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Learning Module

Generation of Energy
Course Packet 01

Electrochemical Methods

Knowledge Area Code : SCIE

Course Code : FCHE0114
Learning Module Code : LM01-FCHE0114
Course Packet Code : LM01- FCHE0114-01
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Course Packet 01
Course Packet 01

Electrochemical Methods

Introduction
This course packet is intended to teach fundamentals of electrochemistry and the application of
electrochemical methods to the generation of energy. Topics to be discussed include redox reactions,
electrode processes and principles of electrochemical devices including batteries and fuel cells. The course
starts at a basic level to ensure that each student starts on a solid footing and to dispel common
misconceptions. It then progresses to cover the core of electrochemical theory that forms the basis for the
techniques that are detailed later in the course. Practical examples, diagrams and images illustrate and
reinforce the subject matter.

Objectives
• Explain the displacement of metals from solution in terms of transfer of electrons.
• Account for changes in the oxidation state of species in terms of their loss or gain of electrons.
• Outline the construction of electrochemical cells and trace the direction of electron flow.
• Define the terms anode, cathode, electrode and electrolyte to describe electrochemical cells.
• Develop awareness and concern about the environmental impacts of electrochemical cells.
• Perform a first-hand investigation to identify the conditions under which a galvanic cell is
produced.
• Perform a first-hand investigation and gather first-hand information to measure the difference
in potential of different combinations of metals in an electrolyte solution.

Learning Management System

Links to Google Classroom and Google Drive will be provided upon orientation.

Duration
Topic 01: Electrochemical Methods
• 12 hours (9 hours self-directed learning with practical exercises and 3 hours assessment)

Delivery Mode
This module is offered online (synchronous or asynchronous).

Assessment with Rubrics

Assessments will be given online.

Requirement with Rubrics

Please see Science Notebook on pages 2-3.

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Electrochemistry deals with the study of the connection between oxidation-reduction reactions
and the flow of electrons. Since the total number of electrons loss must be equal to the total
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number of electrons gain, electrons are very significant in any redox reactions.

REDOX REACTIONS

Redox reaction is a reaction where oxidation of one substance and reduction of other substance
take place simultaneously.

Figure 1. Redox Reaction

Table 1. Oxidation and reduction comparison

Oxidation Reduction
• Gains oxygen • Loses oxygen
• Loses hydrogen • Gains hydrogen
• Loses electrons • Gains electrons
• Increase in oxidation number • Decrease in oxidation number
Example: Example:
Gain of oxygen Loss of oxygen

2 Mg(s) + O2(g) 2 MgO(s) Zn(s) + CuO(s) ZnO(s) +Cu

Loss of hydrogen Gain of hydrogen

H2S(g) + Cl2(g) 2 HCl(g) + S(g) H2 (g) + Cl2(g) 2 HCl(g)

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Table 2. Reducing and oxidizing agents comparison

Oxidizing Agents Reducing Agents

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• Substances that cause oxidation in the • Substances that cause reduction in the
substance they react with substance they react with
• The substance being reduced • The substance being oxidized
• Gains electrons • Loses electrons
Example:
Oxidation (gain of oxygen)

2 CuO(s) + C(s) 2 Cu(s) + CO 2

Reduction (loss of oxygen)

• Oxidation occurs when carbon, C gains oxygen to form carbon dioxide, CO2.
• Reduction occurs when copper(II) oxide, CuO loses oxygen to form copper, Cu.
• Oxidizing agent: copper(II) oxide, CuO (oxidized C into CO2)
• Reducing agent: carbon, C (reduced CuO to Cu)

Oxidation (gain of oxygen)

2 FeO(s) + C(s) 2 Fe(s) + CO 2

Reduction (loss of oxygen)

• Oxidation occurs when carbon, C gains oxygen to form carbon dioxide, CO2.
• Reduction occurs when iron(II) oxide, FeO loses oxygen to form iron, Fe.
• Oxidizing agent: iron(II) oxide, FeO (oxidized C into CO2)
• Reducing agent: carbon, C (reduced FeO to Fe)

Oxidation Number

Oxidation number or oxidation state refers to the number of electrons transferred from one
atom to other atom.

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Table 3. Rules in assigning oxidation numbers

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1) The oxidation number of an atom or 0 0 0 0 0 0

molecule of an element in free state is zero. H2 O2 Cl Na Fe Ca
2) The oxidation numbers of hydrogen and +1 -1 +1 -1 +1 -2
oxygen are +1 and –2 respectively, but H2 O2 Na H2 H2 O2
sometimes oxygen carries a -1 in peroxide
compound and in hydrides, the charge of H2O2 NaH H2O
hydrogen is -1.
3) The sum of oxidation numbers of a compound Carbon dioxide, CO2 : (+4) + (2)(-2) = 0
is zero.
4) The sum of oxidation numbers of polyatomic Sulfate, SO4-2 : (+6) + 4(-2) = -2
ion is equal to the charge of the polyatomic ion.

Worked Example 1.1

Determine the oxidation number of the underlined element.

a) KMnO4

Given: K = +1 O = -2 Let x be the oxidation number of Mn

Solution:

1(+1) + 1(x) + 4(-2) =0

1 + x + (-8) =0

x–7 =0

x = +7 is the oxidation number of Mn

b) Al2(Cr2O7)3

Given: Al = +3 O = -2 Let x be the oxidation number of Cr

Solution:

2(+3) + 6(x) + 21(-2) =0

6 + 6x + (-42) =0

6x – 36 =0
6x = +36

6x = +36
6 6

x = 6 is the oxidation number of Cr

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Figure 2. Oxidation Number and Electron Transfer in Redox Reactions

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Oxidation

2 Na0(s) + Cl20(g) 2 Na+1Cl-1

Reduction

• Oxidation occurs when sodium, Na oxidation number increases from 0 to +1 as it loses

electron to form sodium ion. Na(s) Na+1(aq) + e-
• Reduction occurs when chlorine, Cl oxidation number decreases from 0 to -1 as it gains
electron to form chlorine ion. Cl2(g) + 2e- 2Cl-1(aq)
• Oxidizing agent: chlorine, Cl2
• Reducing agent: sodium, Na

Worked Example 1.2

Identify the oxidizing agent and reducing agent in each of the following equations.

a) 2Fe + 3Cl2 2FeCl3

Solution:

Step 1. Write the oxidation state of each of the element above the chemical symbol from the
reactants to products.
0 0 +3 -1

2Fe + 3Cl2 2FeCl3

Step 2. Identify the element which undergoes a changed in oxidation state.

Oxidation (0 to +3)

0 0 +3 -1

2Fe + 3Cl2 2FeCl3

Reduction (0 to -1)

• Oxidizing agent: chlorine, Cl2

• Reducing agent: iron, Fe

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b) CuO + NH3 N2 + H2O + Cu

Solution:
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Step 1. Write the oxidation state of each of the element above the chemical symbol from the
reactants to products.
+2 -2 -3 +1 0 +1 -2 0

CuO + NH3 N2 + H2O + Cu

Step 2. Identify the element which undergoes a changed in oxidation state.

Reduction (+2 to 0)

+2 -2 -3 +1 0 +1 -2 0

CuO + NH3 N2 + H2O + Cu

Oxidation (-3 to 0)

• Oxidizing agent: copper(II) oxide, CuO

• Reducing agent: ammonia, NH3

Displacement of a Metal from its Salt Solution in Redox Reacon

Displacement reaction is a reaction in which one element (metal or non-metal) displaces

another element (metal or non-metal) from its salt solution.

Figure 3. Metal Reactivity Series

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Figure 4. Displacement of halogen from its halide solution in redox reaction

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BALANCING REDOX REACTIONS

Balancing redox reactions is slightly more complex than balancing standard reactions, but still
follows a relatively simple set of rules. One major difference is the necessity to know the half-
reactions of the involved reactants; a half-reaction table is very useful for this. Half-reactions
are often useful in that two half reactions can be added to get a total net equation. Although
the half-reactions must be known to complete a redox reaction, it is often possible to figure
them out without having to use a half-reaction table. This is demonstrated in the acidic and
basic solution examples. Besides the general rules for neutral conditions, additional rules must
be applied for aqueous reactions in acidic or basic conditions.

Half Equation Method

In this method, the equation is separated into two half-equations; one for oxidation and
one for reduction.

Each equation is balanced by adjusting coefficients and adding H 2O, H+, and e- in this order:

1. Balance elements in the equation other than O and H.

2. Balance the oxygen atoms by adding the appropriate number of water (H 2O) molecules
to the opposite side of the equation.
3. Balance the hydrogen atoms (including those added in step 2 to balance the oxygen
atom) by adding H+ ions to the opposite side of the equation.
4. Add up the charges on each side. Make them equal by adding enough electrons (e-) to
the more positive side. (Rule of thumb: e- and H+ are almost always on the same side.)
5. The e- on each side must be made equal; if they are not equal, they must be multiplied
by appropriate integers (the lowest common multiple) to be made the same.
6. The half-equations are added together, canceling out the electrons to form one
balanced equation. Common terms should also be canceled out.

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(If the equation is being balanced in a basic solution, through the addition of one more
step, the appropriate number of OH- must be added to turn the remaining H+ into
water molecules.)
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7. The equation can now be checked to make sure that it is balanced.

Neutral Conditions

The first step to balance any redox reaction is to separate the reaction into half-
reactions. The substance being reduced will have electrons as reactants, and the oxidized
substance will have electrons as products. Sometimes it is necessary to determine which half-
reaction will be oxidized and which will be reduced. In this case, whichever half-reaction has
a higher reduction potential will be reduced and the other oxidized.

Worked Example 1.3 Balancing in Neutral Solution

Cu+(aq) + Fe(s) Fe3+(aq) + Cu(s)

Step 1: Separate the half-reactions. This yields:

Reduction: Cu+(aq) + e- Cu(s)

Oxidation: Fe(s) Fe3+(aq) + 3e-

Step 2: Balance the electrons in the equations. In this case, the electrons are simply balanced by
multiplying the entire Cu+(aq) + e- → Cu(s) half-reaction by 3 and leaving the other half
reaction as it is. This gives:

Reduction: 3Cu+(aq) + 3e- 3Cu(s)

Oxidation: Fe(s) Fe3+(aq) + 3e-

Step 3: Adding the equations give:

3Cu+(aq) + 3e- + Fe(s) 3Cu(s) + Fe 3+(aq) + 3e-

Step 4. The electrons cancel out and the balanced equation is left.

3Cu+(aq) + 3e- + Fe(s) 3Cu(s) + Fe 3+(aq) + 3e-

3Cu+(aq) + Fe(s) 3Cu(s) + Fe 3+(aq)

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Acidic Conditions

Acidic conditions usually implies a solution with an excess of H + concentration, hence

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making the solution acidic. The balancing starts by separating the reaction into half-reactions.
However, instead of immediately balancing the electrons, balance all the elements in the half-
reactions that are not hydrogen and oxygen. Then, add H2O molecules to balance any oxygen
atoms. Next, balance the hydrogen atoms by adding protons (H+). Now, balance the charge by
adding electrons and scale the electrons (multiply by the lowest common multiple) so that they
will cancel out when added together. Finally, add the two half-reactions and cancel out
common terms.

Worked Example 1.4 Balancing in Acidic Solution

Cr2O72− (aq) + HNO2(aq) Cr3+(aq) + NO3−(aq)

Step 1: Separate the half-reactions. The table provided does not have acidic or basic half-
reactions, so just write out what is known.

Cr2O72− (aq) Cr3+(aq)

HNO2(aq) NO3−(aq)

Step 2: Balance elements other than O and H. In this example, only chromium needs to be
balanced. This gives:

Cr2O72− (aq) 2Cr3+(aq)

HNO2(aq) NO3−(aq)

Step 3: Add H2O to balance oxygen. The chromium reaction needs to be balanced by adding 7
H2O molecules. The other reaction also needs to be balanced by adding one water molecule.
This yields:

Cr2O72−(aq) 2Cr3+(aq) + 7 H2O(l)

HNO2(aq) + H2O(l) NO3−(aq)

Step 4: Balance hydrogen by adding protons (H+). 14 protons need to be added to the left side
of the chromium reaction to balance the 14 hydrogen (2 per water molecule * 7 water
molecules). 3 protons need to be added to the right side of the other reaction.

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

HNO2(aq) + H2O(l) NO3−(aq) + 3 H+(aq)

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Step 5: Balance the charge of each equation with electrons.

(-2) (1) + (+1)(14) = +12 (+3) (2) = +6

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Cr2O7 2− (aq) + 14 H + (aq) 2 Cr 3+ (aq) + 7 H2O(l)

To balance, add 6 electrons (each with a charge of -1) to the left side:

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

For the other reaction, there is no charge on the left and a (3+) + (-1) = 2+ charge on the right. So
add 2 electrons to the right side:

HNO2(aq) + H2O(l) NO3−(aq) + 3 H+(aq) + 2e-

Step 6: Scale the reactions so that the electrons are equal.

The chromium reaction has 6e-.

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

The other reaction has 2e-, so it should be multiplied by 3.

3 • HNO2(aq) + H2O(l) NO3−(aq) + 3 H+(aq) + 2e-
This gives:
3HNO2(aq) + 3H2O(l) 3NO3−(aq) + 9 H+(aq) + 6e-

Step 7: Add the reactions and cancel out common terms.

14 - 9 = 5 H+ 7 - 3 = 4 H 2O

6e- + Cr2O72−(aq) + 14H+(aq) + 3HNO2(aq) + 3H2O(l) 2Cr3+(aq) + 7 H2O(l) + 3NO3−(aq) +

9H+(aq) + 6e-

This gives:
Cr2O72−(aq) + 5H+(aq) + 3HNO2(aq) 2Cr3+(aq) + 4 H2O(l) + 3NO3−(aq)

Basic Conditions

Bases dissolve into OH- ions in solution; hence, balancing redox reactions in basic
conditions requires OH-. Follow the same steps as for acidic conditions. The only difference is
adding hydroxide ions (OH-) to each side of the net reaction to balance any H+. OH- and H+ ions
on the same side of a reaction should be added together to form water. Again, any common
terms can be cancelled out.

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Worked Example 1.5 Balancing in Basic Solution

Ag(s) + Zn2+(aq) Ag2O(aq) + Zn(s)

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Go through all the same steps as if it was in acidic conditions.

Step 1: Separate the half-reactions.

Oxidation: Ag(s) Ag2O(aq)

Reduction: Zn2+(aq) Zn(s)

Step 2: Balance elements other than O and H.

2Ag(s) Ag2O(aq)

Zn2+(aq) Zn(s)

Step 3: Add H2O to balance oxygen.

H2O + 2Ag(s) Ag2O(aq)

Zn2+(aq) Zn(s)

Step 4: Balance hydrogen with protons.

H2O(l) + 2Ag(s) Ag2O(aq) + 2H+(aq)

Zn2+(aq) Zn(s)

Step 5: Balance the charge with e-.

H2O(l) + 2Ag(s) Ag2O(aq) + 2H+(aq) + 2e-

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

Step 6: Scale the reactions so that they have an equal amount of electrons. In this case, it is
already done.

Step 7: Add the reactions and cancel the electrons.

H2O(l) + 2Ag(s) + Zn2+(aq) + 2e- Ag2O(aq) + 2H+(aq) + 2e- + Zn(s)

This gives:
H2O(l) + 2Ag(s) + Zn2+(aq) Ag2O(aq) + 2H+(aq) + Zn(s)

Step 8: Add OH- to balance H+. There are 2 net protons in this equation, so add 2 OH- ions to
each side.

2 OH-(aq) + H2O(l) + 2Ag(s) + Zn2+(aq) Ag2O(aq) + 2H+(aq) + Zn(s) + 2 OH-(aq)

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Step 9: Combine OH- ions and H+ ions that are present on the same side to form water.
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2 OH-(aq) + H2O(l) + 2Ag(s) + Zn2+(aq) Ag2O(aq) + 2H+(aq) + Zn(s) + 2 OH-(aq)

2 OH-(aq) + H2O(l) + 2Ag(s) + Zn2+(aq) Ag2O(aq) + Zn(s) + 2 H2O(l)

Step 10: Cancel common terms.

2 OH-(aq) + 2Ag(s) + Zn2+(aq) Ag2O(aq) + Zn(s) + H2O(l)

ELECTROCHEMICAL CELLS

Electrochemical cells are made up of two metallic conductors called electrodes in contact with
electrical medium called electrolyte. Electrochemical cells spontaneously produce electrical
current called electromotive force (EMF) as a result of the electrical potential that exists
between two reactions. These reactions involve the gaining of electrons (reduction) and the loss
of electrons (oxidation).

Electrochemical cells are of two types:

1. Voltaic cells, also called galvanic cells
2. Electrolytic cells

Figure 5. Electrochemical cells

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Figure 6. Comparison of Electrochemical cells

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Voltaic (Galvanic) Cells

In redox reactions, electrons are transferred from one species to another. If the reaction is
spontaneous, energy is released, which can then be used to do useful work. To harness this
energy, the reaction must be split into two separate half reactions: the oxidation and reduction
reactions. The reactions are put into two different containers and a wire is used to drive the
electrons from one side to the other. In doing so, a Voltaic/ Galvanic Cell is created.

Half Cells

Half of the redox reaction occurs at each half cell. Therefore, we can say that in each half-cell a
half-reaction is taking place. When the two halves are linked together with a wire and a salt
bridge, an electrochemical cell is created.

Figure 7. A half cell and the strip of metal is the electrode

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Electrodes

An electrode is strip of metal on which the reaction takes place. In a voltaic cell, the oxidation
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and reduction of metals occurs at the electrodes. There are two electrodes in a voltaic cell, one
in each half-cell. The cathode is where reduction takes place and oxidation takes place at the
anode.

Standard Hydrogen Electrode

A Standard Hydrogen Electrode (SHE) is an electrode that scientists use for reference on all
half-cell potential reactions. The value of the standard electrode potential is zero, which forms
the basis one needs to calculate cell potentials using different electrodes or different
concentrations. It is important to have this common reference electrode just as it is important
for the International Bureau of Weights and Measures to keep a sealed piece of metal that is
used to reference the S.I. Kilogram.

Flow of Electrons

Electrons always flow from the anode to the cathode or from the oxidation half-cell to the
reduction half cell. In terms of E°cell of the half reactions, the electrons will flow from the more
negative half reaction to the more positive half reaction. A cell diagram is a representation of
an electrochemical cell.

Representing Half Cells: Cell Diagrams

Figure 8. Cell diagram

When drawing a cell diagram, we follow the following conventions. The anode is always
placed on the left side, and the cathode is placed on the right side. The salt bridge is represented
by double vertical lines (||). The difference in the phase of an element is represented by a single
vertical line (|), while changes in oxidation states are represented by commas (,).

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Worked Example 1.6

2Ag+(aq) + Cu(s) ⇌ Cu2+(aq)+ 2Ag(s)

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Step 1: Write the two half-reactions.

Ag+(aq) + e− ⇌ Ag(s)

Cu(s) ⇌ Cu2+(aq) + 2e−

Step 2: Identify the cathode and anode.

Cu(s) is losing electrons thus being oxidized; oxidation occurs at the anode.
Anode (where oxidation occurs): Cu(s) ⇌ Cu2+(aq) + 2e−

Ag+ is gaining electrons thus is being reduced; reduction happens at the cathode.
Cathode (where reduction occurs): Ag+(aq) + e− ⇌ Ag(s)

Step 3: Construct the Cell Diagram.

Cu(s)|Cu2+(aq)||Ag+(aq)|Ag(s)

Cell Voltage/Cell Potential

The readings from the voltmeter give the reaction's cell voltage or potential difference between
its two half-cells. Cell voltage is also known as cell potential or electromotive force (emf) and
it is shown as the symbol E°cell .

The Eo values are tabulated with all solutes at 1 M and all gases at 1 atm. These values are called
standard reduction potentials. Each half-reaction has a different reduction potential, the
difference of two reduction potentials gives the voltage of the electrochemical cell. If E ocell is
positive the reaction is spontaneous and it is a voltaic cell. If the Eocell is negative, the reaction is
non-spontaneous and it is referred to as an electrolytic cell.

Table 4. Standard Reduction Potential Values

Reduction Half-Reaction Standard Reduction Potential (V)

F2(g)+2e- → 2F-(aq) +2.87

O2(g)+4H+(aq)+4e- → 2H2O(l) +1.23

Br2(l)+2e- → 2Br-(aq) +1.09

Ag+(aq)+e- → Ag(s) +0.80

Fe3+(aq)+e- → Fe2+(aq) +0.77

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Table 4. (Cont.)Standard Reduction Potential Values

I2(l)+2e- → 2I+(aq) +0.54

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Cu2+(aq)+2e- → Cu(s) +0.34

Sn4+(aq)+2e- → Sn2+(aq) +0.15

S(s)+2H+(aq)+2e- → H2S(g) +0.14

2H+(aq)+2e- → H2(g) 0.00

Sn2+(aq)+2e- → Sn(g) -0.14

V3+(aq)+e- → V2+(aq) -0.26

Fe2+(aq)+2e- → Fe(s) -0.44

Cr3+(aq)+3e- → Cr(s) -0.74

Zn2+(aq)+2e- → Zn(s) -0.76

Mn2+(aq)+2e- → Mn(s) -1.18

Na+(aq)+e- → Na(s) -2.71

Li+(aq)+e- → Li(s) -3.04

Worked Example 1.6 Calculating E° cell at Standard State

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

Step 1: Write the half-reactions for each process.

Oxidation: Zn(s) → Zn2+(aq) + 2e-

Reduction: Cu2+(aq) + 2e- → Cu(s)

Step 2: Look up the standard potential for the reduction half-reaction.

Cu2+(aq) + 2e- → Cu(s) E⁰red = +0.34 V

Step 3: Look up the standard reduction potential for the reverse of the oxidation reaction and
change the sign.
Zn2+(aq) + 2e- → Zn(s) E⁰red= –0.76 V
Zn(s) → Zn (aq) + 2e-
2+ E⁰ox= +0.76 V

4. Add the cell potentials to get the overall standard cell potential.

E⁰cell = E⁰red + E⁰ox

E⁰cell = +0.34 V + +0.76 V
E⁰cell = +1.1 V (the reaction is spontaneous and the cell is voltaic)

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The Daniell Cell

Redox Reactions at the Electrodes of Daniell Cell

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The Daniell cell is an electrochemical cell named after John Frederic Daniell, the British chemist
who invented it in 1836. It is made up of zinc, Zn plate dipped into zinc sulfate solution and
copper, Cu plate dipped into copper(II) sulfate, CuSO4 solution.

Figure 9. Cell diagram

The electrodes act as a terminal, or a holding place, for electrons. A wire connects the
electrodes, but nothing happens until you put a salt bridge between the two containers. The
salt bridge, normally a U-shaped hollow tube filled with a concentrated salt solution, provides
a way for ions to move from one container to the other to keep the solutions electrically neutral.
With the salt bridge in place, electrons can start to flow.

Table 5. Redox reaction that occurs in the Daniell cell

At the anode (negative terminal) At the cathode (positive terminal)

• Zinc loses electrons and is oxidized to • Copper ion gains electrons and is
zinc ion, Zn+2 reduced to copper metal, Cu.
• Oxidation occurs and zinc acts as • Reduction occurs and copper ion acts as
reducing agent. oxidizing agent.
Zn(s) Zn+2(aq) + 2e- Cu+2(aq) + 2e- Cu(s)
• Electrons generated at the anode move
through the external circuit to the copper
cathode.
Overall reaction that occurs in the Daniell cell
Oxidation (loss of e-)

Zn(s) + Cu+2(aq) Zn+2(aq) + Cu(s)

Reduction (gain of e-)

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This cell will produce a little over one volt. You can get just a little more voltage if you make
the solutions that the electrodes are in very concentrated. Although historically important, it is
no longer used commercially.
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Cells and Batteries

Redox reactions involve the transfer of electrons between two species. The flow of electrons is
an electrical current. Redox reactions can therefore be used to generate electrical current. This
is the basis of batteries and fuel cells.

A cell is a store of chemical energy in a closed system. All reactants and products are contained
within the casing of the cell.

A battery is more than one cell connected together in a series arrangement. When a conductor
is connected across the two terminals, a circuit is formed and electrons flow through it. By
connecting more than one cell together, the electromotive force is increased. The battery voltage
is the sum of the voltages of each of the cells. A battery is a closed system which contains the
high energy reactants and the low energy products in a sealed unit.

Rechargeable and Non-rechargeable Cells

There are two types of cell: non-rechargeable and rechargeable. They are also known as
primary and secondary cells. Primary cells can only be used once. Secondary cells can be
recharged and reused. Smaller cells contain fewer reactants and produce less electrical energy.
However, the reaction voltage doesn’t change with cell size.

Primary cells

A primary cell can only be used once because it transfers stored chemical energy into
electrical energy by a non-reversible chemical reaction. Primary cells are usually cheaper to
buy. They are more reliable as they do not discharge much when they are not in use. This makes
them more useful for applications such as smoke detectors.

Redox Reactions at the Electrodes of Dry Cells

A dry cell is a voltaic cell where electrolyte is a paste.

A. Common dry cell (acidic) – made up of a zinc, Zn container as the anode (negative
terminal) and a carbon, C (graphite) rod as the cathode (positive terminal). The
electrolyte used is a paste containing ammonium chloride NH 4Cl, zinc chloride ZnCl2
and water,H2O.

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Figure 10. A Carbon-Zinc cell

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Table 6. Redox reaction that occurs in the Carbon-Zinc cell

At the anode (negative terminal) At the cathode (positive terminal)

• Zinc loses electrons and is oxidized to • Ammonium ion, NH4+1 gains electrons
zinc ion, Zn+2 and is reduced into ammonia gas,NH3
• Oxidation occurs and zinc acts as and hydrogen gas,H2.
reducing agent. • Reduction occurs and NH4+1 acts as
Zn(s) Zn+2(aq) + 2e- oxidizing agent.
• Electrons generated at the anode move 2NH4+1(aq) + 2e- 2NH3(g) + H2(g)
through the external circuit to the • The formation of bubbles of hydrogen gas
copper cathode. around the carbon electrode is called
polarization of the cell. Manganese(IV)
oxide, MnO2 is used to oxidize the
hydrogen.
Precipitation reaction:
2MnO2(s) + H2(g) Mn2O3(s) +
H2O(l)
• The overall reaction at the cathode is
2NH4+1 + 2MnO2 + 2e- 2NH3 + Mn2O3 +
H2O
Overall reaction that occurs in the common dry cell

Oxidation (loss of e-)

Zn(s) + 2NH4+1(aq) + 2MnO2(s) Zn+2(aq) + 2NH3(g) + Mn2O3(s) + H2O(l)

Reduction (loss of hydrogen)

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Dry cells costs cheap, however they are not rechargeable. They also have poor shelf life. To
increase your battery shelf life, refrigerate it prior to use. Decreasing the temperature would
mean decreasing its reaction rate.
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B. Alkaline Dry Cell – modified example of common dry cell that uses potassium
hydroxide, KOH rather than ammonium chloride NH4Cl in the paste, producing
somewhat different reaction at the electrodes.

Figure 11. A button cell

Oxidation (anode): Zn(l) + 2OH(aq) ZnO(s) + H2O(l) + 2e-

Reduction (cathode): 2MnO2(s) + H2O(l) + 2e- Mn2O3(s) + 2OH(aq)

The alkaline dry cell lasts much longer as the zinc anode corrodes less rapidly under
basic conditions than under acidic conditions. It maintains a steady voltage of about
1.5 V under high current loads and generates about more than half the common dry
cell of the same size.

Other types of alkaline dry cell batteries are the silver battery in which silver metal
serves as an inert cathode to support the reduction of silver oxide (Ag2O) and the
oxidation of zinc (anode) in a basic medium. The type of battery commonly used for
calculators is the mercury cell. In this type of battery, HgO serves as the oxidizing agent
(cathode) in a basic medium, while zinc metal serves as the anode.

Secondary Cells

Secondary Cells are more environment friendly than primary cells as they can be recharged
and reused many times. They are more expensive to buy and require charging equipment.

Redox Reactions at the Electrodes of Rechargeable Batteries

A. Lead Acid Battery - a battery which uses sponge lead, Pb and lead(IV) oxide, PbO2 for the
conversion of the chemical energy into electrical power. The lead acid battery is most
commonly used in the automobiles and power stations because it has higher cell voltage
and lower cost.

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The electrolyte used in the battery is 35% sulfuric acid (commonly called battery acid) and
65% water solution. All lead-acid batteries operate on the same fundamental reactions.
When the sulfuric acid dissolves, its molecules break up into positive hydrogen ions (2H +)
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and sulphate negative ions (SO4—) and move freely.

As the battery discharges, the active materials in the electrodes lead(IV) oxide, PbO2 in
the cathode and sponge lead, Pb in the anode) react with sulfuric acid in the electrolyte to
form lead(II) sulfate and water.

As the battery recharges, the lead(II) sulfate on both electrodes converts back to lead(IV)
oxide, PbO2 in the cathode and and sponge lead, Pb in the anode and the sulfate ions are
driven back to electrolyte solution to form sulfuric acid, H 2SO4.

Figure 12. A lead acid battery

Figure 12. Recharging of lead acid battery Figure 13. Discharging of lead acid battery

discharge
Oxidation (anode): Pb(s) + SO4-2(aq) PbSO4(s) + 2e- = 1.685 V
charge

discharge
Reduction (cathode) : PbO2(s) + 4H+(aq) + SO4-2(aq) PbSO4(s) + 2H2O(l) = 0.356 V
charge
Overall Reaction:
discharge
Pb(s) + PbO2(s) + 4H+(aq) + SO4-2(aq) PbSO 4(s) + 2H2O(l) = 2.041 V
charge

The maximum open circuit voltage that can developed by a single acid cell is 2.041 V. the lead
storage battery used as a power source in automobiles is made up of six lead acid cells. When
hooked in series the produced a total of 12 volts which powers the ignition, power brakes,
power steering and power locks and windows.

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B. Nickel – Cadmium Battery – widely used in portable, electronic equipment and power
tools. The active components of a rechargeable Ni-Cd battery in the charged state consist
of nickel hydroxide (NiOOH) in the cathode and cadmium (Cd) in the anode. For the
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electrolyte, usually caustic solution (potassium hydroxide, KOH) is used. Due to their low
internal resistance and the very good current conducting properties, Ni-Cd cells can supply
extremely high currents and can be recharged rapidly.

Figure 14. A Nickel-Cadmium battery

Oxidation(anode): Cd(s) + 2OH−(aq) Cd(OH)2(s) + 2e−

Reduction (cathode): 2NiOOH(s) + 2H2O(l) + 2e− 2Ni(OH)2(s) + 2OH−(aq)

Overall Reaction:
Cd(s) + 2NiOOH(s) + 2H2O(l) Cd(OH)2(s) + 2Ni(OH)2(s)

The Ni-Cd battery, also called nicads, is lightweight and produces a constant voltage during
discharge. It provides about 1.4 volts. However, nicads suffer from memory discharge. If they
are discharged only partially and then recharged, they develop the tendency to need
recharging after only a short use. These batteries are more efficient if totally discharged before
recharging. Nicads must also be properly disposed because of the toxicity of cadmium and its
compound.

Fuel cells

A fuel cell converts chemical energy into electrical energy in a similar fashion to a battery.
However, a fuel cell is an open system – reactants flow in and products flow out, rather than
being stored in the cell.

Redox Reactions at the Electrodes of Hydrogen Fuel Cells

Hydrogen fuel cells produce electricity through the reaction of hydrogen with oxygen. The
electrolyte used is aqueous potassium hydroxide.

The reaction which takes place in a hydrogen fuel cell is: 2H2 + O2 2H2O

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Figure 15. A Hydrogen fuel cell

The hydrogen molecules enter the left side of the cell. As they contact the anode they release
electrons to form positively charged hydrogen ions. The hydrogen ions cross the permeable
membrane. They will combine with oxygen and free electrons from the cathode to form water
molecules.

Oxidation (anode): 2H2(g) 4H+(aq) + 4e–

Reduction (cathode): 4H+(aq) + O2(g) + 4e 2H2O(g)

The only waste product is water vapour. Hydrogen fuel cell is very much like a battery that
can be recharged while you are drawing power from it. Instead of recharging using electricity,
however, it uses hydrogen and oxygen.

Calculating the energy

Bond energies can be used to calculate the amount of energy given out by the reaction
in a hydrogen fuel cell. Energy is taken in to break bonds, and released when bonds are created.

Table 7. Bond Energies

Bond Bond Energy

(kJ)
H–H 432
O=O 498
O–H 463

Energy for bond-breaking Energy from bond-making

= 2 H-H + O=O = 4 H-O

= (2 x 432) + 498 = 4 x 463

= 1362 kJ 1852 kJ

Total energy change = energy in – energy out

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= 1362 kJ – 1852 kJ = –490 kJ

In exothermic reactions, the products have less enthalpy than reactants, as a result, an
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exothermic reaction is said to have a negative enthalpy reaction. This means that the energy
required to break the bonds in the reactants is less than the energy released when new bonds
form in the products. Excess energy from the reaction is released as heat and light.

Production of hydrogen

Hydrogen is a very reactive element and must be produced by a chemical reaction before it can
be used in a fuel cell. There are currently two main methods of manufacturing hydrogen:
• reaction of hydrocarbons with steam
• electrolysis of acidified water.

Although a hydrogen fuel cell is not directly polluting, processes used to produce hydrogen
can be. Electricity for electrolysis is often produced by fossil fuel power stations. Carbon
dioxide is produced from the reaction of hydrocarbons with steam.

Transporting and storing hydrogen

Hydrogen is an explosive gas with a very low boiling point. It is difficult to transport and store.
Several methods have been developed.

A. Liquid under pressure

Hydrogen can be forced in to liquid state under high pressure. It requires very low temperature
and a special container to prevent it from boiling. This is an expensive method of storage.

B. Adsorption

Hydrogen can be adsorbed on to a solid material. This can take place at low pressure and
close to room temperature. However, currently the materials being used for adsorption must
be replaced regularly.

C. Absorption

Hydrogen can be absorbed by solid materials. Hydrogen atoms enter spaces in metal alloys
lattices, forming hydrides. However, these alloys deteriorate over time and need to be replaced
regularly.

Advantages of hydrogen fuel cells

• Hydrogen has a low density, making vehicles light and efficient.
• Hydrogen gives out more energy per gram than conventional fuels.

Disadvantages of hydrogen fuel cells

• The production, storage and distribution of hydrogen for use in fuel cells relies heavily
on energy from fossil fuels.

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• Pure hydrogen is expensive and highly flammable.

One way around these problems is to replace hydrogen with a more convenient substance.
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Methanol, natural gas and propane have all shown potential for use in fuel cells.

Hydrogen-rich fuels

With the difficulty in transporting and storing hydrogen, some fuel cell vehicles use
hydrogen-rich fuels which are converted to hydrogen by an onboard ‘reformer’.

The reformer uses temperatures of 250–300°C to favour reactions generating hydrogen

gas. Hydrogen-rich fuels include methanol, natural gas and petrol.

Reactions in a direct methanol fuel cell

Oxidation (anode): CH3OH + H2O 6H+ + 6e- + CO2

Reduction (cathode): 3/2O2 + 6H+ + 6e- 3H2O

Overall equation: CH3OH + 3/2O2 2H2O + CO2

Ethanol fuel cell

Ethanol is a less toxic and more energy-dense alcohol than methanol. Research into
developing an ethanol fuel cell is ongoing. Currently, platinum-based catalysts are used to
oxidize ethanol, but don’t achieve complete oxidation. Cheaper, more efficient catalysts
capable of fully oxidizing ethanol are needed.

Ethanol can be made from renewable sources, such as the fermentation of sugar. These
energy resources are considered carbon neutral – the amount of carbon dioxide they release is
equal to the amount absorbed during growth.

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