Chapter seven

Electrochemistry

Introduction
7.2 Electrical conductivity
7.3 Electrochemical Cells
7.3.1 Galvanic cells
7.3.2 Electrolytic cells
7.4 Quantitative aspects of electrolysis
7.5 Applications of Electrochemistry
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 Introduction
 Electrochemistry is a field of chemistry that deals with the
relationship between electrical energy and chemical energy.
 It is a field of chemistry concerned with processes that bring about
chemical reactions (changes) using electricity or generating
electrical energy from chemical reactions.
 Thus, electrical energy and chemical energy are inter-convertible.
The devices that convert chemical energy to electrical energy or
electrical energy to chemical energy are called electrochemical
cells.
 These cells can be classified as electrolytic cells and galvanic or
voltaic cells.
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 Electrolytic cells use electrical energy to bring about chemical
changes that produce many desirable substances in our daily lives.
 Galvanic or voltaic cells convert chemical energy to electrical energy.
The cells we use in flashlight batteries, wrist watches, cameras and
car batteries are examples of Galvanic cells.
 The reactions between the chemicals in these cells are responsible
for the generation of electricity.
Electrical Conductivity
 Electrical conductivity is the capacity of a substance to transmit
electricity.
 The materials that allow the passage of electricity through them
are called electrical conductors.
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 Depending on the nature of the particles responsible for the flow
of electric charges through conductors, electrical conductivity can
be classified as metallic conductivity or electrolytic conductivity.
• Metallic conductivity refers to the transmission of electric
current through metals. This transmission is directly related to
the structure of metals.
• In atoms of metals, the valence electrons are bounded very
loosely to their respective nuclei and move very easily
throughout the metal. This means metals contain electrons that
do not have fixed positions and are relatively free to move.
• These electrons are called free electrons or mobile electrons or
delocalized
12/24/2024 electrons. 4
• Thus, the structure of the metals can be regarded as a series of
positively charged metal ions, or cations, in a sea of negatively
charged electrons.
• The electrons entering the metal displace (repel) the freely
moving electrons at the point of entry. The displaced electrons
occupy new positions by pushing neighboring electrons ahead.
• This will continue until electrons are forced out of the wire at the
opposite end.
• So, metallic conductivity is caused by the flow of mobile
electrons due to repulsion exerted on them from the electrons
entering the metal from the source of electricity.
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 Figure : Sea of electron

• Non-metals are generally non-conductors of electricity, because

they do not have freely moving electrons.
• Graphite is a form of carbon in which the carbon atoms are
bonded in trigonal planar fashion to the three other carbon
atoms, to form inter-connected hexagonal rings.
• Electrons move freely through the hexagonal layers, making
graphite a good conductor of electricity.
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Structure of graphite (The blue colour is added to emphasize the planarity of the carbon layers.)

Electrolytic conductivity
• Electrolytes are substances that transmit electricity in a molten
state or in aqueous solution.
• Based on their degree of ionization or the extent to which they
produce anions and cations, electrolytes can be classified as
strong electrolytes or weak electrolytes.
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• Strong electrolytes ionize almost completely in aqueous
solutions. Weak electrolytes ionize only slightly.
• When electrical potential is applied through an electrolyte
solution, the positive ions (cations) move in one direction and
the negative ions (anions) move in the opposite direction.
• This movement of ions through the electrolyte, brought about
by the application of electricity, is called electrolytic
conductivity.
• Hence, the charge-carriers in electrolytic conductivity are ions
(anions and cations).

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• The substances that do not transmit electricity either in solution
or in a molten state are called non-electrolytes. Ionic compounds
are non-conductors of electricity in the solid state.
• This is because their ions are held at fixed positions and cannot
move. Other examples of non-electrolytes include sugar, ethanol,
oil, benzene, and liquid nitrogen.
Electrolysis
• It is a process in which electrical energy is used to produce
chemical changes.
• This process is carried out in an electrochemical cell known as
an electrolytic or electrolysis cell.
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• A typical electrolysis cell contains a source of direct electric
current, an electrolyte and connecting wires that join the source
to the electrodes.
• During electrolysis, the ions of the electrolyte migrate to the
electrodes of the opposite charge.
• The positive ions are attracted to the cathode and are called
cations. Since the cathode has excess electrons, the cations will
discharge by gaining electrons.
• This process of gaining electrons is called reduction. The
negative ions are attracted by the positive electrode (anode) and
are called anions.
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• These ions are discharged by losing electrons at the anode. This
process of losing electrons is called oxidation.
• Thus, the cathode is the electrode at which reduction occurs and
the anode is the electrode at which oxidation takes place.
• The reaction that takes place at each electrode is known as a
half-cell reaction.
• Oxidation half-reactions occur at the anode and reduction
half reaction at the cathode.
• The net reaction that takes place in the electrolytic cell is known
as a cell reaction.
• This overall reaction is also referred to as an oxidation-reduction
reaction
12/24/2024 or redox reaction. 11
• So electrolysis is a process in which electric energy is used to
bring about an oxidation reduction reaction.
• It is also defined as the decomposition of an electrolyte, using
electricity. The process of electrolysis includes electrolyzing
aqueous solutions of electrolytes.
Electrolysis of Molten (Fused) Electrolytes
 When ionic solids melt, they dissociates into positive and
negative ions that are not held in fixed positions.
 To understand the chemical reactions that occur during
electrolysis, consider a hypothetical electrolyte, MX, that
dissociate into M+ and X–.
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• During electrolysis, the cations, M+ ions, move toward the
cathode, gain one electron each and become M atoms.
• The anions, X– ions, move toward the anode, lose one electron
and become X atoms.
• The reaction at each electrode and the entire reaction in the
electrolytic cell are represented by the following equation.
cathode reaction M++ 1e-→M (reduction half reaction)

Anode reaction X- → X + 1e- (oxidation half reaction)

Cell reaction: M+ + X– →electrolysis M + X (Oxidation-reduction)

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• It is very important to realize that the number of electrons gained by the
cations at the cathode is exactly equal to the number of electrons lost by
anions at the anode during electrolysis.
• This is true for any oxidation-reduction (redox) reaction. Moreover, oxidation
and reduction reactions proceed simultaneously.
• Reduction and oxidation cannot occur separately. Oxidation is always
accompanied by reduction and there cannot be reduction in the absence of
oxidation, and vice versa.
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Preferential Discharge
• If more than one cations or anions reach an electrode, only one of them
preferentially gets discharged at one electrode.
• Thus, there is a choice amongst the ions that will get discharged on an
electrode.
• This is termed the preferential discharge of ions during electrolysis.
• The preferential discharge of ions is affected by the nature of the electrodes,
the positions of the ions in the electrochemical series and the concentration
of the ions in the electrolyte.
Nature of the electrodes
• Inert electrodes, like graphite or platinum, do not affect the product of
electrolysis, but reactive or active electrodes, like copper, can affect the
product of electrolysis.

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• For example, in the electrolysis of copper sulphate solutions, using graphite
electrodes, oxygen gas is liberated at the anode and copper metal is deposited
at the cathode, as shown below.
CuSO4(aq) —→ Cu2+(aq) + SO42– (aq)

Anode : 4OH– (aq) —→ O2 (g) + 2H2O (l) + 4e–

Cathode: Cu2+(aq) + 2e– —→ Cu (s)
• However, if the electrolysis of copper sulphate is performed using copper
electrodes, the copper electrode at the anode dissolves and copper metal will
be deposited at the cathode, as indicated below.
• Anode : Cu (s) —→ Cu2+(aq) + 2e–
• Cathode: Cu2+(aq) + 2e– —→ Cu(s)
The position of the ions in the electrochemical series
The reactivity series or activity series is an empirical series of metals, in
order of "reactivity" from highest to lowest.
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• The reactivity series is sometimes quoted in the reverse order of standard
electrode potentials:
Li > K > Sr > Ca > Na > Mg > Al > Zn > Cr > Fe > Cd > Co > Ni > Sn > Pb > H > Cu >
Ag > Hg > Pt > Au
• The positions of lithium and sodium are changed on such a series; gold and
platinum are also inverted, although this has little practical significance as
both metals are highly unreactive.
• Standard electrode potentials offer a quantitative measure of the power of a
reducing agent, rather than the qualitative considerations of other reactivity
series.
• However, they are only valid for standard conditions. In particular, they only
apply to reactions in aqueous solution.

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• Even with this provision, the electrode potentials of lithium and sodium, and
hence their positions in the electrochemical series, appear anomalous.
• The order of reactivity, as shown by the vigor of the reaction with water or
the speed at which the metal surface tarnishing in air, appears to be:
potassium > sodium > lithium > alkaline earth metals

+
Li –
+ F
K
+

The
Na
The ease of

2+ 2–
Mg SO 4

ease
3+
Al –
2+
Mn NO– 3

of
2+ Cl
Fe2+

Zn
e
g
r
a
h
sc
i
d

di s c h a
r ge
3+ 2–
Cr CO 3
increase

increase
2+
Cd
2+
Pb –
3+ Br
Fe
d o wn w a rd

+ d o wn ward –
H l
2+
Cu –
+ OH
Ag
3+
Au S2–
12/24/2024 18
• The ions that are lower in the electrochemical series get discharged in
preference to those above them.
• For example, if a solution has potassium ions and copper ions, the copper
ions will accept electrons, and get discharged as copper atoms first.
• The potassium ions will not be affected.
• In general, if two or more positive ions migrate to the cathode, the ion
lower in the series is discharged preferentially.
• Similarly, if two or more negative ions migrate to the anode, the ion
lower in the series is discharged preferentially.
Concentration of the ions in the electrolyte
• If an electrolyte contains a higher concentration of ions that are higher
in the electrochemical series than of those that are lower, then the
higher ions get discharged in preference to the lower ones.

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• For example, a solution of sodium chloride in water contains two types of
anions i.e., the chloride (Cl–) ions and the hydroxide (OH–) ions.
• The hydroxide ions are lower in the electrochemical series than the chloride
ions.
• But if the concentration of chloride ions is much higher than that of the
hydroxide ions, then the chloride ions get discharged first.

Quantitative Aspects of Electrolysis

• The quantitative treatment of electrolysis was developed primarily by
Michael Faraday in the year 1834.
• His early research on electrolysis led him to propose a relationship between
the amount of current passed through a solution and the amount of
substance decomposed or produced by the current.

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Faraday's First Law of Electrolysis
• Faraday's First Law states that “the amount of substance consumed or
produced at one of the electrodes in an electrolytic cell is directly
proportional to the amount of electricity that passes through the cell”.
• If m is the mass of a substance librated or deposited at an electrode due to
the passage of charge Q,
• then according to Faraday's first law of electrolysis,
m ∝ Q or m = zQ
Where z is a constant of proportionality and is called electrochemical
equivalent of the substance. It has the same charge which passes due to a
steady current I flowing for time t, then the above equation can be written as:
m=z×I×t
z×Q
the general formula of Faraday’s first law is given by : m = . where, m
is mass of the substance deposited or liberated, I is current in amperes, t is
time in seconds, F is Faradays constant, n is the number of moles of electrons
lost or gained, and M is the molar mass of the substance.
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• For example, in the electrolysis of molten NaCl, the cathode reaction tells us
that one Na atom is produced when one Na+ ion accepts an electron from the
cathode.
• To reduce 1 mole of Na+ ions, we must supply one mole of electrons (6.02 ×
1023 electrons) to the cathode.
Example 4.4
How many moles of chlorine, magnesium and aluminium are formed when 2, 2
and 3 moles of charge are passed through three different solution containing
chloride, magnesium and aluminium ions respectively?
Solution:

• The stoichiometry of the anode reaction shows that oxidation of two Cl – ions

yields one chlorine molecule and releases two electrons. Therefore, the formation

of 1 mole of chlorine results in 2 moles of electrons supplied by the Cl – ions to

the anode. Similarly, it takes 2 moles of electrons to reduce 1 mole of Mg 2+22ions

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 2Cl–(l) → Cl2(g) + 2e–

Mg2+ (aq) + 2e– → Mg(s)

3+ –
• Al (l) + 3e
In an electrolysis → Al(s)
experiment, we generally measure the current in amperes
(A) that pass through an electrolytic cell in a given period of time.
• By definition, 1 coulomb of charge is transferred when a 1 ampere current
flows for 1 second:
1C=1A×1s
• The charge on 1 mole of electrons is 96,500 C, which is obtained by
multiplying 1 mol (6.02 × 1023 electrons) with the charge of electron (1.602 ×
10–19 C).
• Charge of 1 mol of electrons = 6.02 × 1023 electrons × 1.602 ×10–19 C
96, 485 C ≈ 96,500 C = 1 F (one faraday) Therefore, 1F = 96,500 C.mol –1
12/24/2024 23
 Example in your text book Grade 12
1. Calculate the mass of calcium metal and chlorine gas that can be produced
when a current of 0.452 A is passed through molten CaCl2 for 1.5 h.
2. A current of 1.26 A is passed through an electrolytic cell containing an
aqueous solution of H2SO4 for 7.44 h. Write the half-cell reactions and
calculate the volume of the gases generated at STP (Note that at STP, P = 1
atm, and T = 0°C or 273 K).

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Faraday's Second Law of Electrolysis

Faraday's second law of electrolysis states that “when the same quantity of
charge (Q) is passed through different electrolytes, then the masses of different
substances deposited (m1, m2, m3,...) at the respective electrodes will be directly

proportional to their equivalent masses (E1, E2, E3,...).”

m∝E
or, m1 ∝ E1, m2 ∝ E2, and m3 ∝ E3 etc.
Replacing the proportionality by a proportionality constant k, the equations
become:
M1/E1 = M2/E2 = M3/E3 = ....
=k
The law can be illustrated by passing the same quantity of electric current
through three solutions containing H2SO4, CuSO4 and AgNO3, connected in
series, as shown in Figure
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 Voltage
source

e–

Anode Anode

Anode cathode cathode cathode

H2SO4(aq) CuSO4(aq) AgNO3(aq)

Figure 4.6 Solutions connected in series to a battery.

In the first solution, hydrogen and oxygen are liberated. In the second solution
copper is deposited and in the third, silver is deposited.

Mass of hydrogen M a s s of c op p e r M a s s of silv e r

E qu iv a le n t m a ss of H 2 =Equivalent mass of copper =Equivalent mass of silver

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 Example 4.7
Calculate the mass of copper deposited by the electrolysis of copper (II)
sulphate solution placed in series with a silver nitrate solution, when 0.108
g of silver is being deposited.
Solution:
The equivalent mass of silver and copper can be obtained from their
reduction half-reaction:

+ −
Ag (a q) + 1e → Ag(s), E = 108 g / m ol = 108 g / eq
Ag
1
2+ −
Cu (a q) + 2e = 63.5 g / m ol = 31.7 5 g / e q
→ Cu(s), E
Cu
2
The mass of Ag is 0.108 g, and you are asked to find the mass of copper.
m E × m
Ag m Cu
Cu Ag
= ⇒ m Cu =
E E E
Ag Cu Ag
31.75 g/eq × 0.108 g
= 0.032 g of Cu is deposited
108 g/eq

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Galvanic (Voltaic) Cells
• In a Galvanic cell, the reaction that occurs inside the cell is a
spontaneous redox reaction.
• The reaction that occurs inside the cell will proceed on its own
without any external influence.
• This reaction enables a galvanic cell to generate electricity.
Therefore, Galvanic cells are electrochemical cells in which
spontaneous redox reactions generate electricity.
• They convert chemical energy into electrical energy.
• Galvanic or voltaic cells are classified into primary cells,
secondary cells, and fuel cells.
12/24/2024 28
Primary Cells

• Primary galvanic cells are those cells that are not rechargeable. This is
because the electrode reaction as well as the entire cell reaction cannot be
reversed on recharging.
• Once the chemicals in the cells that serve as reactants are completely used
up, it is not possible to recover them by charging the cells.
• Examples of primary cells include Daniel’s cell and zinc-carbon
(Leclanche) dry cells.
• The common feature of all Galvanic cells is that they contain two
electrodes in contact with an electrolyte.
• The electrolyte in a Galvanic cell can be in the form of a solution or a paste.
• The cells containing electrolytes in the form of solution are called wet
cells, and those containing electrolytes in the form of paste are called dry
cells.
12/24/2024 29
• An example of a wet primary cell is the Daniel cell. It consists of a zinc strip
placed in ZnSO4 solution in one compartment and a copper strip placed in

copper sulphate, CuSO4, solution in another compartment.

• Each compartment is called a half-cell, and the reactions occurring in each
compartment are called half-cell reactions.
• The solutions in the two compartments are linked by a salt bridge as shown
in Figure.

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• The zinc atoms from the zinc electrode lose two electrons each and become
zinc ions, Zn2+.
• The ions enter into the solution, and the electrons remain on the electrode
and flow through the external wire to the copper electrode.
• This situation causes the zinc electrode to be negative and the solution to have
an overall positive charge.
• On the other hand, in the compartment containing the copper electrode,
copper ions, Cu2+, from the solution move to the cathode and gain two
electrons each, to become copper atoms and deposit on the surface of the
copper electrode.
• This condition causes the electrode to be positive and the solution to have a
negative charge.

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• Note that the anode is the negative electrode and the cathode is
the positive electrode in galvanic cells, as opposed to the
situation in an electrolytic cell.
• But, it is always oxidation that occurs at the anode and
reduction at the cathode.
The half-cell reactions and the cell reaction in Daniel cells are
represented as
Anode reaction: Zn (s) → Zn2+ (aq) + 2e–
Cathode reaction: Cu2+ (aq) + 2e- → Cu (s)
Cell reaction: Zn (s) + Cu2+ (aq) → Zn2+ (aq) + Cu (s)
• Due to the oxidation-reduction reaction in the cell, the Daniel
cell generates electricity.
12/24/2024 32
What is the purpose of the salt bridge?
a. To maintain electrical neutrality between the two solutions.
• In this process the anions (negative ions) from the salt bridge diffuse into the
solution containing the zinc electrodes,
• and the cations (positive ions) diffuse into the solution containing the copper
electrode to compensate for the excess positive and negative charges,
respectively;
b allow electrical contact between the two solutions;
c prevent mixing of the electrode solutions
• Although, wet cells like the Daniel cell can serve as a source of electricity, they
are not portable since they contain solutions.
• Due to this practical problem of using wet cells, dry cells were developed.

12/24/2024 33
• In a dry cell, a moist electrolyte paste is used instead of
solutions.
• This cell was invented by Georges Leclanche, a French chemist.
• A zinc-carbon dry cell, which is also called a Leclanche cell is
used in devices like portable radios and flashlights.
• The cell consists of a zinc cup that serves as the anode. The zinc
cup is filled with a paste of manganese (IV) oxide, zinc chloride,
ammonium chloride and powdered carbon.
• A graphite rod, immersed in this paste, serves as the cathode.

12/24/2024 34
 Figure 3.8 Zinc-carbon dry cell (Leclanche cell).

• A zinc-carbon dry cell produces electricity as a result of a

spontaneous redox reaction.
• Oxidation occurs at the zinc cup.
Oxidation: Zn (s) → Zn2+ (aq) + 2e–
• Reduction takes place at the graphite (carbon) electrode.
2MnO2 (s) + 2NH+4 (aq) + 2e–→ Mn2O3 (s) + 2NH3 (aq) + H2O (l)
12/24/2024 35
• A build up of ammonia gas around the cathode may disrupt the
current.
• However, this is prevented by the reaction between Zn2+ and NH3

to form a complex ion, [Zn(NH3)2]2+ which crystallizes as a

chloride salt.
Zn2+ (aq) + 2NH3 (g) + 2Cl– (aq) → Zn(NH3)2 Cl2 (s)

The overall reaction occurring in a Leclanche cell is:

Zn (s) + 2MnO2 (s) + 2NH4Cl (aq) → Zn(NH3)2Cl2 (s) + Mn2O3 (s)

+ H2O (l)
There are other examples of dry cells, such as the alkaline dry
cell, silver oxide cell, and copper oxide cell.
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Cell Notation
• A cell notation allows us to describe a Galvanic cell without
drawing a diagram. It is a shorthand representation of a Galvanic
cell.
• For example, a Daniel cell in which the electrolyte concentrations
are each 1 molar is represented as

+
Zn(s) |Zn2 (1 M) || Cu2+(1 M) |Cu(s)
• The anode is written on the left. The cathode on the right and
concentrations and other data are given in parentheses.
• The vertical line (|) indicates phase boundaries, and the double
vertical
12/24/2024
line (||) indicates a salt bridge or a porous partition 37
Standard Reduction Potentials
• The cell potential is the difference between two electrode potentials, one
associated with the cathode and the other associated with the anode.
• By convention, the potential associated with each electrode is chosen to be the
potential for reduction to occur at the electrode.
• Thus, standard electrode potentials (electrode potentials at a concentration of
1 M) are tabulated for reduction reactions and are denoted as Eo red.

• The cell potential (Eocell) is Eored (cathode) minus the standard reduction

potential of the anode reaction, Eo red (anode):

Eo cell= Eo red (cathode) – Eo red (anode)

• Because every Galvanic cell involves two half-cells, it is not possible to directly
measure the standard reduction potential of a half-reaction.

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• However, if we assign a standard reduction potential to a certain reference
half-reaction, we can then determine the standard reduction potentials of
the other half-reactions, relative to that reference.
• The reference half-reaction is the reduction of H+(aq) to H2(g) under
standard conditions, which is given a standard reduction potential of exactly
0.0 V.
2H+ (aq, 1M) + 2e– → H2(g, 1 atm); Eored = 0.0 V
• An electrode designed to produce this half-reaction is called a standard
hydrogen electrode (SHE).
• SHE consists of platinum wire connected to a piece of platinum foil covered
with finely-divided platinum that serves as an inert surface for the reaction.
• The electrode is encased in a glass tube, so that hydrogen gas can bubble
over the platinum, and the solution contains H+(aq) under standard (1 M)
12/24/2024 39
conditions.
 Voltmeter

e–

Zn
Salt bridge
H2 gas at 1 atm

Cotton plugs Pt electrode

1 M HCl
1 M ZnSO4

Figure: Standard Hydrogen Electrode

The spontaneous reaction in Figure , is the oxidation of zinc and the reduction of
H+ : Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g)
In the Figure , above;
i) The Zn2+ | Zn electrode is the anode, and the SHE is the cathode.
ii) The cell voltage is 0.76 V.
By using the defined standard reduction potential of H+ , we can determine the
standard
12/24/2024 reduction potential for Zn2+ | Zn half-reaction: 40
 Eocell = Eored (cathode) – Eored (anode)

0.76 V = 0.0 V – Eored (anode)

Eored (anode) = –0.76 V

• Therefore, a standard reduction potential of –0.76 V can be assigned to the
reduction of Zn2+ to Zn:
Zn2+ (aq, 1M) + 2e– → Zn(s); Eored = –0.76 V
• Note that we write the reaction as a reduction, even though it occurs in reverse as
oxidation.
• Whenever we assign a potential to a half-reaction, we write the reaction as a
reduction.
• The standard reduction potentials for other half-reactions are established in the way that
we did for the Zn2+ | Zn half-reaction.

12/24/2024 41
• The Eored values apply to the half-cell reactions as read in the forward (left to
right) direction.
• The more positive Eored is the greater tendency for the substance to be
reduced. For example,
F2(g, 1 atm) + 2e– → 2F–(1M), Eored = +2.87 V

• the reaction has the highest Eo value for all of the half-cell reactions. Thus,

F2 is the strongest oxidizing agent because it has the greatest tendency to be

reduced.
• At the other extreme is the reaction, which has the most negative Eored value.
Thus, Li+ is the weakest oxidizing agent, because it is the most difficult
species to be reduced.
• Alternatively, Li metal is the strongest reducing agent since it gets oxidized
12/24/2024 42
• Changing the stoichiometric coefficients of a half-cell reaction does not affect
the value of Eored, because electrode potentials are intensive properties.

• This means that the value of Eored is unaffected by the size of the electrodes or
the amount of solutions present but is dependent on the concentration of the
solutions and the pressure of a gas (if any).
For example,
I2(s) + 2e– → 2I– (1M); Eored = +0.53 V
but Eo does not change if we multiply the half-reaction by 2:
2I2(s) + 4e– → 4I– (1M); Eored = +0.53 V
• The sign of Eored changes, but its magnitude remains the same when we
reverse a reaction.
• The more positive the reduction potential, the greater the tendency to accept
electrons.
• As a result, when two half-cells are coupled, the reaction with higher (more
positive) reduction potential proceeds as reduction, while the other proceeds
12/24/2024 43
as oxidation
 Example 4.9
A Galvanic cell consists of a Mg electrode in 1.0 M Mg(NO 3)2 solution and
a Ag electrode in 1.0 M AgNO 3 solution. Calculate the standard cell
potential (emf) of this cell at 25°C.
Solution:
+
Using Table 4.2, it can be noticed that Ag will oxidize Mg:
2+ – o
Anode (oxidation) : Mg(s) → Mg (1 M) + 2e ; E red = +2.37 V
+ – o
Cathode (reduction) : 2Ag (1 M) + 2e → 2Ag(s); E red = +0.80 V
+ 2+
Overall reaction : Mg(s) + 2Ag (1 M) → Mg (1 M) + 2Ag(s)
o
E cell = 2.37 V + 0.80 V = +3.17 V
Note that, in order to balance the overall reaction, we multiplied the cathode
o
reaction by 2. We can do so because, E red is an intensive property, which
o
means it is not affected by this procedure. We can also find the E cell by
using the principle stated in number 6 above.
+ – + o
Ag (1.0 M) + e → Ag (s), E red = +0.80 V (Cathode: higher reduction potential)
2+ – o
Mg (1.0 M) + 2e → Mg(s), E red = – 2.37 V (Anode: lower reduction potential)
o o o
E red = E red (cathode) – E red (anode)
o + o 2+
E red (Ag /Ag) – E red (Mg /Mg)
0.80 V – (–2.37 V) = +3.17 V
o
The positive value of E cell shows that the forward reaction is favoured.
12/24/2024 44
Secondary Cells
• Unlike primary cells, secondary cells are rechargeable. The electrode
reactions can be reversed, and the original reactants can be regenerated.
• This can be achieved by passing a direct current through the cell. The process
is called charging or recharging.
• A secondary cell needs to be recharged when it stops producing electricity. A
lead storage battery, is an example of a secondary cell.
• A lead Storage Battery is the common automobile battery that usually
delivers either 6 or 12 volts, depending on the number of cells used in its
construction.
• The inside of the battery consists of galvanic cells connected in series.
• A fully-charged lead-acid cell is made up of a stack of alternating lead and
lead (IV) oxide plates isolated from each other by porous separators.

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• The individual cells contain a number of lead anodes connected
together, plus a number of cathodes composed of PbO2, also
joined together.
• These electrodes are immersed in 35% sulphuric acid, which
serves as an electrolyte.
• A single lead-storage cell delivers 2 volts. Therefore, a 12 V
battery contains six cells connected in series.

Figure : Lead - Storage Battery.

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• When a lead-storage battery is in operation (on discharge), the following
reactions occur at the electrodes:
Anode reactions: Pb (s) + SO24– (aq) → PbSO4 (s) + 2e–

Cathode reactions: PbO(s) + 4H+(aq) + SO42– (aq) + 2e–→ PbSO4 (s) + 2H2O (l)
And the over all reaction is
Pb (s) + PbO2 (s) + 4H+ (aq) + 2SO24– (aq) → 2PbSO4 (s) + 2H2O (l)

• From the electrode reactions it can be noticed that PbSO4 is produced at both
electrodes. Unlike primary cells a lead-storage battery is rechargeable when
the battery runs down.
• The electrode reactions can be reversed by placing a potential across the
electrodes that is slightly larger than that which the battery can deliver.
• The reaction that takes place on recharging a lead storage battery is given by
the following equation. 2PbSO4 (s) + 2H2O (l) →Pb (s) + PbO2 (s) + 2H2SO4
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(aq)
Industrial Applications of Electrolysis
• Each day, our lives are touched directly or indirectly by the products of
electrolysis.
• Electrolysis has important industrial applications. It is used for:
a) The production of chemicals like sodium hydroxide, from electrolysis of
brine (concentrated NaCl solution), using inert electrodes.
• The reactions that take place at the electrodes (when graphite electrodes are
used) are as follows:

Anode reaction: 2Cl– (aq) →Cl2 (g) + 2e–

Cathode reaction: 2H2O (l) + 2e– → H2 (g) + 2OH–(aq)

The overall cell reaction is:

2NaCl (aq) + 2H2O (l) → 2Na+ (aq) + 2OH–(aq) + Cl2 (g) + H2 (g)
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b) For the production of metals and non-metals.
• The non-metals like H2, Cl2, F 2 etc are manufactured on an industrial scale
by the process called electrolysis.
• The metal aluminium is extracted industrially by the Hall Process. This
process involves the electrolysis of molten alumina (Al2O3) mixed with some

amount of cryolite, Na3AlF6.

• The role of cryolite is to reduce the melting point of alumina from 2000°C to
1000°C. The vessel holding the molten mixture (Figure) is made up of iron
lined with carbon, which serves as the cathode. Carbon (graphite) rods that
serve as the anode are inserted into the melt. When the molten mixture is
electrolyzed, pure aluminium is produced. The reactions at the electrodes
are:
Anode reaction: 6O2– ( l ) → 3O2 (g) + 12e–
Cathode reaction: 4Al3+ ( l ) + 12e– → 4Al(l)
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3+ 2–
 Figure Production of Aluminum by Hall Process

c) For the Purification of Metals

• Another important application of electrolysis is the purification of metals like
copper.
• When first separated from its ore, copper metal is about 99% pure with
nickel, silver, gold and platinum as major impurities.
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• In the refining process, the impure copper is used as the anode, copper metal
of high purity used as cathode, and copper sulphate, CuSO4 solution and

aqueous H2SO4 as the electrolyte.

• When electrolysis is carried out, copper and impurities that are more easily
oxidized than copper, such as nickel, will go into the solution.
• Copper passes through the solution and deposits on the cathode, while the
impurities remain in solution.
• Impurities like silver and gold are less easily oxidized and do not dissolve but
fall away from the anode as ‘sludge’.
• The electrode reaction in the purification of copper is the following:
Anode reaction: Cu (s) → Cu2+ (aq) + 2e−
Cathode reaction: Cu2+ (aq) + 2e− → Cu (s)
• During the process, the size of the impure copper anode decreases and that of
the pure copper cathode increases.
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Figure Purification of Copper by Electrolysis
• Always remember that, in the purification of metals by electrolysis, the
impure metal should be used as the anode, the pure form of the metal as the
cathode and an electrolyte should contain soluble salt (ions) of the metal to
be purified.
• The process of purifying metals by electrolysis is called electrorefining.
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d) Electroplating
• Electroplating is a process of covering the surface of a metal (metal article)
with a thin layer of another metal.
• Using this process, metals that easily corrode can be protected by a thin
coating of another metal that resists corrosion.
• For example, tin cans are steel cans with a thin coating of tin, and chrome-
plated bumpers are used for automobiles.
• Thus, the main objective of electroplating is to protect an article from
corrosion and to give articles a beautiful appearance.
• In the process of electroplating, the pure plating metal should be used as the
anode, the article (metal) to be plated the as cathode and a solution
containing ions of the plating metal as the electrolyte.

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• For example, to produce a silver-plated copper article, say, a medal, one
should use silver as the anode, the copper medal as the cathode and silver
nitrate solution as the electrolyte

D.C. source

Copper medal
Silver (Anode ) (cathode)

AgNO3 (solution )

Figure Electroplating Copper medal with Silver.

The reactions that occur at the electrodes during electroplating are:

Anode reaction: Ag (s) → Ag+ (aq) + 1e−
Cathode reaction: Ag+ (aq) + 1e– → Ag (s)
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