓𝟔. 𝟎; 𝑶 = 𝟏𝟔. 𝟎 𝒈𝒎𝒐𝒍−𝟏
20
Balanced half equations are:
𝑴𝒏𝑶− 𝟒 + 𝟖𝑯 + + 𝟓𝒆− → 𝑴𝒏𝟐+ + 𝟒𝑯 𝑶
𝟐 (i)
𝑭𝒆𝟐+ → 𝑭𝒆𝟑+ + 𝒆− (ii)
Multiply equation (ii) by 5 and add it to equation (i) to cancel the electrons
𝑀𝑛𝑂4− + 8𝐻 + + 5𝑒 − → 𝑀𝑛2+ + 4𝐻2 𝑂
5𝐹𝑒 2+ → 5𝐹𝑒 3+ + 5𝑒 −
𝑴𝒏𝑶− 𝟒 + 5𝑭𝒆 𝟐+ + 𝟖𝑯+ → 𝑴𝒏𝟐+ + 𝟓𝑭𝒆𝟑+ + 𝟒𝑯 𝑶
𝟐
# of moles of 𝑀𝑛𝑂4− = 22.5 𝑥 10−3 𝑥0.0150
= 3.380 𝑥 10−4 mol
From the balanced redox equation
# of moles of 𝐹𝑒 2+ = 5 𝑥 # of moles of 𝑀𝑛𝑂4−
= 5 𝑥3.380 𝑥 10−4
= 1.69 𝑥 10−3 moles
21
 Number of moles of 𝐹𝑒 2+ in 250 𝑐𝑚3 solution can be obtained thus:
# of moles of 𝐹𝑒 2+ in 25.0 𝑐𝑚3
# of moles of 𝐹𝑒 2+ in 250 𝑐𝑚3 = 𝑥250 𝑐𝑚 3
25.0 𝑐𝑚3
2+ 3 1.69 𝑥 10−3 moles 3
# of moles of 𝐹𝑒 in 250 𝑐𝑚 = 𝑥 250 𝑐𝑚
25.0 𝑐𝑚3
# of moles of 𝐹𝑒 2+ in 250 𝑐𝑚3 = 1.69 𝑥 10−2 moles = moles of the salt
8.492𝑔
Molar mass of salt = = 502.5 𝑔 𝑚𝑜𝑙 −1
1.69 𝑥 10−2 𝑚𝑜𝑙
Formula mass of the salt: (𝑁𝐻4 )2 𝑆𝑂4 𝐹𝑒𝑆𝑂4 . 𝑛𝐻2 𝑂 is
2(14) + 8(1) + 32 + 4(16) + 56 + 32+ 4(16) + n(18) = 502.5
284 + 18n = 502.5
502.5 −284
n=
18
n = 12
The formula of the salt is (𝑵𝑯𝟒 )𝟐 𝑺𝑶𝟒 𝑭𝒆𝑺𝑶𝟒 . 𝟏𝟐𝑯𝟐 𝑶 22
A 25.0 𝑐𝑚3 portion of sodium ethanedioate solution of concentration 0.30
𝑚𝑜𝑙𝑑𝑚−3 is warmed and titrated against a solution of 𝐾𝑀𝑛𝑂4 . 45.0 𝑐𝑚3 of
𝐾𝑀𝑛𝑂4 is required for the titration. What is the concentration of 𝐾𝑀𝑛𝑂4 in:
𝒊 𝒎𝒐𝒍𝒅𝒎−𝟑 𝒊𝒊 𝒈𝒅𝒎−𝟑
Solution
The redox reaction is:
𝑀𝑛𝑂4 − + 𝐶2 𝑂4 2− → 𝑀𝑛2+ + 𝐶𝑂2
The balanced half equations are:
𝑀𝑛𝑂4 − + 8𝐻 + + 5𝑒 − → 𝑀𝑛2+ + 4𝐻2 𝑂 (𝑖)
𝐶2 𝑂4 2− → 2𝐶𝑂2 + 2𝑒 − (𝑖𝑖)
Multiply equation (i) by 2 and equation (ii) by 5 and add together to cancel out the
electrons:
2𝑀𝑛𝑂4 − + 16𝐻 + + 10𝑒 − → 2𝑀𝑛2+ + 8𝐻2 𝑂 (𝑖𝑖𝑖)
2−
5𝐶2 𝑂4 → 10𝐶𝑂2 + 10𝑒 − 𝑖𝑣
𝟐𝑴𝒏𝑶𝟒 − +5𝑪𝟐 𝑶𝟒 𝟐− + 𝟏𝟔𝑯+ → 𝟐𝑴𝒏𝟐+ + 𝟏𝟎𝑪𝑶𝟐 + 𝟖𝑯𝟐 𝑶
23
No. of moles of 𝐶2 𝑂4 2− (𝑖𝑛 𝑁𝑎2 𝐶𝑟2 𝑂4 . 2𝐻2 𝑂) = 25 𝑥 10−3 𝑥 0.3
= 7.50 𝑥 10−3 𝑚𝑜𝑙.
From the balanced redox equation:
− 2 −
No. of moles of 𝑀𝑛𝑂4 = 𝑛𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶2 𝑂4
5
2
= 𝑥 7.5 𝑥 10−3
5
= 3.0 𝑥 10−3 𝑚𝑜𝑙
# 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓𝐾𝑀𝑛𝑂4
𝑖 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑖𝑛 𝑚𝑜𝑙𝑑𝑚−3 𝑜𝑓 𝐾𝑀𝑛𝑂4 = 3
−3
𝑉𝑜𝑙𝑢𝑚𝑒 𝑖𝑛 𝑑𝑚
3.0 𝑥 10 𝑚𝑜𝑙
=
45 𝑥 10−3 𝑑𝑚3
= 𝟎. 𝟎𝟔𝟕 𝒎𝒐𝒍 𝒅𝒎−𝟑
𝑖𝑖 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 (𝑔𝑑𝑚−3 ) = 𝐶𝑜𝑛𝑐. 𝑚𝑜𝑙𝑑𝑚−3 𝑥 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 of 𝑲𝑴𝒏𝑶𝟒
= 0.067 𝑚𝑜𝑙𝑑𝑚−3 𝑥 158 𝑔𝑚𝑜𝑙 −1
= 𝟏𝟎. 𝟓𝟖 𝒈𝒅𝒎−𝟑 24
 Galvanic Cells
A Galvanic or voltaic cell is an experimental apparatus that is used to generate
electricity through the use of a spontaneous redox reaction. The essential
components of a voltaic cell consist of a Zinc bar which is immersed in a
𝑍𝑛𝑆𝑂4 solution and a copper bar immersed in a 𝐶𝑢𝑆𝑂4 solution. The cell operates
on the principle that the oxidation of Zn to 𝑍𝑛2+ and the reduction of 𝐶𝑢2+ to Cu
can be made to take place spontaneously in separate locations with the transfer of
electrons between them occurring through an external wire. The Zinc and Copper
bars are called electrodes. This particular arrangement of electrodes is called the
Daniel Cell. The anode in a galvanic cell is the electrode where oxidation takes
place and the cathode is the electrode where reduction occurs.
For the Daniel cell, the half-cell reactions, that is, the oxidation and reductions at
the electrodes, are: Zinc electrode (anode): 𝑍𝑛(𝑠) → 𝑍𝑛2+ 𝑎𝑞 + 2𝑒 −
2+
Cu electrode (Cathode): 𝐶𝑢(𝑎𝑞) + 2𝑒 − → 𝐶𝑢(𝑠)
Note that the two solutions should be separated to prevent a chemical reaction
2+
between the two. 𝐶𝑢(𝑎𝑞) + 𝑍𝑛(𝑠) → 𝐶𝑢(𝑠) + 𝑍𝑛2+ 𝑎𝑞 . Otherwise no useful work will
be obtained. 25
To complete the electrical circuit, the solutions must be connected by a conducting
medium through which the cations and anions can move from one electrode
compartment to the other. This requirement is satisfied by a salt bridge, which in
its simplest form, is an inverted U tube containing an inert electrolyte solution,
such as KCl or 𝑁𝐻4 𝑁𝑂3 , whose ions will not react with other ions in solution or
with the electrodes.

© 𝑊𝑖𝑘𝑖𝑝𝑒𝑑𝑖𝑎 26
During the cause of the overall redox reaction, electrons flow externally from the
anode (Zn electrode) through the wire and voltmeter to the cathode (Cu electrode)
In the solution, the cations (𝑍𝑛2+ , 𝐶𝑢2+ 𝑎𝑛𝑑 𝐾 + ) move towards the cathode,
whilst the anion (𝑆𝑂42− ) move towards the anode. Without the salt bridge
connecting the two solutions, the build up of positive charge in the anode
compartment (due to the formation of 𝑍𝑛2+ ions) and negative charge in the
cathode compartment (created when some of the 𝐶𝑢2+ ions are reduced to Ag)
would quickly prevent the cell from operating.
An electric current flows from the anode to the cathode because there is a
difference in electrical potential energy difference between the electrodes.
Experimentally, the difference in electrical potential between the anode and
cathode is measured by the voltmeter and the reading (in volts) is called cell
voltage.

27
The conventional notation for representing galvanic cells is the cell diagram. If we
assume that the concentrations of 𝑍𝑛2+ 𝑎𝑛𝑑 𝐶𝑢2+ ions are 1M, the cell diagram is

𝑍𝑛 𝑠 ห 𝑍𝑛2+ 1 𝑀 ฮ 𝐶𝑢2+ 1 𝑀 ȁ𝐶𝑢

The single vertical line represents a phase boundary. For example the Zinc
electrode is a solid and the 𝑍𝑛2+ ions (from 𝑍𝑛𝑆𝑂4 ) are in solution. Thus we draw
a line to separate between Zn and 𝑍𝑛2+ to show the phase boundary. The double
vertical lines denote the salt bridge.

By convention, the anode is written first, to the left of the double lines and the
other components appear on the other in which we would encounter them in
moving from the anode to the cathode.

However, two other terms, electromotive force or emf (E) and cell potential are
also used to denote cell voltage. 28
 Standard Reduction Potentials
When the concentrations of the 𝐶𝑢2+ and 𝑍𝑛2+ ions are both 1.0 M, we will
find out that the voltage or the emf of the Daniel cell is 1.10V. This voltage must be
related directly to the redox reactions. Just as the overall cell reaction can be
thought of as the sum of two half-cell reactions, the measured emf of the cell can
be treated as the sum of the electrode potentials at the Zn and Cu electrodes.
Knowing on of these electrode potentials, we could obtain the other by subtraction
from 1.10 V. it is impossible to measure the potential of just one electrode, but if
we arbitrarily set the potential value of a particular electrode at zero, we can use it
to determine the relative potentials of other electrodes. The hydrogen electrode,
serves as a reference for the purpose. Hydrogen gas is bubbled into HCl solution at
25 °C. The platinum electrode has two functions. First, it provides a surface on
which the dissociation of hydrogen molecules can take place:
𝐻2 → 2𝐻 + + 2𝑒 −
Second it serves as an electrical conductor to the external circuit.
Under standard-state conditions (when the pressure of 𝐻2 is 1 amt and the
concentration of the HCl solution is 1 M) the potential for the reduction of 𝐻 + at
25°C is taken to be exactly zero. 29
 2𝐻 + 1 𝑀 + 2𝑒 − → 𝐻2 1𝑎𝑡𝑚 𝐸° = 0 V
The superscript "°" denotes standard – state conditions, and the 𝐸 ° is the standard
electrode reduction potential, or the voltage associated with a reduction reaction
at an electrode when all solutes are 1 M and all gases are at 1 atm. Thus, the
standard reduction potential of the hydrogen electrode is defined as zero. The
hydrogen electrode is called the standard hydrogen electrode (SHE).
We can use the SHE to measure the potentials of other kinds of electrodes.
Consider the cell diagram below:
𝑍𝑛 𝑠 ห 𝑍𝑛2+ 1 𝑀 ԡ 𝐻 + 1 𝑀 ห 𝐻2 (1 𝑎𝑡𝑚) ȁ𝑃𝑡(𝑠)
As mentioned earlier, the Pt electrode provides the surface on which the reduction
takes place. When all reactants are in their standard states (that is, 𝐻2 at 1 atm,
𝐻 + and 𝑍𝑛2+ ions at 1M), the emf of the cell is 0.76 v at 25°C. we can write the
half-cell reaction as:
30
 Anode (oxidation): 𝑍𝑛(𝑠) → 𝑍𝑛2+ (1 𝑀) + 2𝑒 −
Cathode (reduction): 2𝐻 + 1 𝑀 + 2𝑒 − → 𝐻2 ( 1 amt)
Overall: 𝑍𝑛(𝑠) + 2𝐻 + (1 M) → 𝑍𝑛2+ 1 𝑀 + 𝐻2 ( 1 amt)
°
By convention, the standard emf of the cell, 𝐸𝑐𝑒𝑙𝑙, which is composed of a
contribution from the anode and a contribution from the cathode, is given by
° ° °
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
° °
Where both 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 and 𝐸𝑎𝑛𝑜𝑑𝑒 are the standard reduction potentials of the
electrodes. For the Zn-SHE cell, we write:
°
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝐻° + /𝐻2 − 𝐸𝑍𝑛°
2+ /𝑍𝑛

Where the subscripts 𝐻 + /𝐻2 means 2𝐻 + + 2𝑒 − → 𝐻2 and the superscript

𝑍𝑛2+ /𝑍𝑛 means 𝑍𝑛2+ + 2𝑒 − → 𝑍𝑛. Thus the standard electrode potential of
°
Zinc, 𝐸𝑍𝑛 2+ /𝑍𝑛 is − 0.76 V.

31
The standard electrode potential of copper can be obtained in a similar fashion, by
using a cell with a copper electrode and the SHE. In this case, the copper electrode
is the cathode because its mass increases during the operation of the cell, as is
consistent with the reduction reaction:
2+
𝐶𝑢(𝑎𝑞) + 2𝑒 − → 𝐶𝑢(𝑠)
The cell diagram is
𝑃𝑡(𝑠) ห𝐻2 1 𝑎𝑡𝑚 ȁ 𝐻 + 1 𝑀 ฮ 𝐶𝑢2+ 1 𝑀 ቚ𝐶𝑢(𝑠)
And the half-cell reactions are:
Anode (oxidation): 𝐻2 1 𝑎𝑡𝑚 → 2𝐻 + 1 𝑀 + 2𝑒 −
Cathode (Reduction): 𝐶𝑢2+ 1 𝑀 + 2𝑒 − → 𝐶𝑢 𝑠
Overall: 𝐻2 1 𝑎𝑡𝑚 + 𝐶𝑢2+ 1 𝑀 → 2𝐻 + (1 𝑀) + 𝐶𝑢(𝑠)
Under standard - state conditions and at 25°C, the emf of the cell is 0.34 V, so we
write
° ° °
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒 32
 ° °
0.34 V = 𝐸𝐶𝑢 2+ /𝐶𝑢 − 𝐸𝐻 + /𝐻2
°
0.34 V = 𝐸𝐶𝑢 2+ /𝐶𝑢 - 0

°
𝐸𝐶𝑢 2+ /𝐶𝑢 = 0.34 V + 0

°
𝐸𝐶𝑢 2+ /𝐶𝑢 = 0.34 V

°
In this case the standard reduction potential of copper, 𝐸𝐶𝑢 2+ /𝐶𝑢 is 0.34 V, where

the subscript means 𝐶𝑢2+ + 2𝑒 − → 𝐶𝑢 𝑠 .

For the Daniel cell, we can write
Anode (Oxidation): 𝑍𝑛(𝑠) → 𝑍𝑛2+ (1 𝑀) + 2𝑒 −
cathode (Reduction): 𝐶𝑢2+ 1 𝑀 + 2𝑒 − → 𝐶𝑢 𝑠
Overall: 𝑍𝑛(𝑠) + 𝐶𝑢2+ 1 𝑀 → 𝑍𝑛2+ (1 𝑀) + 𝐶𝑢 𝑠
° ° °
The emf of the cell is: 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒 33
 ° °
𝐸𝐶𝑢 2+ /𝐶𝑢 - 𝐸𝑍𝑛2+ /𝑍𝑛
= 0.34 v – (-0.76 V)
= 1.10 V
This example illustrates how we can use the sign of the emf of a cell to predict the
spontaneity of a redox reaction. Under standard-state conditions for reactants and
products, the redox reaction is spontaneous in the forward direction if the
standard emf of the cell is positive. If it is negative, the reaction is spontaneous in
°
the opposite direction. It is important to note that a negative 𝐸𝑐𝑒𝑙𝑙 does not mean
that a reaction will not occur if the reactants are mixed at 1 M concentrations. It
merely means that the equilibrium of the redox reaction, when reached, will lie to
the left.

34
Note the following:
1. The 𝐸 ° values apply to the half-cell reactions as read in the forward direction.
2. The more positive 𝐸 ° is, the greater the tendency for the substance to be
reduced.
3. The half-cell reactions are reversible. Depending on the conditions, any
electrode can act either as an anode or as a cathode.
4. Under standard-state conditions, any species on the left of a given half-cell
reaction will react spontaneously with a species that appears on the right of
any half-cell reaction located below it in the electrode potential series. This
principle is sometimes called the diagonal rule.
5. Changing the stoichiometric coefficients of a half-cell reaction does not affect
the value of 𝐸 ° because electrode potentials are intensive properties.
6. Like ∆𝐻, ∆𝐺 𝑎𝑛𝑑 ∆𝑆, the sign of 𝐸 ° changes but its magnitude remains the
same when we reverse a reaction. 35
Example 1: Predict what will happen if molecular bromine 𝐵𝑟2 is added to a
solution containing NaCl and NaI at 25° 𝐶. Assume all species are in their standard
states.
To predict what redox reaction(s) will take place, we need to compare the standard
reduction potentials for the following half-reactions:
𝐶𝑙2 (1 𝑎𝑡𝑚) + 2𝑒 − → 2𝐶𝑙 − 𝐸 ° = 1.36 𝑉
𝐵𝑟2(𝑙) + 2𝑒 − → 2𝐵𝑟 − 𝐸 ° = 1.07 V
𝐼2(𝑠) + 2𝑒 − → 2𝐼 − 𝐸 ° = 0.53 𝑉
Applying the diagonal rule we see that 𝐵𝑟2 will oxidize 𝐼 − but will not oxidize 𝐶𝑙 − .
Therefore the only redox reaction that will occur appreciably under standard
conditions is
Oxidation: 2𝐼 − 1 𝑀 → 𝐼2(𝑠) + 2𝑒 −
Reduction: 𝐵𝑟2(𝑙) + 2𝑒 − → 2𝐵𝑟 − (1 𝑀)
Overall: 2𝐼 − 1 𝑀 + 𝐵𝑟2(𝑙) → 𝐼2(𝑠) + 2𝐵𝑟 − (1 𝑀)
Note: 𝑁𝑎+ ions are inert and do not enter into the redox reaction. 36
A galvanic cell consists of a Mg electrode in a 1.0 M (𝑀𝑔𝑁𝑂3 )2 solution and a Ag
electrode in a 1.0 M 𝐴𝑔𝑁𝑂3 solution. Calculate the standard emf of the
electrochemical cell at 25° 𝐶.
𝐴𝑔+ ( 1.0 𝑀) + 𝑒 − → 𝐴𝑔(𝑠) 𝐸 ° = 0.80 𝑉
𝑀𝑔2+ (1.0 𝑀) + 2𝑒 − → 𝑀𝑔(𝑠) 𝐸 ° = −2.37 𝑉
Applying the diagonal rule, we see that 𝐴𝑔+ will oxidize Mg:
Oxidation: 𝑀𝑔(𝑠) → 𝑀𝑔2+ (1.0 𝑀) + 2𝑒 −
Reduction: 2𝐴𝑔2+ 1 𝑀 + 2𝑒 − → 2𝐴𝑔(𝑠)
Overall: 𝑀𝑔(𝑠) + 2𝐴𝑔2+ 1 𝑀 → 𝑀𝑔2+ (1.0 𝑀) + 2𝐴𝑔(𝑠)
° ° °
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
° °
= 𝐸𝐴𝑔 + /𝐴𝑔 − 𝐸𝑀𝑔2+ /𝑀𝑔

= 0.80 V – (- 2.37 V)
= 3.17 V
37
 Spontaneity of Redox Reactions
In a galvanic cell, chemical energy is converted to electrical energy. Electrical
energy in this case is the product of the emf of the cell and the total electrical
charge (in coulombs) that passes through the cell:
Electrical energy = volts x coulombs
= joules
The total change is determined by the number of moles of electrons (n) that pass
through the circuit. By definition
Total charge = nF
Where F, the faraday constant, is the electrical charge contained in 1 mole of
electrons. Experiments have shown that 1 faraday is equivalent to 965,000
coulombs.
1 F = 96, 500C/mol
Since 1 J = 1 C x 1 V
38
 We can also express the units of faraday as
1 F = 96, 500 J/V.mol
The measured emf is the maximum voltage that the cell can achieve. This value is used to
calculate the maximum amount of electrical energy that can be obtained from the
chemical reaction. The energy is used to do electrical work. Therefore
𝑤𝑚𝑎𝑥 = 𝑤𝑒𝑙𝑒
= − 𝑛𝐹𝐸𝑐𝑒𝑙𝑙
Where 𝑤𝑚𝑎𝑥 is the maximum amount of work that can be done. The negative sign on the
right hand side indicates that the electrical work is done by the system on the
surroundings. Specifically, the change in free energy ∆𝐺 represents the maximum
amount of useful work that can be obtained from a reaction:
∆𝐺 = 𝑤𝑚𝑎𝑥
Therefore, we can write
∆𝐺 = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙 ……………………. (I)
Both n and F are positive quantities and ∆𝐺 is negative for s spontaneous process, so
𝐸𝑐𝑒𝑙𝑙 must be positive. 39
For reactions in which reactants and products are in their standard states, equation
°
(I) becomes ∆𝐺 ° = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙 ……………………………….. (II)
Where 𝐸𝑐𝑒𝑙𝑙 is positive for a spontaneous reaction.
The 𝐸𝑐𝑒𝑙𝑙 to the equilibrium constant (K) of a redox reaction can be related. The
∆𝐺 ° for a reaction is related to its equilibrium constant as
∆𝐺 ° = −𝑅𝑇 ln 𝐾
If we combine equations (I) and (II) we obtain
°
−𝑛𝐹𝐸𝑐𝑒𝑙𝑙 = −𝑅𝑇 ln 𝐾
Solving for 𝐸𝑐𝑒𝑙𝑙
−𝑅𝑇
= 𝐸𝑐𝑒𝑙𝑙 = ln 𝐾……… (III)
− 𝑛𝐹
Where T = 298K, equation (III) can be simplified by substituting for R and F.
𝐽
8.314𝐾.𝑚𝑜𝑙 298𝐾
𝐸𝑐𝑒𝑙𝑙 = 96,500𝐽 ln K
𝑛( 𝑉 .𝑚𝑜𝑙)
40
 0.0257 𝑉
𝐸𝑐𝑒𝑙𝑙 = ln 𝐾 … … … … … (IV)
𝑛
Alternatively, equation (IV) can be written using base-10 logarithm for K
0.0257 𝑉
𝐸𝑐𝑒𝑙𝑙 = l𝑜𝑔 𝐾 … … … … … (V)
𝑛
Thus, if any one of thethree quantities ∆𝐺 ° , 𝐾 or 𝐸𝑐𝑒𝑙𝑙 is known,
the other two can
be calculated using equation (I), (IV) or (V).
Example
Calculate the equilibrium constant for this reaction at 25° 𝐶
𝑆𝑛(𝑠) + 2𝐶𝑢2+(𝑎𝑞) ↔ 𝑆𝑛2+(𝑎𝑞) + 2𝐶𝑢 + (𝑎𝑞)
The 𝐸 ° 𝑓𝑜𝑟 𝑆𝑛2+ /𝑆𝑛 = −0.14 𝑉 𝑎𝑛𝑑 𝐶𝑢2+ /𝐶𝑢 = 0.15 𝑉
The two half-reactions for the overall process are:
Oxidation: 𝑆𝑛(𝑠) → 𝑆𝑛2+ 𝑎𝑞 + 2𝑒 −
Reduction: 𝐶𝑢2+(𝑎𝑞) + 2𝑒 − → 2𝐶𝑢 +(𝑎𝑞)
41
 𝐸 ° = 𝐸 ° (𝐶𝑢2+ /𝐶𝑢+ ) − 𝐸 ° (𝑆𝑛2+ /𝑆𝑛)
= 0.15 V – (-0.14)
0.29 V
𝑛𝐸 °
ln 𝐾 =
0.0257 𝑉
In the overall reaction, we find n=2.
2 𝑥 0.29 𝑉
Therefore, ln 𝐾 = = 22.6
0.0257 𝑉
𝐾 = 𝑒 22.6 = 6.5 𝑥 109
Home work
Calculate the equilibrium constant for the following reaction at 25° 𝐶.
𝐹𝑒 2+(𝑎𝑞) + 2𝐴𝑔(𝑠) ↔ 𝐹𝑒(𝑠) + 2𝐴𝑔+ (𝑎𝑞)
42
Calculate the standard free-energy change for the following reaction at 25°C.
2𝐴𝑢(𝑠) + 3𝐶𝑎2+ 1 𝑀 → 2𝐴𝑢3+ 1 𝑀 + 3𝐶𝑎(𝑠)
To calculate the ∆𝐺 ° for the reaction we need to know the 𝐸 ° value for the redox
process. The half-reactions for the process are as follows:
Oxidation: 2𝐴𝑢(𝑠) → 2𝐴𝑢3+ 1 𝑀 + 6𝑒 −
Reduction: 3𝐶𝑎2+ 1 𝑀 + 6𝑒 − → 3𝐶𝑎(𝑠)
The 𝐸 °𝐴𝑢3+ /𝐴𝑢 = 1.50 V and 𝐸 °𝐶𝑎2+ /𝐶𝑎 = -2.87 V.
° ° °
Therefore, 𝐸 = 𝐸 𝐶𝑎2+ /𝐶𝑎 - 𝐸 𝐴𝑢3+ /𝐴𝑢
= -2.87 V – 1.50 V
= -4.37 V
∆𝐺 ° = −𝑛𝐹𝐸 °
Where F is faraday’s constant = 96500 C
The overall reaction shows n = 6, therefore 43
 𝐽
∆𝐺 ° =−6(96500 . 𝑚𝑜𝑙)(−4.37 𝑉)
𝑉
= 2.53 𝑥 106 𝐽/𝑚𝑜𝑙
= 2.53 𝑥 103 𝐾𝐽/𝑚𝑜𝑙
Note: The large positive value of ∆𝐺 ° tells us that the reaction is not spontaneous
under standard-state conditions at 25°C.
Calculate ∆𝐺 ° for the following reaction at 25°C.
2𝐴𝑙 3+(𝑎𝑞) + 3𝑀𝑔(𝑠) ↔ 2𝐴𝑙(𝑠) + 3𝑀𝑔2+(𝑎𝑞)

Note the relationships between ∆𝑮° , 𝑲 𝒂𝒏𝒅 𝑬°𝒄𝒆𝒍𝒍

∆𝑮° 𝑲 𝑬° 𝒄𝒆𝒍𝒍 Reaction under standard-state Conditions
Negative >1 Positive Spontaneous (forward reaction)
0 =1 0At equilibrium
Positive <1 Negative Nonspontaneous (forward reaction)
44
 The Effect of Concentration on the cell Emf
There is a mathematical relationship between the emf of the cell and the
concentrations of the reactants and products in a redox reaction under non-
standard conditions.
The equation is derived as follows:
Consider a redox reaction of the type: aA + bB→ cC + dD.
The relationship between ∆𝐺 𝑎𝑛𝑑 ∆𝐺 ° which can be derived from thermodynamics
is, ∆𝐺 = ∆𝐺 ° + 𝑅𝑇𝑙𝑛 𝑄 … … … … … … . . (𝑣𝑖)
Where R is the gas constant (8.314 J/K.mol), T is the absolute temperature of the
reaction and Q is the reaction quotient.
45
 According to equation (I) ∆𝐺 = −𝑛𝐹𝐸 𝑎𝑛𝑑
Equation (II) ∆𝐺 ° = −𝑛𝐹𝐸 °
Substituting into equation (VI) gives
−𝑛𝐹𝐸 = −𝑛𝐹𝐸 ° + 𝑅𝑇 ln 𝑄
Dividing the equation through by −𝑛𝐹 gives
−𝑛𝐹𝐸 −𝑛𝐹𝐸 ° + 𝑅𝑇 ln 𝑄
=
−𝑛𝐹 −𝑛𝐹
𝑅𝑇
𝐸= 𝐸° − ln 𝑄 (Nernst Equation)…………(VII)
𝑛𝐹

° 0.0592 𝑣
At 298 K, equation (VII) becomes 𝐸 = 𝐸 − l𝑛 𝑄 … … … . (𝑉𝐼𝐼𝐼)
𝑛

Equation (VIII) can be expressed using base-10 logarithm of Q

46
 0.0592 𝑣
𝐸= 𝐸° − l𝑜𝑔 𝑄 … … … . (𝐼𝑋)
𝑛
At equilibrium, there is no net transfer of electrons, so E = 0 and Q = K, where F is
the equilibrium constant.
The Nernst equation enables us to calculate E as a function of reactant and product
concentrations in a redox reaction. For example, for the Daniel cell:
2+
𝑍𝑛(𝑠) + 𝐶𝑢(𝑎𝑞) → 𝑍𝑛2+ 𝑎𝑞 + 𝐶𝑢(𝑠)
The Nernst equation for this cell at 25°C can be written as
0.0257 𝑉 𝑍𝑛2+
𝐸 = 1.10𝑉 − ln
2 𝐶𝑢2+
𝑍𝑛2+ 𝑍𝑛2+
If the ratio ൗ 𝐶𝑢2+ is less than 1, ln ൗ 𝐶𝑢2+ is a negative number, so that
the second term on the right-hand side of this equation is positive. Under this
condition E is greater than the standard emf E°. If the ratio is greater than 1, E is
smaller than E°. 47
 Exercise
Predict whether the following reaction would proceed spontaneously as written at
298K.
𝐶𝑜(𝑠) + 𝐹𝑒 2+ (𝑎𝑞) → 𝐶𝑜 2+
(𝑎𝑞) + 𝐹𝑒(𝑠)
Given that 𝐶𝑜2+ = 0.15 M and 𝐹𝑒 2+ = 0.68 M.
We can use the value of E for the redox process to determine the spontaneity of
the reaction. To do so, we need to know E° and ln Q in the Nernst equation. The
half-reactions are:
Oxidation: 𝐶𝑜(𝑠) → 𝐶𝑜2+
(𝑎𝑞) + 2𝑒 +

Reduction: 𝐹𝑒 2+
(𝑎𝑞) + 2𝑒 − → 𝐹𝑒
(𝑠)
The standard electrode potential for
𝐸 ° 𝐶𝑜2+ /𝐶𝑜 = −0.28 𝑉 𝑎𝑛𝑑 𝐸 °𝐹𝑒 2+ /𝐹𝑒 = −0.44 𝑉.
The standard emf is E° = 𝐸 °𝐹𝑒 2+ /𝐹𝑒 - 𝐸 ° 𝐶𝑜2+ /𝐶𝑜
48
 = -0.44 V – (-0.28 V)
= 0.16 V
From equation IX, we write
0.0257 𝐶𝑜 2+
𝐸 = 𝐸° − ln 2+
𝑛 𝐹𝑒

0.0257 0.15
𝐸 = −0.16 𝑉 − ln
2 0.68
= 0.16 V + 0.019 V
= -0.14 V
Since E is negative, the reaction is not spontaneous in the direction written.

49
 Concentration Cells
Because electrode potentials depends on ion concentrations, it is possible to
construct a cell from two half-cells composed of the same material but differing in
ion concentrations. Such a cell is called a concentration cell.
Consider a solution in which zinc electrodes are put into two aqueous solutions of
zinc sulphate at 0.10 M and 1.0 M concentrations. The two solutions are connected
by a salt bridge, and the electrodes are joined by a piece of wire in an arrangement
like the one shown in the previous slides.
According to Le Chatelier’s principle, the tendency for the reduction:
𝑍𝑛2+(𝑎𝑞) + 2𝑒 − → 𝑍𝑛(𝑠)
Increases with increasing concentration of 𝑍𝑛2+ ions. Therefore, reduction should
occur in the more concentrated compartment and oxidation should take place on
the more dilute side. The cell diagram is
𝑍𝑛 𝑠 ห𝑍𝑛2+ (0.10 𝑀) ฯ𝑍𝑛2+ (1.0 𝑀) ቚ𝑍𝑛(𝑠) 50
And the half-reactions are
Oxidation: 𝑍𝑛 𝑠 → 𝑍𝑛2+ 0.10 𝑀 + 2𝑒 −
Reduction: 𝑍𝑛2+ 1.0 𝑀 + 2𝑒 − → 𝑍𝑛 𝑠
Overall: 𝑍𝑛2+ 1.0 𝑀 → 𝑍𝑛2+ 0.10 𝑀
The emf of the cell is

2+
°
0.0257 𝑉 𝑍𝑛 𝑑𝑖𝑙
𝐸= 𝐸 − ln
2 𝑍𝑛2+ 𝑐𝑜𝑛𝑐.
Where the subscripts “dil” and “conc.” refer to the 0.10 M and 1.0 M
concentrations, respectively. The 𝐸 ° for this cell is zero (the same electrode and the
same type of ions are involved), so
0.0257 𝑉 0.10
𝐸=0 − ln
2 1.0
= 0.0296 V 51
The emf of concentration cells is usually small and decreases continually during the
operation of the cell as the concentration in the two compartments approach each
other. When the concentrations of the ions in the two compartments are the
same, E becomes zero, and no further change occurs.
Batteries
A battery is a galvanic cell, or a series of combined galvanic cells, that can be used
as a source of direct electric current at a constant voltage. Although the operations
of a battery is similar in principle to that of the galvanic cell, however, a battery has
the advantage of being completely self-contained and requiring no auxiliary
components such as salt bridges.
The Dry Cell Battery
The most common dry cell, that is, a cell without fluid compartment, is the
Leclanche cell used in flashlights and transistors radios. The anode of the cell
consists of a Zinc can or container that is in contact with manganese
dioxide (𝑀𝑛𝑂2 ) and an electrolyte. The electrolyte consists of ammonium chloride
and zinc chloride in water, to which starch is added to thicken the solution to a
paste like consistency so that it is less likely to leak. A carbon rod serves as the
cathode, which is immersed in the electrolyte in the center of the cell. 52
The cell reactions are:
Anode: 𝑍𝑛(𝑠) → 𝑍𝑛2+(𝑎𝑞) + 2𝑒 −
+
Cathode: 2𝑁𝐻4(𝑎𝑞) + 2𝑀𝑛𝑂2(𝑠) + 2𝑒 − → 𝑀𝑛2 𝑂3(𝑠) + 2𝑁𝐻3(𝑎𝑞) + 𝐻2 𝑂(𝑙)
+
Overall: 𝑍𝑛(𝑠) + 2𝑁𝐻4(𝑎𝑞) + 2𝑀𝑛𝑂2(𝑠) → 𝑍𝑛2+(𝑎𝑞) + 2𝑁𝐻3(𝑎𝑞) + 𝐻2 𝑂(𝑙) + 𝑀𝑛2 𝑂3(𝑠) .
The voltage produced by a dry cell is about 1.5 V.
Mercury Battery
The mercury battery is used extensively in medicine and electronic industries and
is more expensive than the common dry cell. Contained in a stainless steel cylinder,
the mercury battery consists of Zinc anode (amalgamated with mercury) in contact
with a strongly alkaline electrolyte containing zinc oxide and mercury(II) oxide.
The cell reaction is:
Anode: 𝑍𝑛 𝐻𝑔 + 2𝑂𝐻 −(𝑎𝑞) → 𝑍𝑛𝑂(𝑠) + 𝐻2 𝑂(𝑙) + 2𝑒 −
Cathode: 𝐻𝑔𝑂(𝑠) + 𝐻2 𝑂(𝑙) + 2𝑒 − → 𝐻𝑔(𝑙) + 2𝑂𝐻 −(𝑎𝑞)
Overall: 𝑍𝑛 𝐻𝑔 + 𝐻𝑔𝑂(𝑠) → 𝑍𝑛𝑂(𝑠) + 𝐻𝑔(𝑙)
53
Since there is no change in electrolyte composition during operation, the overall
cell reaction involves only solid substances – the mercury battery provides a more
constant voltage (1.35 V) than the Leclanche Cell. It also has a considerably higher
capacity and longer life. This qualities make the mercury battery ideal for use in
pacemakers, hearing aids, electric watches, and light meters.
The Lead Storage Battery
The lead storage battery commonly used in automobiles consists of six identical
cells joined together in series. Each cell has a lead anode and a cathode made of
lead dioxide packed on a metal plate. Both the cathode and the anode are
immersed in an aqueous solution of sulfuric acid, which acts as an electrolyte. The
cell reactions are:
Anode: 𝑃𝑏(𝑠) + 𝑆𝑂42−(𝑎𝑞) → 𝑃𝑏𝑆𝑂4(𝑠) + 2𝑒 −
Cathode: 𝑃𝑏𝑂2(𝑠) + 4𝐻 +(𝑎𝑞) + 𝑆𝑂42−(𝑎𝑞) + 2𝑒 − → 𝑃𝑏𝑆𝑂4(𝑠) + 2𝐻2 𝑂(𝑙)
Overall: 𝑃𝑏(𝑠) + 𝑃𝑏𝑂2(𝑠) + 4𝐻 +(𝑎𝑞) + 2𝑆𝑂42−(𝑎𝑞) → 2𝑃𝑏𝑆𝑂4(𝑠) + 2𝐻2 𝑂(𝑙)
54
Under normal cell conditions, each cell produces 2 V; a total of 12 V from the six
cells is used to power the ignition circuit of the automobile and its electrical
systems.
Unlike the Leclanche cell and the mercury batter, the lead storage battery is
rechargeable. Recharging the battery means reversing the normal electrochemical
reaction by applying external voltage to the cathode and anode. This type of
process is called electrolysis.
𝑃𝑏𝑆𝑂4(𝑠) + 2𝑒 − → 𝑃𝑏(𝑠) + 𝑆𝑂42−(𝑎𝑞)
𝑃𝑏𝑆𝑂4(𝑠) + 2𝐻2 𝑂(𝑙) → 𝑃𝑏𝑂2(𝑠) + 4𝐻 +(𝑎𝑞) + 𝑆𝑂42−(𝑎𝑞) + 2𝑒 −
Overall: 2𝑃𝑏𝑆𝑂4(𝑠) + 2𝐻2 𝑂(𝑙) → 𝑃𝑏(𝑠) + 𝑃𝑏𝑂2(𝑠) 𝑃𝑏𝑂2(𝑠) + 4𝐻+(𝑎𝑞) + 2𝑆𝑂42−(𝑎𝑞)
The overall reaction is exactly opposite of the normal cell reaction
The Solid-State Lithium Battery
This battery employs a solid (rather than an aqueous solution or a water-based
paste) as the electrolyte connecting the electrodes. The advantage in choosing
lithium as the anode is that it has the most negative 𝐸 ° value. Furthermore,
Lithium is a light weight metal so that only 6.941 g of Li (its molar mass) are
needed to produce I mole of electrons. 55
The electrolyte is a polymer material that permits the passage of ions but not the
electrons. The cathode is made of either 𝑇𝑖𝑆2 𝑜𝑟 𝑉6 𝑂13 . The cell voltage of a solid-
state lithium battery can be as high as 3V, and it can be recharged in the same way
as a lead storage battery.
Fuel Cells
Fossil fuels are a major source of energy, but conversion of fossil fuel into electrical
energy is a highly inefficient process. Consider the combustion of methane:
𝐶𝐻4(𝑔) + 2𝑂2(𝑔) → 𝐶𝑂2(𝑔) + 2𝐻2 𝑂(𝑙) + 𝑒𝑛𝑒𝑟𝑔𝑦
To generate electricity, heat produced by the reaction is first used to convert water
to steam, which then drives a turbine that drives a generator. An appreciable
fraction of the energy released in the form of heat is lost to the surroundings at
each step. Because combustion reactions are redox reactions, it is more desirable
to carry them out directly by electrochemical means, thereby greatly increasing the
efficiency of power production. This is accomplished by a device called a fuel cell, a
galvanic cell that requires a continuously supply of reactants to keep functioning.
56
A hydrogen-oxygen fuel cell consists of an electrolyte solution such as KOH solution
and two inert electrodes. The hydrogen and oxygen gases are bubbled through the
anode and cathode compartments where the following reactions take place:

Anode: 2𝐻2(𝑔) + 4𝑂𝐻 −(𝑎𝑞) → 4𝐻2 𝑂(𝑙) + 4𝑒 −

Cathode: 𝑂2(𝑔) + 2𝐻2 𝑂(𝑙) + 4𝑒 − → 4𝑂𝐻 −(𝑎𝑞)

Overall: 2𝐻2(𝑔) + 𝑂2(𝑔) → 2𝐻2 𝑂(𝑙)

The standard emf of the cell can be calculated as follows:

° ° °
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒

= 0.40 V – (-0.83)

= 1.23 V 57
Thus the cell reaction is spontaneous under standard state conditions. Properly
designed fuel cells may be as much as 70% efficient, about twice as efficient as an
internal combustion engine. In addition, fuel cell generators are free of the noise,
vibration, heat transfer, thermal pollution and other problems normally associated
with conventional power plants. A major problem of fuel cells is the lack of cheap
electrocatalysts able to function efficiently for long periods f time without
contamination.
Corrosion
Corrosion is the term usually applied to the deterioration of metals by an
electrochemical process. Rust on iron, tarnish on silver, and the green patina
formed on copper and brass are a few examples of corrosion. 58
The most familiar example of corrosion is the formation of rust on iron. Oxygen gas
and water must be present for iron to rust. A region of the metal’s surface serves
as the anode, where oxidation takes place:
𝐹𝑒(𝑠) → 𝐹𝑒 2+(𝑎𝑞) + 2𝑒 −
The electrons given up by iron reduce atmospheric oxygen to water at the cathode,
which is another region of the same metal’s surface:
𝑂2(𝑔) + 4𝐻 +(𝑎𝑞) + 4𝑒 − → 2𝐻2 𝑂(𝑙)
The overall redox reaction is:
2𝐹𝑒(𝑠) + 𝑂2(𝑔) + 4𝐻 +(𝑎𝑞) → 2𝐹𝑒 2+(𝑎𝑞) + 2𝐻2 𝑂(𝑙)

° °
𝐸 ° 𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
= 1.23 V – (-0.44 V)
= 1.67 V
59
Note that this reaction occurs in an acidic medium; the 𝐻 + ions are supplied in
part by the reaction of atmospheric carbon dioxide with water to form carbonic
acid 𝐻2 𝐶𝑂3 .
The 𝐹𝑒 2+ ions formed at the anode are further oxidized by oxygen:
4𝐹𝑒 2+(𝑎𝑞) + 𝑂2(𝑔) + 4 + 2𝑥 𝐻2 𝑂(𝑙) → 2𝐹𝑒2 𝑂3 ∙ 𝑥𝐻2 𝑂(𝑠) + 8𝐻 + (𝑎𝑞)
This hydrated form of iron(III) oxide is known as rust. The amount of water
associated with the iron oxide varies, so we represent the formula as:
𝐹𝑒2 𝑂3 ∙ 𝑥𝐻2 𝑂(𝑠)
Electrolysis
Electrolysis is the process in which electrical energy is used to cause a
nonspontaneous chemical reaction to occur. An electrolytic cell is an apparatus for
carrying out electrolysis.
60
 Voltmeter
VV Current
Electrons
+
Battery
-
Anode Cathode
. A
. + .
... -- . Ammeter
. +
. .
.. . - .. .

A simple electrolytic cell

61
Electrolyte: Is a compound which when in molten form, or dissolved in a suitable
solvent, will conduct electricity. An electrolyte always contains ions, and hence
they are electrovalent or ionic compounds. Examples of electrolytes are:
• Aqueous sodium chloride (Ions in solution are: 𝑁𝑎+(𝑎𝑞) 𝑎𝑛𝑑 𝐶𝑙 − (𝑎𝑞) )
• Aqueous sulphuric acid ( ions in solution are: 2𝐻 +(𝑎𝑞) 𝑎𝑛𝑑 𝑆𝑂42−(𝑎𝑞) )
• Aqueous silver nitrate ( ions in solution are: 𝐴𝑔+ (𝑎𝑞) 𝑎𝑛𝑑 𝑁𝑂3− (𝑎𝑞)
Non- electrolyte: this is a compound which does not conduct electric current
either in solution of in molten form. They are covalent compounds which contain
molecules but not ions. Examples 𝐶𝐶𝑙4 (𝑎𝑞) , 𝐶𝑆2 (𝑎𝑞) etc.
Electrodes: These are two poles, made of carbo or metals through which electric
current enters or leaves an electrolyte. They are the cathode and the anode.
 The anode - Is the positive electrode through which electrons leave the
electrolyte.
 The Cathode – Is the negative electrode through which electrons enter the
electrolyte. 62
 During electrolysis, positive ions enter the negative electrode. They are called
cations.
 The negative ions enter the positive electrode. These are called anions.
The Electrochemical series
This is the arrangement of the cations and anions, in order of their relative ease of
discharge at the cathode and at the anode respectively. The list of ions in order of
ease of discharge is called the electrochemical series. In the electrolysis of a
solution containing a mixture of ions, ions below will be discharged in preference
to the ions above it in the electrochemical series. The ease of discharge of ions
increases down the electrochemical series, whilst the chemical reactivity
decreases.

63
 64

Ease of discharge increases down the table

𝑺𝑶𝟐−

𝑶𝑯−
𝑵𝑶− 𝟑

𝑩𝒓−
𝑪𝒍−
𝟒
𝑭−

𝑰−
𝑀𝑔2+

𝐻3 𝑂+

𝐴𝑢3+
𝑃𝑏 2+

𝐶𝑢2+
𝐶𝑎2+

𝑍𝑛2+
𝐹𝑒 2+
𝑆𝑛2+
𝐴𝑙3+
𝑁𝑎+

𝐴𝑔+
𝐾+

Ease of discharge increases down the table

 Factors affecting the discharge of ions during Electrolysis
1. Position of ions in the redox series – when two ions migrate to an electrode
during electrolysis, the ion that is below in the redox series is discharged in
preference to the one above it. For example, if 𝑁𝑎+ 𝑎𝑛𝑑 𝐻3 𝑂+ migrate to the
cathode during electrolysis, 𝐻3 𝑂+ ions will be discharged in preference of 𝑁𝑎+
because 𝐻3 𝑂+ is below in the redox series. This is applicable for dilute
solutions.
2. Concentration – for concentrated solutions, the more concentrated ion is
discharged in preference of the less concentrated regardless its position in the
redox series. For example, during the electrolysis of brine, 𝐶𝑙 − 𝑎𝑛𝑑 𝑂𝐻 −
migrated to the anode. Although 𝐶𝑙 − is above 𝑂𝐻 − in the redox series, it is
however discharged in preference of 𝑂𝐻 − because of its concentration.
3. Affinity – special electrodes have special affinity for certain and will however
discharge them regardless of the position in the redox series. In the electrolysis
of dilute NaCl using mercury cathode, the mercury having a high affinity for
sodium will discharge it to form a complex called Sodium Amalgam (Na/Hg). 65
 Steps in Electrolysis
• Identify the substances in solution
• Identify the ions in solution
• Migration of ions to the electrodes
• Preferential discharge of ions at the electrodes
• Reactions at the electrodes
• Compounds formed at the electrodes
• Ions left in solution
• Nature of the solution left in solution

66
Perform the electrolysis of the following using graphite electrodes:
1. Electrolysis of dilute NaCl and
2. Electrolysis of Brine
Applications of electrolysis
• Extraction of metals
• Extraction of caustic soda
• Purification of copper
• Electroplating

67
 Quantitative Aspects of Electrolysis
Faraday’s first Law:
The mass of a product (m) deposited or liberated at any electrode during
electrolysis is directly proportional to the quantity of electricity or charge (Q)
passed.
That is: 𝑚 𝛼 𝑄
𝑚 = 𝑧𝑄
Where m = mass of the product of electrolysis and
Q = quantity of electricity passed
Z is a constant of proportionality and is known as electrochemical equivalent
Quantity of electricity (coulombs) is related to current as:
Q = It………………………. (I)
𝑚𝛼𝐼𝑥𝑡
𝑚 = 𝑧𝐼𝑡 … … … … … … . (II)
Where I is the current passed for t seconds 68
 Second law
The masses of different substances deposited or liberated where the same
quantity of electricity is passed through different electrolytes connected in series
are proportional to their chemical equivalent masses.
𝑚 𝛼 𝐸…………………………………………. (III)
Where E is the chemical equivalent, and is defined as
𝑚𝑟
𝑚= ………………………………………. (IV)
𝑛
Where, 𝑚𝑟 is the atomic mass of the metal and 𝑛 is the unit charge of the ion
(valence of the ion).
Combining the two laws [that is equations (II) and (III)] :
𝑚 𝛼 𝐸𝐼𝑡
𝐸𝐼𝑡
𝑚= 𝑔𝑟𝑎𝑚𝑠……………………… (V)
96500
𝑚 = 𝑍𝐼𝑡……………………………………… (VI) 69
Where z is the electrochemical equivalent and from above it is:
𝐸
𝑧= ……………………………………… VII
96500
Substituting equation (VI) into equation (VII) gives:
𝑚𝑟
𝑧= ………………………………….….(VIII)
96500𝑛
𝑚𝑟 𝐼𝑡
∴𝑚 = ……………………………........(IX)
96500𝑛

Worked Example
A direct current of 100mA flows for 4 hours through three cells in series. They
contain solutions of sodium chloride, copper(II) tetraoxosulphate (VI) and gold(III)
trioxonitrate (V). Calculate the mass of metal deposited in each cell.
[Na = 23; Cu = 63.5; Au = 197 𝑔𝑚𝑜𝑙 −1 ]
70
 Solution
I = 100 mA = 0.1A
t = 4 x 60 x 60 =14400s
Q = It = 0.1A x 14400s
= 1440 Coulombs
1st cell: 𝑁𝑎𝐶𝑙(𝑎𝑞) ↔ 𝑁𝑎+(𝑎𝑞) + 𝐶𝑙 −(𝑎𝑞)
At the cathode: 𝑁𝑎+(𝑎𝑞) + 𝑒 − → 𝑁𝑎(𝑠)
1 mole of Na liberate 96500C
∴ 𝑥 𝑚𝑜𝑙𝑒 𝑁𝑎 𝑤𝑖𝑙𝑙 𝑙𝑖𝑏𝑒𝑟𝑎𝑡𝑒 = 1440C
1440𝑐 𝑥 1
𝑥=
96500𝑐
𝑥 = 0.0149 𝑚𝑜𝑙𝑒
𝑚𝑎𝑠𝑠 = 𝑁𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑥 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠
mass = 0.0149 x 23
= 0.34g Na 71
2nd cell: 3rd Cell:
𝐶𝑢𝑆𝑂4(𝑎𝑞) ↔ 𝐶𝑢2+(𝑎𝑞) + 𝑆𝑂42−(𝑎𝑞) 𝐴𝑢 𝑁𝑂3 3(𝑎𝑞) ↔ 𝐴𝑢3+(𝑎𝑞) + 3𝑁𝑂3− (𝑎𝑞)
At the cathode: 𝐶𝑢2+(𝑎𝑞) + 2𝑒 − → 𝐶𝑢(𝑠) At the cathode:
1 mole Cu was liberated by 2 x 96500C 𝐴𝑢3+(𝑎𝑞) + 3𝑒 − → 𝐴𝑢(𝑠)
3 𝑥 96500𝐶 𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑 1 𝑚𝑜𝑙𝑒 𝐴𝑢
X mole Cu will liberate 1440C 1440𝐶 𝑤𝑖𝑙𝑙 𝑑𝑒𝑝𝑜𝑠𝑖𝑡 𝑥 𝑚𝑜𝑙𝑒 𝐴𝑢
X=
1 𝑥 1440 1440𝐶
2 𝑥 96500 𝑥=
3 𝑥 96500𝐶
X = 0.34 mole
Mass = 0.0075 x 63.5 𝑥 = 0.005 𝑚𝑜𝑙𝑒
Mass = 0.48g Cu. 𝑚𝑎𝑠𝑠 = 0.005 𝑚𝑜𝑙𝑒 𝑥 197𝑔𝑚𝑜𝑙 −1
𝒎𝒂𝒔𝒔 = 𝟎. 𝟗𝟗𝒈 𝑨𝒖

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