ABSTRACT

There are numerous features in this

book that are designed to make
learning Electrochemistry more
effective and more enjoyable

Sir Layan
Physical Chemistry Section

ELECTROCHEMISTRY
CHEMISTRY A LEVEL

APP/CALL SIR LAYAN 0774 372 589 FOR ANY ASSISTANCE

ELECTROCHEMISTRY
Electrode Potentials
Consider Electrode Potential of Zinc

Mz+ Mz+ Mz+

++
+
• When a metal is dipped into a solution containing its ions, an equilibrium is set up between
the metal rod and its ions.
• There is a tendency for metal atoms to lose electrons and go in solution as ions.
M(s) Mz+ (aq) + ze

• There is also a tendency for metal ions to gain electrons and to deposit on the surface of
metal rod as metal atoms.
Mz+ (aq) + ze M(s)

• An equilibrium is therefore established between the metal and its ions in the solution.
Mz+ (aq) + ze ⇌ M(s)

• At equilibrium a potential difference is set up between the solution and the metal.
• The potential difference cannot be measured directly.
• The potential difference is measured between the metal/metal ion system and another
system
• The potential difference value between the two system is referred to as the electrode
potential, E.
• The system we use for comparison is the standard hydrogen electrode.

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The Standard Hydrogen Electrode
• The standard reference cell used is a half-cell known as the standard hydrogen electrode,
S.H.E shown below and it is called S.H.E because the ‘electrode’ is hydrogen gas in contact
with its ions, H+.
• The potential difference recorded between the electrode M and the SHE is known as the
electrode potential (or reduction potential) of electrode M.
• In this set up, it is necessary to make sure that the standard conditions are employed and
this makes the comparison of electrode potentials of different electrodes meaningful.

Half Equation for SHE

2H+ + 2e ⇌ H2

• By convention, the SHE is assigned a voltage of zero.

• The value recorded by the voltmeter when the SHE is connected to an electrode M is
therefore attributed to the electrode. This value is known as the electrode potential of the
electrode M.
Platinised Platinum is used because:
i. The Pt metal provides an inert surface for this reaction and does not ionize in the acidic
medium in which it is immersed.
ii. It acts as a catalyst (Transition metal) since hydrogen on its own does not easily dissociate
into hydrogen ions.
iii. It provides an increased surface area for the reaction to take place.

Salt Bridge
• It is an absorbent material e.g. filter paper soaked with relatively inert electrolyte usually
KCl and NaCl because they are chemically inert.
• Salt bridge maintains electrical neutrality or charge balance between electric cells.
• Salt bridge helps to complete the circuit.
• Salt bridge prevent the two solutions from both electric cells from mixing.
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Standard Electrode Potentials
• The standard electrode potential (Eθ) of an electrode is the potential difference between a
half cell made up of that electrode and its ions, and a standard hydrogen electrode, under
standard state conditions.

Measuring standard electrode potentials

• There are three main types of half-cell whose Eᴓ value can be obtained when connected to a
standard hydrogen electrode.
metal/metal ion half-cell
non-metal/non-metal ion half-cell
ion/ion half-cell.
Half-cells containing metals and metal ions

• Figure below shows how to measure the Eθ value for a Zn2+/Zn half-cell.
• The voltage of the Zn2+/Zn half-cell is –0.76 V. The zinc is the negative terminal (negative
pole) of the cell and the hydrogen electrode is the positive terminal.
The two half-equations are:

• The Eθ values show us that Zn2+ions are more difficult to reduce than H+ ions (they have a
more negative Eθ value).
• Zn2+ ions are less likely to gain electrons than H+ ions.
• So, Zn will lose electrons to the H+/H2 half-cell and H+ ions will gain electrons from the
Zn2+/Zn half-cell.

• Reduction takes place at the positive terminal of the cell. For example, in the Zn2+/Zn; H+/H2
cell.
• Oxidation takes place at the negative terminal of the cell. For example, in the Zn2+/Zn: H+/H2
cell

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Half-cells containing non-metals and non-metal ions
• In half-cells that do not contain a metal, electrical contact with the solution is made by using
platinum wire or platinum foil as an electrode.
• Figure below shows a Cl2/Cl– half-cell connected to a standard hydrogen electrode. The
voltage of the Cl2/Cl– half-cell is +1.36 V. So, the Cl2/Cl– half-cell forms the positive terminal
of the cell and the hydrogen electrode is the negative terminal.
The two half-equations are:

• The Eθ values show us that Cl2 molecules are easier to reduce than H+ ions (they have a
more positive Eθ value).
• Cl2 molecules are more likely to gain electrons than H+ ions.
• So Cl2 molecules will gain electrons from the H+/H2 half-cell and H2 molecules will lose
electrons to the Cl2/Cl– half-cell.

Half-cells containing ions of the same element in different oxidation states

• Half-cells can contain two ions of different oxidation states derived from the same element.
• For example, a mixture of MnO4-, Mn2+ and H+ ions can form a half-cell using a platinum
electrode.
Half Equation Under Acidic Condition

• The H+ ions are included because they are essential for the conversion of MnO4– (manganate
(VII) ions) to Mn2+ ions.

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Half-cell contains
1.00 mol dm–3 MnO4–(aq) ions
1.00 mol dm–3 Mn2+(aq) ions
1.00 mol dm–3 H+(aq) ions

Drawbacks of Eθ values
1. The concentration varies as the reaction progresses
2. Some of the metals react very rapidly as the reaction proceeds and as a result the voltage
becomes difficult to note
3. Some of the metals react very slowly as the reaction proceeds and as a result the voltage
becomes difficult to note

Electrochemical Series
• This is an arrangement of the metals in order of their standard electrode potentials, starting
with the most negative (that is, the most positive if the electrode potentials are considered
in reverse).
• By convention, the electrode potential refers to the reduction reaction. So, the electrons
appear on the left-hand side of the half-equation. For example:

A metal which is high in the reactivity series (large and negative electrode potential), for
example, Mg shows the following properties
i. it readily gives up electrons to form ions. These electrons are gained by another substance
in a redox reaction. This other substance is therefore reduced. In other words, a metal with
a large and negative electrode potential (high up the electrochemical series) is a good
reducing agent.
Mg(s) Mg2+(aq) + 2e
ii. It is very reactive.

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On the other hand, a metal which is at the bottom of the electrochemical series
i. Does not readily give up electrons. Instead, its ions readily gain electrons (for example,
from a metal higher in the series) to form the neutral metal, e.g.
Ag+(aq) + e Ag(s)

Assignment

Using Eθ values to predict cell voltages

• Eθ values to calculate the voltage of an electrochemical cell made up of two half-cells, even
when neither of them is a standard hydrogen electrode.
• The voltage measured is the difference between the Eθ values of the two half-cells
• The value is referred to as the standard cell potential.
Consider the two half equations below

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Interpreting the half equations

• Since the value of Ag+/Ag is positive it shows that Ag+ ions readily gain electrons to form the
neutral metal Ag.
Ag+(aq) + e Ag(s) (Eθ1 = +0.80V)

• Since the value of Zn2+/Zn is less positive compared to that of Ag+/Ag and this shows that
Zn has a tendency of losing electrons therefore both the equation and the sign of the Eθ
value are reversed.
Zn(s) Zn2+(aq) + 2e (Eθ2 = +0.76)
Standard Cell Potential = Eθ1 + Eθ2
= +1.56V
Consider the two half equations below

Interpreting the half equations

• Since the value of Fe3+/Fe2+ is more positive, it shows that Fe3+ ions readily gain electrons to
form Fe2+.
Fe3+(aq) + e Fe2+(aq) (Eθ1 = +0.77V)

• Since the value of Cu2+/Cu is less positive compared to that of Fe3+/Fe2+ and this shows that
Cu has a tendency of losing electrons therefore both the equation and sign of the Eθ value
are reversed.
Cu(s) Cu2+(aq) + 2e (Eθ2 = -0.34)
Standard Cell Potential = Eθ1 + Eθ2
= (+0.77V) + (-0.34V)
= +0.43V

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Movement and Direction of electrons
• The electrons move through the wires in the external circuit. They do not travel through the
electrolyte solution.
• Electrons flow from the negative pole (loss of electrons) to the positive pole (gain of
electrons). It may help you to remember that the more positive pole attracts the negative
electrons.

Terminals on the electric cell

• The positive pole is the cathode because that is where reduction is taking place and the
negative pole is the anode because that is where oxidation is a taking place.

The Shorthand Representation

• It can also be referred to as the convectional representation of an electric cell.
• When writing the short hand representation, we always start with the shorthand of the half
equation were oxidation is taking place.
• Solid components are always separated from gaseous, aqueous or liquids with a solid bold
straight line.
• Two half cells are combined with a salt bridge which is represented as a double dotted line
• We the complete the shorthand representation by writing the shorthand of the half
equation where reduction is taking place.

Consider Zn2+ / Zn and Cu2+ / Cu

Zn(s) Zn2+(aq) Cu2+(aq) Cu (s)

Consider Mn2+ / Mn and H2O / H2

Mn(s) Mn2+ (aq) 2H2O(l) ; H2 (g) + 2OH-(aq) Pt (s)

Effect of Concentration on Eθ values

• According to the Le Chatelier’s principle to redox equilibria. If we increase the
concentration of the species on the left of the equation, the position of equilibrium will shift
to the right. So, the value of Eθ becomes more positive / less negative.
Consider the Equation below

• If the [Zn2+] is greater than 1.00 mol dm–3, the value of E becomes less negative / more
positive (for example −0.61 V).
• If [Zn2+] is less than 1.00 mol dm–3, the value of E becomes more negative / less positive
(for example −0.80 V).

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Predicting Feasibility of reactions
• After combining two half equations to form one full equation ,the overall standard cell
potential should be calculated.
• If the calculated voltage is positive ,it implies that the reaction is feasible.
• If the calculated voltage is negative ,it implies that the reaction will not spontaneously occur
and we conclude that the reaction is not feasible.
• The feasibility of a reaction based on Eθ values is no guarantee that a reaction will proceed
quickly. Some reactions are feasible, but they proceed so slowly that they do not seemto be
taking place.
Consider the feasibility of the following reactions
1. Cr2O72- and Cl-
2. Pb2+ and Ni
3. Co2+ and MnO4-
4. Zn2+ and SO2

Electrolysis
• Electrolysis the decomposition of a compound into its elements by an electric current.

Uses of electrolysis
• to extract useful metals from their ores.
• to produce useful by-products such as chlorine gas.
• to purify metals.

Electrolytic Cell
• Electrolysis is carried out in an electrolytic cell.
An electrolytic cell consists of:

• The electrolyte which is the compound being decomposed. It is either a molten ionic
compound or a concentrated aqueous solution of ions. Solid ionic compounds and covalent
compounds cannot be used because they do not conduct electricity.
• The electrodes which are rods made from graphite or a metal which conducts electricity to
and from the electrolyte.
Anode is the positive electrode.
Cathode is the negative electrode.
• External power supply of direct current and a complete d.c. circuit.

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Redox reactions in electrolysis
• During electrolysis, the cations are attracted to the cathode while the anions are attracted to
the anode.
• At the cathode, cations gain electrons and are reduced. Reduction occurs at the cathode.
• At the anode, anions lose electrons and are oxidised. Oxidation occurs at the anode.

Electrolysis of Molten Sodium Chloride

Ions Present
Na+, Cl-
At the Cathode

• Na+ is attracted and the cathode and then discharged at the cathode. Na+ gains an electron
and Na metal is deposited at the cathode as shown by the equation below
Na⁺+ e⁻ Na
At the anode

• Cl- is attracted and the anode and then discharged at the anode. Cl- loses an electron and Cl
atom is deposited at the cathode as shown by the equation below.
• Since Chlorine exists as diatomic molecule at r.t.p the Cl atoms react together forming Cl2
2Cl- Cl2 + 2e⁻

• Sodium metal and chlorine gas are produced.

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Electrolysis of Aqueous Sodium Chloride
Ions Present
Na+, Cl-, OH- and H+
At the Cathode

• H+ and Na+ ions are attracted at the cathode and then H+ ion is discharged at the cathode
because it is below Na+ ion in the electrochemical series. H+ gains an electron and becomes
H atom. H atom reacts with another H atom since it exists as a diatomic molecule at r.t.p and
is deposited at the cathode as shown by the equation below.
2H⁺(aq) + 2e⁻ H2(g)

At the anode
• OH- and Cl- ions are attracted at the anode and then OH- is discharged at the anode because
OH⁻ is lower in the electrochemical series than Cl-.
• OH- loses electrons and O2 atom is deposited at the cathode as shown by the equation
below.
4OH-(aq) O2(g) + 2H2O(l) + 4e⁻

• H2O and Oxygen gas are produced.

Factors That Determine the Selective Discharge of Ions in An Electrolytic Cell

Position of the ion in the electrochemical series

• The lower it is in the electrochemical series, the higher the possibility for it to be
discharged.
Concentration of the ions

• the higher the concentration of the ion, the higher the possibility for it to be discharged.

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Electrolysis of Acidified Water
Electrolysis of Dilute H2SO4
• Water is made up of hydrogen and oxygen (H2O). Electric current is passed through
acidified water.
• The water is acidified to increase the electrical conductivity of water.
• The hydrogen and oxygen are split up by the electric current.
• Platinum electrodes are used.

Ions Present
H+, OH- and SO42-
Reaction at Anode

• OH- and SO42- ions are attracted at the anode and then OH- is discharged at the anode
because OH⁻ is lower in the electrochemical series than SO42-.
• OH- loses electrons at anode to become O2 and H2O.
4OH-(aq) O2(g) + 2H2O(l) + 4e⁻
Reaction at Cathode

• H+ ions are attracted at the cathode and then H+ is selectively discharged at the cathode
• H+ gains electrons and H2 gas is deposited at the cathode as shown by the equation below.
2H+(aq) + 2e H2(g)
Overall Equation

• Both equations must be balanced first. The cathode equation is short 2 electrons. Hence, we
should first even them by multiplying cathode equation by 2.
4OH- O2 + 2H2O + 4e ×1
2H+ + 2e- H2 ×2
2H2O(l) O2(g) + 2H2(g)
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Extraction of Aluminium from Bauxite Ore
• Bauxite is impure aluminium oxide, Al2O3. The impurities are iron oxides, silicon dioxide
and titanium dioxide. Bauxite is the major aluminium ore.
• The first step is to purify the bauxite to get pure aluminium oxide, Al2O3.
• Molten aluminium oxide is electrolysed in a solution of cryolite, Na3AlF6 to give out the
required aluminium metal.
• Graphite is used as an electrode because it has got a high melting point hence it resists high
temperatures in the electrolytic cell. Graphite also has the advantage of being relatively
cheap.
The function of dissolving aluminium oxide in large amount of cryolite is to:
i. lower the melting point of the electrolyte from about 2140 °C to 970 °C (It acts as a flux)
ii. improve the electrical conductivity of the electrolyte.
Electrolysis of aluminium oxide is carried out in long narrow cells using carbon (graphite)
electrodes.

Ions Present
Na+, AlF63-, Al3+, O2-
At the Anode

• O2- and AlF63- ions are attracted at the anode and then O2- is selectively discharged at the
anode.
• O2- loses electrons and O2 gas is deposited at the cathode as shown by the equation below.
2O2-(aq) O2(g) + 4e⁻

• But due to high temperatures under which the reaction is occurring, the oxygen gas
released will oxidise the hot carbon electrodes to carbon dioxide and carbon monoxide.
• So, the electrodes have to be replaced from time to time.
C(s) + O2(g) CO2(g)

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Combining the two equations at the anode, the overall equation becomes
2O2-(aq) + C(s) CO2(g) + 4e⁻
At the Cathode

• Na+ and Al3+ ions are attracted at the cathode and then Al3+ is selectively discharged at the
cathode.
• Al3+ gains electrons and Al atom is deposited at the cathode as shown by the equation
below.
Al3+(aq) + 3e Al(s)

• Aluminium is denser than the electrolyte. It drops to the bottom of the electrolytic cell and
is removed using a suction tube or through a tap hole.
Overall Equation
This can be obtained by combining half equations from the anode and cathode
2O2- + C CO2 + 4e⁻ ×3
Al3+ + 3e Al ×4
4Al3+ + 6O2- + 3C 3CO2 + 4Al
2Al2O3(l) + 3C(s) 3CO2(g) + 4Al(s)

• This equation is an oversimplification because it gives the wrong impression that Al2O3 is
reduced by carbon to Al metal.
• The conversion of Al2O3 to Al in this process is not achieved by the use of a reducing agent,
but by the use of an electric current (as a reducing agent, carbon is too weak to reduce
Al2O3).

Uses of Aluminium in relation to its property

Use Property
Making cooking pots Resist corrosion
Good conductor of heat
Overhead power pots Light
Resistant to corrosion
Good conductor of electricity
Aircraft bodies Light

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Electrolysis of brine
• Brine is concentrated aqueous solution of sodium chloride. It is obtained from sea water or
by dissolving rock salt in water.
• Electrolysis of brine is used to produce chlorine, hydrogen and sodium hydroxide. A
diaphragm cell is used to carry out this reaction.

• The electrolyte level in the anode compartment is kept higher than in the cathode
compartment. This ensures the flow of the solution is always towards the cathode
compartment. This reduces the possibility of backflow of sodium hydroxide solution formed
which can reacts with chlorine at the anode to form unwanted by products such as NaClO or
NaClO3.
• Titanium is used as an electrode because it resists corrosion.
Ions Present
Na+, Cl-, H+, OH-
At the Anode

• Cl- and OH- ions are attracted at the anode and then Cl- is selectively discharged at the anode
because Cl⁻ is in a far greater concentration than OH⁻.
• Cl- loses electrons and Cl2 gas is deposited at the anode as shown by the equation below.
2Cl-(aq) Cl2(g) + 2e⁻

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At the Cathode

• Na+ and H+ ions are attracted at the cathode and then H+ is selectively discharged at the
cathode because H⁺ is lower in the electrochemical series.
• H+ gains electrons and H2 gas is deposited at the cathode as shown by the equation below.
2H+(aq) + 2e H2 (g)

• Na+ ions therefore accumulate in the cathode compartment and they attract OH- ions from
the anode compartment. The solution in the cathode compartment therefore gradually
becomes richer in NaOH and this solution is drained out.
Overall Reaction
2Cl-(aq) + 2H+(aq) H2(g) + Cl2(g)

• The electrolysis of brine therefore produces three products; hydrogen, chlorine and NaOH.
• The net equation for the electrolytic process is
2NaCl (aq) + 2H2O (l) Cl2 (g) + 2NaOH (aq) + H2 (g)

• This equation is useful in determining the ratio in which the three products are produced.
The ratio of Cl2: NaOH: H2 is 1: 2: 1.
• However, this reaction is an oversimplification and is misleading. It gives the wrong
impression that NaCl has a reaction with water. NaCl does not react with water but simply
dissolves in it.

Uses of Products obtained from electrolysis of brine

Sodium Hydroxide Chlorine Hydrogen
Used in the Manufacture of Used in the Manufacture of Used in the Manufacture of
Soap Organic Solvents Margarine
Bleaching Agents Household bleaches Ammonia
Pulp and Paper CFCs Metals from their ores

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Electrolytic purification of copper
• Copper is purified to be used for electrical wiring because 99.99% of purity is required for
efficient transmission of electrical energy. Even small amounts of impurity reduce its
conductivity greatly.
Electrolytic purification of copper is carried out in cells using:
i. an electrolyte of copper (II) sulphate solution acidified with sulfuric acid.
ii. an anode of impure copper.
iii. a cathode of pure copper.

At the anode

• The copper anodes dissolve through oxidation, releasing Cu2+ ions, which then migrate to
the cathode.
Cu(s) Cu2+(aq) + 2e

• The anodes therefore get thinner whilst the cathodes gain mass and become thicker. The
impurities in the anode settle down as anode 'sludge'.
• The purification process removes certain impurities, particularly zinc, gold and silver.
• Electrode potentials can be used to explain how these impurities are removed from the
impure copper.

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 • The conversion of zinc metal to Zn2+ has a positive reduction potential (reverse of equation
(i) that is, at the anode, any zinc in the copper easily turns to Zn2+ ions.
• On the other hand, the reduction of Zn2+ ions to zinc metal has a negative reduction
potential, that is, the reduction of Zn2+ ions to zinc metal is not likely in aqueous solution.
The ions therefore stay in solution.
• The reduction potentials of silver and gold are more positive than that of copper (they are
more stable). These two impurities do not easily dissolve at the anode.
• Instead, they remain in their solid metallic state and drop to the bottom of the cell as the
impure copper anode dissolves.
At the Cathode

• At the cathode, Cu2+ ions are reduced, forming copper metal, which sticks onto the cathode.
Cu2+(aq) + 2e- Cu(s)

• Copper ions are transferred from the anode to the cathode. As a result, the cathode gets
thicker and the anode get thinner.
• The concentration of copper (II) sulphate solution does not change because the number of
moles of Cu²⁺ions formed at the anode is exactly the same as the number of moles of
Cu²⁺ions discharged at the cathode.

Other Cells
1. Fuel Cell
2. Lead Acid Accumulator
3. Dry Cell

Fuel Cell
• A fuel cell consists of a fuel and an oxidant.
• There are different types of fuel cells which use different forms of fuels.
These fuels include
i. Hydrogen
ii. Hydrocarbons
iii. Alcohols

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The Hydrogen Oxygen Fuel Cell
• This consists of a hydrogen gas which is a fuel and an oxidant which is oxygen gas.
• Fuels convert chemical energy to electrical energy
• The energy conversion is about 60-70% which is a high percentage i.e. fuel cells are
efficient.

An Alkaline Hydrogen Fuel Cell

• An alkali or an acid can be used as an electrolyte.

At the Anode

• At the anode, catalytic oxidation of hydrogen gas occurs to produce H+ ions.

H₂(g) 2H⁺(aq) + 2e⁻ (1)

• The anode (negative electrode) is made of porous graphite which is coated with a catalyst of
nickel and nickel (II) oxide. The graphite electrode provides an inert surface on which
hydrogen is oxidized, catalysed by nickel and nickel (II) oxide.
• Apart from acting as an electrolyte, the alkali supplies OH⁻ ions which remove the H⁺ ions
produced in reaction.
2OH⁻(aq) + 2H⁺ (aq) 2H₂O(l) (2)

• This speed up the anode reaction by pushing the position of the equilibrium of equation 1 to
the right, that is, more hydrogen gas molecules are oxidized to replace the OH⁻ ions that are
lost from the equilibrium as water (Le Chatelier’s principle).
Combining Equations 1 and 2
H₂(g) 2H⁺(aq) + 2e⁻ [oxidation]
2OH⁻(aq) + 2H⁺(aq) 2H₂O(l) [neutralization]

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Anode overall half equation
H₂(g) + 2OH⁻(aq) 2H₂O(l) + 2e Eθ = +0.83V

• Note that the oxidation of hydrogen gas in the absence of OH⁻ ions (reaction 1) would give
an Eθ value of zero. The presence of OH⁻ ions therefore makes the Eθ value more positive,
and the oxidation half reaction more feasible.
• The anode reaction produces electrons which then travel in the external circuit towards the
cathode. This flow of electrons can be used to operate a device (the load).
At the Cathode

• An O atom is reduced by gaining two electrons which come from the anode via an external
circuit.
O + 2e O2⁻

• Since there are two oxygen atoms in a molecule of oxygen, a total of four electrons would be
gained per molecule of oxygen.
O2 + 4e 2O2⁻ (3)

• The oxide ions are too unstable to have an independent existence. They rapidly react with
water, to produce OH⁻ ions.
2O2⁻(aq) + H₂O(l) 4OH⁻(aq) (4)

By combining equations (3) and (4), we obtain the reduction (cathode) half equation
O₂(g) + 4e⁻ 2O2⁻(aq)
2O2⁻(aq) + 2H₂O(l) 4OH⁻(aq)
Cathode Overall half equation
O₂ (g) + 4e⁻ + 2H₂O (l) 4OH⁻(aq) Eθ = +0.40V

• The cathode is porous graphite coated with nickel which catalyses the reduction of oxygen.
The OH⁻ ions generated at the cathode continuously diffuse through the cell to the anode,
where they aid the oxidation of hydrogen.

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Combining the Anode and Cathode Half Equations
Anode 2H₂(g) + 4OH⁻(aq) 4H₂O(l) + 4e (Eθ = +0.83V)
Cathode O₂(g) + 4e⁻ + 2H₂O(l) 4OH⁻(aq) (Eθ = +0.40V)
Net 2H₂(g) + O₂(g) 2H₂O(l) (Eθ = +1.23)

• Notice that the same amount of OH- ions that are used at the negative electrode are
produced at the positive electrode. The concentration of electrolyte is therefore expected to
remain constant

Acid Hydrogen Fuel Cell

• It is possible to use an acid as an electrolyte.
• Concentrated or liquid Phosphoric acid is commonly used as an electrolyte.
• The electrodes are made of carbon paper coated with a finely dispersed platinum catalyst.

At the Anode

• At the anode, hydrogen is oxidized

2H₂(g) 4H⁺(aq) + 2e⁻ [oxidation] (Eθ = 0.00V)
At the Cathode

• At the cathode, oxygen is reduced in the presence of an acid.

O₂(g) + 4H+(aq) + 4e⁻ 2H2O(aq) (Eθ = +1.23V)
Combining the Anode and Cathode Half Equations
Anode 2H2(g) 4H+(aq) + 4e (Eθ = 0.00V)
Cathode O₂(g) + 4H+(aq) + 4e⁻ 2H₂O(l) (Eθ = +1.23V)
Net 2H₂(g) + O₂(g) 2H₂O(l) (Eθ = +1.23)

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 • The Eθ cell is not changed by changing the electrolyte. Overally, hydrogen ions consumed at
the cathode are generated at the anode. Concentration of electrolyte therefore remains
constant

Uses of a fuel cell

• For empowering car batteries.
• To provide water for Astronauts from urine.
• For heating and lighting in homes.

Advantages of a Fuel cell

• It works indefinitely i.e. it can supply a continuous current, which is suitable in devices
which require a steady and reliable source of current, for example, in a spaceship.
• It is one of the greenest sources of energy to be developed. There is no pollution associated
with it, since the sole product of the reaction is water.
• It is efficient and only a little amount of energy is lost during the conversion of chemical
energy to electrical energy.

Disadvantages
• It produces a low voltage and current.
• The development of a fuel cell is rather expensive. This has limited the widespread use of
fuel cells.
• The storage of hydrogen still presents a problem because of its explosive nature.
• The fuel cell is large and cumbersome. Once more, this prevents it from being a versatile
source of electrical energy.
• The source of hydrogen gas is still a challenge since it is not found in air. Producing
hydrogen by the electrolysis of water is not a solution to the energy problem since the
process consumes huge quantities of electrical energy. A method has been developed for
producing hydrogen gas from methane, but the demands of the process makes its
application limited.

Alcohol Fuel Cell

Proton Exchange Membrane (H+)

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At the Anode

• Alcohol (methanol) and water are adsorbed on a catalyst usually made up of platinum and
ruthenium and lose protons until CO2 is formed.
CH3OH + H2O CO2 + 6H+ + 6e
At the Cathode

• H+ ions are transferred to the cathode were oxygen accepts electrons and is reduced to form
water.
𝟑
𝟐
O2 + 6H+ + 6e- 3H2O

Overall equation
𝟑
CH3OH + 𝟐 O2 CO2 + 2H2O

Anion Exchange Membrane (OH-) or O2-

At the Anode

• Hydroxide ions adsorb on the surface of the catalyst where they react with alcohol at the
anode. Alcohol (methanol) is oxidised to CO2.
• Water and electrons are produced.
CH3OH + 6OH- CO2 + 5H2O + 6e
At the Cathode

• Oxygen accepts electrons and is reduced to OH-. OH- are then transferred through the
electrolyte to the anode.
𝟑
O2 + 3H2O + 6e- 6OH-
𝟐

Overall equation
𝟑
CH3OH + 𝟐 O2 CO2 + 2H2O

Advantages of alcohol and hydrocarbons fuel cell over hydrogen fuel cell
• Available at low cost compared to pure hydrogen
• Higher storage density

Disadvantages of alcohol and hydrocarbons fuel cell over hydrogen fuel cell
• They produce CO2 which can lead to acid rain, greenhouse effect and global warming

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The LEAD-ACID BATTERY
• This is a well-known example of a secondary (rechargeable) battery.
• The anode (negative electrode) is a plate of lead metal.
• The cathode is lead (IV) oxide, PbO2, present as a coat on a lead metal plate.

During discharge
At the cathode (positive terminal)

• PbO2 is reduced to Pb2+. The Pb2+ ions immediately combine with SO42- ions from H2SO4 to
form white and insoluble PbSO4.
At the anode (negative terminal)

• The lead plates are oxidized to Pb2+. Once more, the Pb2+ ions combine with SO42- ions to
form PbSO4.
The two half equations are shown below
cathode reduction half reaction PbO2(s) + 4H+ + 2e Pb2++ 2H2O (Eθ = +1.87V) (1)
anode oxidation half reaction Pb(s) Pb2+ + 2e (Eθ = +0.13V) (2)
PbO2(s) + 4H++ Pb(s) 2Pb2+ + 2H2O (Eθ =+2.00V)

• Note that the reduction potential for equation (1) is more positive than the one quoted in
the Data Booklet (+1.47V). This is because the acid (H+) used in the battery is fairly
concentrated and this drives the equilibrium to the right, that is, the reaction becomes more
favourable in the forward direction.

During Charging
• The major advantage of the lead-acid battery is that it can be recharged. This is done by
passing an electric current from an external source into the battery.
• This current is then passed into the battery. The flow of electrons in to the battery
essentially reverses the anode and cathode half reactions.
• Half of the Pb2+ produced in reaction are reduced to Pb metal, which is deposited on the
negative (anode) lead metal plate. The rest of the Pb2+ are oxidized to PbO2(s) which forms a
deposit on the positive (cathode) lead metal plate.
Pb2+ + 2e Pb(s) (Eθ = -0.13)
Pb2++ 2H2O PbO2(s) + 4H++ 2e – (Eθ =-1.87)

Advantages of Lead acid battery

• They can be recharged
• Large current
• Large Voltage

Disadvantages of Lead acid battery

• Not portable and it is heavy due to the presence of lead and sulphuric acid.
• It leaks and needs careful disposal because lead compounds are poisonous.

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Dry Cell
• The most common dry cell is the Zinc-Carbon cell. The cell is said to be dry because it does
not contain liquids.

Advantages
• They have a reliable voltage.
• They are portable.
• The do not leak.

Disadvantages
• They have a low voltage.
• They have a low current.
• Most of them can be recharged.

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Quantitative Electrolysis
• It is possible to calculate the amount of substance produced during electrolysis, for
example, the amount of metal deposited at the cathode and the volume of gas produced at
the anode.

Electric Charge
• The quantity of electricity passed during electrolysis is measured in coulombs (C). This
quantity, also known as electric charge, Q, depends on the duration (time) of the process
and also on the size of current.

• The mass of a substance produced at (or removed from) an electrode during electrolysis is
proportional to the quantity of electricity (in coulombs) which passes through the
electrolyte.

Faraday Constant
• The quantity of electricity is often expressed in terms of a unit called the Faraday (symbol
F).
• Since 1 electron has a charge of -1.60 × 10–19C and 1 mole of electrons contains 6.02 × 1023
particles.
Therefore, 1 mole of an electron has a charge of:
F= L×e
L = Avogadro’s number
E = Charge of the electron
–1.60 × 10–19 C x (6, 022 x 1023) = 96 352 C

• This figure, often rounded off to 96 500C/mol, is known as the Faraday constant, F.
Amount of metal deposited at the cathode during electrolysis

• A metal is deposited by the reduction of its ions at the cathode as shown below
Mz+(aq)+ ze ⇌ M(s)

• The number of coulombs required to discharge 1 mole of a metal from its ions (MZ+) is given
by the equation below
Q = zF

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 • where z is the size of charge on the ion and F is the Faraday constant.
From the equation above
1 mole of metal is equivalent to zF Coulombs

1 mol of metal discharged zF (Coulombs)

Less 1 (Coulombs)
1
• Therefore, one Coulomb produces moles of metal discharged
𝑧×𝐹
Thus, the total number of moles of metals atoms discharged is given by the equation below
1
N = Number of Coulombs that flows through the circuit (It) × moles
𝑧×𝐹
Hence mass = number of moles × Mr
𝑀𝑟 × 𝐼𝑡
Mass Deposited =
𝐹×𝑧

• Mass, m of metal deposited during electrolysis is directly proportional to charge Q.

Graph showing direct variation between charge and mass of metal deposited during electrolysis.

𝑀𝑟
slope = 𝐹×𝑍

Volume of gas produced during electrolysis

• When calculating volume of gases produced during electrolysis molar gas volumes are used
At 250C/298K and 1atm thus at r.t.p
1 mole = 24 dm3
At 0C/273K and 1atm thus at s.t.p
1 mole = 22.4 dm3

• Therefore, it implies that using the number of moles calculated from the equation above we
can calculate the volume of the gas produced.

27 | P a g e
Determination of Avogadro’s constant or electronic charge
• We can use an electrolytic method to find a value for the Avogadro constant by calculating
the charge associated with 1 mole of electrons.
Apparatus
DC Supply, Ammeter, Rheostat (Variable Resistor), Stopwatch, Switch, Electronic Balance, and
Other Electrolysis Equipment.
Diagram

Procedure
1. The cathode is cleaned and weighed using the electronic balance and record the initial mass
M1 before being placed in the copper (II) sulphate solution.
2. Set up the apparatus as shown by the diagram above.
3. Simultaneously close the switch and start the stopwatch
4. The circuit is completed and the current set by adjusting the variable resistor.
5. Note and record the current (I) flowing in the circuit from the ammeter.
6. The current is maintained for some time e.g. exactly 40 minutes at which point the circuit is
opened and simultaneously stop the stopwatch.
7. The cathode is removed from the solution and carefully washed with distilled water to remove
any copper (II) sulphate solution.
8. Distilled water is removed from the cathode by rinsing it with propanone in which the water
dissolves.
9. The cathode is finally dried by allowing the propanone to evaporate from its surface.
10. The cathode is reweighed using the electronic balance and record the final mass M2.

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Treatment of results
Mass Deposited (m) = Final mass (M2) – Initial Mass (M1)

• Substitute the recorded values of current and time t in seconds together with mass in the
formula shown below
𝑀𝑟 × 𝐼𝑡
Mass Deposited =
𝐹×𝑧
But, Faradays constant F= L×e
L = Avogadro’s number and e = Charge of the electron
𝑀𝑟 × 𝐼𝑡
Mass Deposited =
𝐿×𝑒×𝑧

• If asked to determine the Avogadro’s constant, we make L subject of the formula and if we
are asked to determine the charge of the electron, we make e subject of the formula.

Other Possible Design Questions

1) If asked to Determine Faraday Constant make F subject of the formula.
2) If asked to determine the relationship between mass and charge, u repeat the experiment at
different time intervals and deduce the mass per each time interval and draw a graph of mass
against electric charge.

Questions on Electrolysis
1) A constant current of 20.0A was passed through an electrolytic cell containing CuSO4(aq). The
anode in this cell was made of impure copper, and the cathode was made from pure copper. After
10 hours it was found that 225g of pure copper had been deposited on the cathode. Calculate the
following, using appropriate data from the Data Booklet.
a) number of moles of copper produced at the cathode
b) number of moles of electrons needed to produce this copper
c) number of moles of electrons that passed through the cell.
2) Hence calculate the percentage of the current through the cell that was actually used to discharge
the copper metal at the cathode. Explain why your answer is not 100%.
3) When a constant current of 10A was passed through copper (II) sulphate solution for 7 minutes,
1.38g of copper was discharged at the cathode. Use this information to calculate a value for
a) the Avogadro constant, L and comment on the value.
b) the Faraday constant, F.
4) A current of 12A is passed for 150 minutes through aqueous sodium sulphate using inert
electrodes.
a) What is the volume of gas liberated at the cathode at s.t.p?
5) 30g of a metal X was discharged by electrolysis, according to the equation.
X3+(aq) + 3e- ⇌ X (s)
a) Given that the electrolysis was done for 24 125 seconds with a constant current of 2.4A, deduce
the identity of metal X.

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