2/28/2023

Water can undergo electrolysis to form hydrogen gas and

oxygen gas according to the following reaction:

2H2O(l) →H2(g)+O2(g)

This reaction is very important because hydrogen gas has the

potential to be used as an energy source. The electrolytic cell for
this reaction consists of two electrodes, submerged in an
electrolyte and connected to a source of electric current (Figure
13.7).
The oxidation half-reactionoxidation half-reaction is as follows:
The reduction half-reactionreduction half-reaction is as
follows:
figure 13.7: Hofmann apparatus for the electrolysis of water.
2H2O(l)→O2(g) + 4H+(aq) + 4e− 2H+(aq) + 2e−→H2(g)

1
2/28/2023

2
 2/28/2023

+ -

e– e–
e– e–
Anode Cathode

Cl- H+
H+
Cl-
Na+
OH- 2Cl-
Na+ NaOH OH- Na+

3
 2/28/2023

4.4. Industrial Application of Electrolysis

• The purpose of electrolysis is to split up ionic compounds using electricity to

produce useful products.
• Electrolysis is used a lot in industry and is a multi-billion pound industry. It is used
to produce all of the Copper, Aluminium, Chlorine and Caustic Soda (sodium
hydroxide) that we use today as well as to produce gold and silver plated jewellery
and chrome-plated taps and bicycle parts.

4
 2/28/2023

4.4. Industrial Application of Electrolysis

Learning objective
 Mention the industrial application of electrochemistry
 Explain electroplating and Electrorefining
 Explain how electrolysis is used in the production of some metals, nonmetals and compounds

Focused Questions
1. What are the purposes of electroplating and electrorefining?

2. Where do we put the plating metal and the metal to be plated, during electroplating?

3. What is chrome plating? How is it done?

4. Describe the electrorefining of copper. Include the appropriate chemical equations.

4.4.1 Electroplating and Electrorefining of Metals

What is electroplating?
1. Electroplating is a process of covering the surface of a metal with a thin layer of
another metal.

2. Deposition of a thin layer of metal on a surface by an electrical process involving

oxidation-reduction. Electroplating is often also called "electrodeposition“.

3. Electroplating produces a very thin coating of these expensive metals on the

surfaces of cheaper metals.

The main purpose of electroplating is

 to protect a metal from corrosion
 to give a beautiful appearance.

Electroplating can enhance:

 Chemical properties---increase corrosion resistance
 Physical properties---increase thickness of part
 Mechanical properties---increase tensile strength & hardness

5
 2/28/2023

How it works?

The condition required during electroplating process are:-

1) The metal to be plated must be cathode.
2) The anode should be made up of metal we want to plate on the object.
3) Cation of the metal we want to plate on the object must present in the solution.

For example, to produce a silver-plated copper article, say, a Medals,

e– e– What happen to those ions during electroplating process??

e–
Oxidation e–
Battery Reduction Anode reaction: Oxidation
Anode Cathode Ag (s) → Ag+(aq) + 1e-

Cathode reaction: Reduction

Cu Ag+(aq) + 1e- → Ag (s)
Ag NO3- metal
metal NO3- Ag+
NO3- Ag+
Ag+ 2. Electroplating with Chrome, Chrome plating
Ag+ NO3- Ag+ NO3- Ag+ NO3-  A thin layer of chromium is deposited on another metal.

 The electrolyte is prepared from CrO3 in dilute H2SO4

Figure 4.1 Electroplating Copper with Silver
Silver nitrate solution  The over all reduction reaction occurred at the cathode is
as the electrolyte

CrO3 (aq) + 6H+(aq) + 6e- → Cr (s) + 3H2O (l)

What is electrorefining?
Electrorefining is defined as the process of refining or purification of impure metals by electrolysis.
It is another important application of elctrochemistry.

In an electrorefining process, the anode is the impure metal and the impurities must be lost during the
passage of the metal from the anode to the cathode during electrolysis.

The electrode reactions are,

Anode reaction: Cathode reaction:
M → Mn+ + ne- Mn+ + ne- → M

For example, purification of impure copper is one common application of electrorefining method

Electrorefining of Copper The electrode reaction in the purification

of copper is

Oxidation Reduction Anode reaction:

Cu (s) → Cu2+(aq) + 2e-

Cathode reaction:
Cu2+(aq) + 2e- → Cu (s)
Cu2+ SO4-2

Cu2+
During the process, the size of the impure
SO4-2 Cu2+
Cu2+
Cu2+
copper anode decreases and that of the
Impurities SO4-2 pure copper cathode increases.

6
 2/28/2023

4.4.2 Extraction of Metals by Electrolysis

 Alkali metals, alkaline earth metals and Aluminum are extracted from their compound by
electrolysis.
 The method of extraction depends on the reactivity of the metal being extracted.
 This can be discovered using the reactivity series.
increasing reactivity

Extracted using
electrolysis
Therefore, electrolytic reduction rather than chemical
reduction is often used to obtain active metals from their
compounds.

Extracted by
reduction with
carbon

How Aluminium is extracted from its ore?

 Aluminium is a reactive metal that is found in the ore

bauxite combined with oxygen as aluminium oxide.
 Electrolysis breaks down the Al2O3 into Aluminium and
Oxygen.
Bauxite, Aluminium ore
Aluminium oxide  Aluminium + oxygen
2 Al2O3 (l)  4 Al (l) + 3 O2 (g)

Why is it not possible to extract aluminium by heating its ore with carbon?

Aluminium ore (bauxite) has a very high melting point (2050 ºC).
For electrolysis, the ore is dissolved in a compound called cryolite (Na3AlF6), which lowers the
melting point to 700 ºC.

What redox processes occur at the electrodes during the electrolysis of aluminium oxide (Al2O3)?

At the negative electrode: At the positive electrode:

Al3+ + 3e-  Al (reduction) 2O2-  O2 + 4e- (oxidation)

7
 2/28/2023

4.4.3. Manufacture of Nonmetals and some Compounds

 Non-metals such as Fluorine (F2), Chlorine (Cl2), hydrogen (H2), and oxygen (O2) are
prepared by electrolysis.
 Electrolysis is also used in the preparation of compounds such as sodium hydroxide (NaOH).

1. Fluorine (F2)
Fluorine is prepared by the electrolysis of a molten mixture of KF and HF.

Anode: oxidation
2F- (aq)  F2 (g) + 2e- Overall cell reaction:
Cathode: reduction 2F- (aq) + H+ (aq)  F2 (g) + H- (aq)
H+ (aq) + 2e-  H- (aq)

2. Hydrogen (H2), and oxygen (O2)

H2 and O2 are also prepared by the electrolysis of dilute sodium chloride. And also from electrolysis of
water

At the Anode:
 anions OH- and Cl- move toward the anode
 The position of OH- ions in the electrochemical series is higher
than that of Cl- ion.
 Hydroxide ions are preferentially discharged (oxidized) to form
oxygen gas.
4OH- (aq)  2H2O (l)+ O2 (g) + 4e-

At the Cathode:
Figure:- electrolysis of dilute sodium chloride  cations Na+ and H+ moves toward the anode
 The position of H+ ions in the electrochemical series is lower
than that of Na+ ions.
 Hydroxide ions are preferentially discharged (reduced) form
hydrogen gas.
2H+ (aq) + 2e-  2H2(g)

Overall reaction
4OH- (aq) +4H+ (aq)  2H2O (l)+ O2 (g) + 4H2(g)

8
 2/28/2023

2. Chlorine (Cl2)
Chlorine is manufactured by the electrolysis of a molten sodium chloride or concentrated sodium chloride
(brine) solution.

Method 1: Electrolysis of molten sodium chloride (NaCl)

At the negative electrode:

Na+ + 1e-  Na (reduction) Overall reaction:
Sodium Chloride Sodium + Chlorine
At the positive electrode: 2NaCl2 (l)  Na (l) + Cl2 (g)
2Cl-  Cl2 + 2e- (oxidation)

Electrolysis of molten sodium chloride

Method 2: Electrolysis of concentrated Nacl (brine) solution

e– e– Overall Reaction is:
e– e– 2NaCl (aq) + 2H2O (l)  2NaOH (aq) + + Cl2 (g) + H2 (g)
Anode or
Cathode
2Cl– (aq)  Cl2 (g) + 2e– 2Cl– (aq) + 2H+ (aq)  Cl2 (g) + H2 (g)
2H+ (aq) + 2e–  H2 (g)

Cl- H+ Chlorine ions are preferentially discharge than that

Cl-
H+ of hydroxide ions because of higher concentration
Na+
OH-
of chlorine ions.
Na+ NaOH OH- Na+

NaOH forms and Electrolysis of conc. sodium chloride solution

sinks to the bottom

4.5 VOLTAIC (GALVANIC) CELLS

Expected Learning Outcomes

 Draw and label a Zn-Cu galvanic cell, using ZnSO4 and CuSO4 solutions
 Identify the cathode, anode and electrolyte of a given Galvanic cell
 Calculate the electrode potentials and cell potentials using Nernst equation
 Compare and contrast electrolytic and Galvanic cells

What is Galvanic Cells?

 A galvanic (voltaic) cell is a device in which chemical energy is
converted into electrical energy.
 A galvanic cell uses a spontaneous redox reaction to generate electricity.

Zn(s) + CuSO4 (aq)  ZnSO4(aq) + Cu(s)

 This means the reaction will proceed on its own without any external energy or
influence.
 In galvanic cell, the redox reaction involves the transfer of electrons from reducing
agent to oxidizing agents.

9
 2/28/2023

4.5.1 Construction of Zn-Cu Galvanic Cell

Focused Questions

1. What are the anode and the cathode in a Zn-Cu Galvanic cell?
2. Write the half-reactions at each half-cells of a Zn-Cu Galvanic cell .
3. How does the salt bridge maintain the electroneutrality of a solution?
4. What makes a Galvanic cell different from an electrolytic cell?

Two types of electrochemical cell

Galvanic cell: produces electricity as a result of spontaneous
reactions occurring inside it
Electrolytic cell: where a non-spontaneous reaction is driven
by an external source of current

Such a cell was invented by the British Chemist John Daniell in 1836.

10
 2/28/2023

4.5.1 Construction of Zn-Cu Galvanic Cell

 Basic set-up of Galvanic cells:

1. Two electrodes (anode and cathode)
 Anode
 The electrode at which oxidation occur
 The negative electrode –electro donor Anode - + Cathode
 Cathode
 The electrode at which reduction occur
 The positive electrode- electron gain
2. Salt bridge-
Figure 4.7 Daniell cell
 an inverted U-tube filled with an electrolyte and it
does not interfere with the operation of the cell.
 Such as KCl, KNO3 solutions Electrolytes
 Its main role is to maintain the electroneutrality of a solution

3. Electrolytes
 are substances that conduct electricity, either in an
aqueous solution or in a molten state

4. Voltmeter (wire)- external connection between electrodes

 Connect the Negative terminal to anode
 Connect the positive terminal to cathode

Justification of Zn-Cu Galvanic cell

Battery

–V+ Cathode
Anode e– e–
Salt bridge
KCl
Zn electrode Cu electrode

Zn2+ Zn
Left hand Right hand
Cl– K+ compartment
compartment
Cu Cu2+

ZnSO4 (aq) CuSO4 (aq)

Left hand compartment Right hand compartment

 It is a negative terminal  It is positive terminal of the cell
 donate electrons  receives electrons
 Oxidation half-reaction occur  Reduction half-reaction occur

Oxidation: Zn(s)  Zn2+(aq) + 2e– Reduction:Cu2+(aq) + 2e–  Cu(s)

The net cell reaction: Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s)

11
 2/28/2023

What makes a Galvanic cell different from an electrolytic cell?

Galvanic cell Electrolytic cell

Energy Chemical potential energy is converted to An external supply of electrical energy causes a
changes electrical energy chemical reaction to occur.
Chemical
Spontaneous reactions Non-spontaneous reactions
reactions
is negative terminal , is positive terminal ,
Anode
oxidation occurs at anode oxidation occurs at anode
is positive terminal, is negative terminal,
Cathode
reduction occurs at cathode reduction occurs at cathode

Electrons flow from negative electrode to Electrons flow from positive electrode to
Direction of
positive electrode negative electrode
electricity
(- ive to + ive) (+ ive to - ive )

two half-cells, one electrode in each,

Cell set-up one cell, both electrodes in cell, no salt-bridge
connected by a salt-bridge

Electrolyte are kept separate from one another, and are The cathode and anode are in the same
solution(s) connected by a salt bridge electrolyte

Cell Potential Ecell > 0 and DG < 0 Ecell < 0 and DG > 0

Electrolysis e.g. of water, NaCl,

Applications Batteries
Electroplating, Electrorefining

4.5.2 Cell Notation

How do you represent Galvanic cells without drawing a diagram?

Figure 4.7 Daniell cell

It is a shorthand representation of a Galvanic cell.

A cell notation allows us to describe a Galvanic cell without drawing a diagram.

12
 2/28/2023

4.5.2 Cell Notation

While writing a cell, the anode is written on the left and the cathode on the right.

anode | anode electrolyte (M) || cathode electrolyte (M) | cathode

Phase boundaries Salt bridge Phase boundaries

For example, Daniell cell

Figure 4.7 Daniell cell

Exercise 4.8
Q1. Write the cell notation for a Galvanic cell consisting of an Al electrode placed in 1 M
Al(NO3)3 solution and a Ag electrode placed in a 1 M AgNO3 solution.

Answer

Al(s) | Al(NO3)3(1M) || AgNO3(1M) | Ag(s)

Q2. Write the anode and cathode half-cell reaction of the following of galvanic cells

Mg(s)| Mg+2(aq) || Al+3(aq) |Al(s)

Answer
Anode: Mg(s)  Mg+2 (aq) + 2e-

Cathode: Al+3 (aq) + 3e-  Al(s)

13
 2/28/2023

4.5.3 Standard Reduction Potentials

What is the difference between standard reduction potential and cell potential?

 The cell potential is the potential difference between two electrode

potentials.

 The cell potential (Ecell) is equal to the electrode potential of the

cathode electrode minus the electrode potential of the anode Anode Cathode
electrode.

Where, Ecathode is the reduction potential of the cathode electrode

Eanode is reduction potential of the anode electrode.

 Standard cell potential (Eºcell)

 the cell potential measured under standard conditions
 pressure = 101,3 kPa(1atm)
 temperature = 298 K (25 ℃)
 concentration = 1M

14
 2/28/2023

How is Eºred of a half-reaction determined experimentally?

• Eºred is the electrode potential measured under standard condition relative to the Standard
hydrogen electrode.

• it is impossible to determine the reduction potential of a single electrode (Eºred) because it

involves two half-cells.
Consider:
Zn2+ Zn Zn2+ + 2e- EºZn/Zn2+ = ?
SO42-
Zn
electrode Zn2+ can not determined because the reaction must be coupled.
SO42-

Anode

• The electrode chosen as a reference is called the standard hydrogen electrode (SHE).
•
• The reduction half-reaction chosen as the reference is
2H+ (aq) + 2e- H2 (g), Eº= 0.00 V

All other half-cells are measured in comparison to this reaction.

How is EºZn2+/zn and EºCu2+/Cu determined?

To determine Eº for a another half reaction, SHE is used as reference electrode.

Now consider the reaction:-

0.76 V

Eºcell = Eºred (cathode) - Eºred (anode)

Eºcell = 0.76 V = 0.0V - Eºred (anode)
Eºred (anode) = -0.76 V
Therefore, Eºred (Zn2+/Zn) = -0.76 V, reduction reaction

Zn(s) | Zn2+ (1.0 M) || Cu2+(1.0M) | Cu(s)

1.10 V
Eºcell = 1.10 V
Eºcell = Eºred (cathode) - Eºred (anode)
recall, EºZn2+/Zn = -0.76 V
Therefore, Eºcell = EºCu2+/cu - Eº Zn2+/Zn
1.10 V = EºCu2+/cu – (-0.76 V)
EºCu2+/cu = +0.34 V

15
 2/28/2023

The more positive Eºred is the greater

Eºred tendency for the substance to be reduced .

the highest positive Eº value

F2 is the strongest oxidizing agent because it

has the greatest tendency to be reduced.

Under standard state conditions, any species

Increasing Strength as Oxidizing agents

on the left of a given cell reaction reacts
spontaneously with a species that appears on
Increasing Strength as reducing agents

the right of any half-cell reaction

Li+ is the weakest oxidizing agent, because it is the

most difficult species to be reduced

Has the most negative Eº value

Table 4.2 Standard Reduction Potential in Aqueous Solution at 25°C.

The standard electrode potentials of a number of electrodes

arranged in the decreasing order is called the electrochemical
series.
Increasing Strength as Oxidizing agents

The magnitude of Eº is a measure of the tendency of the

Increasing Strength as reducing agents

half-cell reaction to occur in the forward direction.

Under standard state conditions, any species on the left of a

given cell reaction reacts spontaneously with a species that
appears on the right of any half-cell reaction

16
 2/28/2023

Table 4.2 Standard Reduction Potential in Aqueous Solution at 25°C.

Eºred

More positive Eº

 More positive Eº
 More easily electron is gained

Increasing Strength as Oxidizing agents

 More easily reduced
 Better oxidizing agents
Example:-

 F2 is the strongest oxidizing agent

Increasing Strength as reducing agents

 it has the greatest tendency to be reduced.

 More negative Eº
 More easily electron is lose
 More easily oxidized
 Better reducing agents
Example:-

 Li+ is the strongest reducing agent,

 it is the most difficult species to be reduced.

More negative Eº

Table 4.2 Standard Reduction Potential in Aqueous Solution at 25°C.

 More positive Eº
 More easily electron is gained
Increasing Strength as Oxidizing agents

 More easily reduced

 Better oxidizing agents
 More negative Eº
 More easily electron is lose
 More easily oxidized
 Better reducing agents
Increasing Strength as reducing agents

The standard electrode potentials of a number of electrodes

arranged in the decreasing order is called the electrochemical
series.
The magnitude of Eº is a measure of the tendency of the half-
cell reaction to occur in the forward direction (direction of
reduction).

17
 2/28/2023

Justification

1. Under standard state conditions, any species on the left of a given cell reaction reacts spontaneously
with a species that appears on the right of any half-cell reaction

2. 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
as oxidation.

Changing the stoichiometric coefficients of a half-cell reaction does

not affect the value of Eºred, because electrode potentials are intensive
properties.

Li+ is the weakest oxidizing agent, because it is the

most difficult species to be reduced

Has the most negative Eº value

18
 2/28/2023

We use batteries throughout our day-to-day lives. Cell phones use lithium-ion batteries, cars use lead-acid batteries
(Figure 13.1 (left)), while silver-oxide batteries (Figure 13.1 (top right)) are used in watches. Some batteries are
rechargeable (Figure 13.1 (bottom right)), while others cannot be recharged and have to be thrown away.

a) A car battery, b) rechargeable AA batteries and c) watch batteries.

A battery consists of multiple electrochemical cells. And within each cell there are electrochemical reactions taking
place. This can be seen in the lemon battery experiment shown in Figure 13.2. Each lemon is a cell in the battery, which
consists of three lemon cells. The reactions the copper and zinc undergo in the lemons are electrochemical reactions,
and a current is produced.

Figure 13.2: A current is produced by connecting lemons with zinc and copper metal. The reactions taking place here are elect rochemical reactions.

Electrochemical reactions, and electrochemical cells are covered in this chapter. Before going into any more detail
however, it is important to revise oxidation and reduction, as well as redox reactions and how to balance them, as these
concepts are very important in electrochemistry.

19
2/28/2023

20
2/28/2023

21
2/28/2023

22
2/28/2023

23