Chemistry Grade 12

Unit 4:Electrochemistry

Section 1

Kalayou Hiluf (PhD)

MU
Discussion Outline
 Revision from Previous section

What is electrochemistry?
 is a field of chemistry that deals the relationship b/n electricity and chemistry.
Electrochemistry = Electricity + Chemistry

 A device that convert chemical energy to electrical energy or electrical energy to

chemical energy s called as Electrochemical
s.
cells

Two Type of Electrochemical cells: electrolytic and galvanic cells

1. Electrolytic cells:-
 Convert electrical energy to chemical energy.
 a non-spontaneous reaction

2. Galvanic cells:-
 Convert chemical energy to electrical energy.
 spontaneous reactions
 Cont… Revision

Electrolyte
 is a substance which conducts an electric current in molten state or aqueous solution.
Anode
 is the electrode where oxidation occurs.
 It is connected to the positive terminal of the battery.
e
Cathode
 is the electrode where reduction occur.
 It is connected to the negative terminal of the battery. e e

Anion
 is a negative ion and is attracted to the anode.

Cation
 is a positive ion and is attracted to the cathode.
 Cont… Revision

What are reduction and oxidation (Redox) reactions?

e
 Oxidation is loss of electrons

e e
 Reduction is gain of electron

What is Redox reaction?

 involves both loss and gain of electron

An Ox Red Cat
Oxidation occur at the Anode Reduction occur at the Cathode
 4.4. Industrial Application of Electrolysis

Learning objective

 List down the industrial application of electrochemistry

 Define and explain electroplating and Electrorefining

 Explain how electrolysis is used in the production of some metals, nonmetals
and compounds
 What is electrolysis?

 is a process in which electrical energy is used to produce chemical changes.

 The electrical energy causes the ionic compound to split up and form new substances.

Electrolysis, mean “ to break apart” (lysis) using electricity”

 The purpose of electrolysis is to produce useful products using electricity.

The main applications of electrolysis are:

 Electroplating

 Refining of Metals

 Extraction of Metals

 Production of Chemicals such as Cl2

 4.4.1 Electroplating of metals

What is electroplating?

 Electroplating is a process of covering the surface of a metal with a thin layer of

another metal by electrolysis.

 Electroplating is used for protection against corrosion and for decoration.

 Electroplating is often also called "electrodeposition“.

There are different type of electroplating, including

1) Silver and gold plating,
2) Chromium plating ,
3) Nickel plating, and
4) Tin plating

For example, how to produce a silver-plated copper article

 Silver-plated copper article, say, a Silver-medal

Gold Silver Bronze

Winner athletics Medals

 What happen to those ions during electroplating process??
In electroplating,
 The object to be plated is the cathode.
 The metal used for electroplating is made the anode.
 The electrolyte is a solution of ions of the metal used for plating

e e

Battery
Anode e Cathode
e
e
Ag Copper
Silver Ag+
electrode
electrode NO3 -
NO3-
Ag+ Ag+
NO3-

Ag+
Ag+ NO3- Ag+ NO3- Ag+ NO3- Reduction
Oxidation
Figure 4.1 Electroplating Copper with Silver
Cathode reaction:
Anode reaction: Ag+(aq) + 1e- → Ag (s)
Ag (s) → Ag+(aq) + 1e-
Silver nitrate solution
as the electrolyte
 What happen to those ions during electroplating process??
In electroplating,
 The object to be plated is the cathode.
 The metal used for electroplating is made the anode.
 The electrolyte is a solution of ions of the metal used for plating

e e

Battery
Anode e Cathode
e
e
Ag Copper
Silver
electrode
electrode NO3 -
NO3-
Ag+ Ag+
NO3-

Ag+

Ag+ NO3- Ag+ NO3- Ag+ NO3- Reduction

Oxidation
Figure 4.1 Electroplating Copper with Silver
Cathode reaction:
Anode reaction: Ag+(aq) + 1e- → Ag (s)
Ag (s) → Ag+(aq) + 1e-
Silver nitrate solution
as the electrolyte
 2. Electroplating with Chrome, Chrome plating

 A thin layer of chromium is deposited on another metal.

 The electrolyte is prepared from CrO3 in dilute H2SO4

 The over all reduction reaction occurred at the cathode is

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

Chrome-plated material
 What is electrorefining?

Electrorefining is defined as the process of refining or purification of impure metals by electrolysis.

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

The electrode reaction in the purification of

Oxidation Reduction copper is

Anode reaction:
Cu (s) → Cu2+(aq) + 2e-
Cu2+ SO4-2
Cathode reaction:
Cu2+
Cu2+(aq) + 2e- → Cu (s)
SO4-2 Cu2+
Cu2+
Cu2+ During the process, the size of the impure
Impurities SO4-2
copper anode decreases and that of the pure
Figure: Electrorefining of Copper copper cathode increases.
 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
 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

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

Overall reaction
4OH- (aq) +4H+ (aq)  2H2O (l)+ O2 (g) + 4H2(g)
 3. Chlorine (Cl2)

Chlorine is manufactured by electrolysis methods.

1. Molten sodium chloride (NaCl)
2. Concentrated sodium chloride (brine) solution.
 Method 1: Electrolysis of molten sodium chloride (NaCl).
e

Cations migrate
Na+ Anions migrate
toward -ive electrode
(-) Cl- (+) toward +ive electrode
e
e
Cathode Anode
Cl-
Na+ Cl- Na+
Reduction reaction Oxidation reaction
Na+ + e-  Na 2Cl-  Cl2 + 2e-
Molten NaCl

Overall Cell Reaction

2Na+ + 2Cl-  2Na (l) + Cl2 (g)
 Method 2: Electrolysis of concentrated Nacl (brine) solution

e e

e
Anode e Cathode
 OH- and Cl- Cl- H+  Na+ and H+
Cl- H+
Cl- ions are discharge H+ ions are discharge
OH- Na+
2Cl– (aq)  Cl2 (g) + 2e– Na+ NaOH OH- Na+ 2H+ (aq) + 2e–  H2 (g)

NaOH forms and sinks

to the bottom

Overall Reaction is: 2NaCl (aq) + 2H2O (l)  2NaOH (aq) + Cl2 (g) + H2 (g)
Section 2
 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.
 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+
Anode Cathode
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)

 What makes a Galvanic cell different from an electrolytic cell?

Galvanic cell Electrolytic cell

Energy
Chemical potential energy is converted An external supply of electrical energy
changes
to electrical energy causes a chemical reaction to occur.

Chemical Non-spontaneous reactions

Spontaneous reactions
reactions .
Anode is negative terminal, is positive terminal ,

Cathode is positive terminal, is negative terminal,

Direction of Electrons flow from negative electrode
Electrons flow from positive electrode
electricity to positive electrode
to negative electrode

Cell set-up two half-cells, one electrode in each, one cell, both electrodes in cell, no
connected by a salt-bridge salt-bridge
Electrolyte are kept separate from one another, and The cathode and anode are in the same
solution(s) are 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, full cells
Electroplating, Electrorefining
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
 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
SO42- coupled.

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
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 or increasing order is
called the electrochemical series.

The Eº will be positive if the metal ion is more

easily reduced than the hydrogen ion.

Increasing Strength of Oxidizing agents

For example,
Increasing Strength of reducing agents

-the Eº for the copper electrode is +0.34 V.

SHE, Reference Point

The Eº will be negative if the metal ion is more

difficult to reduce than the hydrogen ion.
For example,
- The Eº for the zinc electrode is -0.76 V.
Table 4.2 Standard Reduction Potential in Aqueous Solution at 25°C.

More positive Eº

 More positive Eº
 More easily electron is gained
 More easily reduced
 Better oxidizing agents
Example:-
Increasing Strength as reducing agents

Increasing Strength as Oxidizing agents

 F2 is the strongest oxidizing agent
 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
Cu
Table 4.2 Standard Reduction Potential in Aqueous Solution at 25°C.

• The reaction with higher (more positive) reduction

potential proceeds as reduction, while the other
proceeds as oxidation.
In the case of the Daniell cell,

Cathode
Increasing Strength as reducing agents

Increasing Strength as Oxidizing agents

Anode

Therefore, Zn spontaneously reduces Cu2+ to form

Zn2+ and Cu

This principle is sometimes called the diagonal rule.

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 that is located it below in table 4.2.
Cu
Table 4.2 Standard Reduction Potential in Aqueous Solution at 25°C.

Changing the stoichometric coefficients of a half-cell

reaction does not affect the value of Eºred.
For example
Increasing Strength as reducing agents

Increasing Strength as Oxidizing agents

The sign of Eºred. changes, but its magnitude remains
the same when we reverse a reaction.
Example:
Al+3 (aq) + 3e-  Al(s) Eº = -1.66 V
The reverse reaction is Oxidation
Al(s)  Al+3 (aq) + 3e- Eº = +1.66 V
Solution:
From Table 4.2, Page number 192-193, it can be noticed that Cd2+ will oxidize Cr:
Cd2+ (1.0 M) + 2e– → Cd (s), Eored = -0.41 V ( Cathode: higher reduction potential )
Cr3+ (1.0 M) + 3e– → Cr (s), Eored = -0.74 V (anode: lower reduction potential)
Note that, in order to balance the overall reaction, we multiplied the cathode
reaction by 3 while anode reaction by 2.
Overall cell reaction: 3Cd2+ (aq) + 2Cr (s), → 3Cd (s) + 2Cr3+(aq),
Eocell = Eored (cathode) - Eored (anode)
= Eored (Cd2+/Cd) - Eored (Cr3+/Cr)
= (-0.41 V) – (-0.74 V)
= -0.41 V + 0.74 V
= + 0.33 V
The positive value of Eocell shows that the forward reaction is spontaneous.
 4.5.4 Electromotive Force (emf )

 The driving force that allows the electrons to overcome this resistance and move around
the circuit is called electromotive force (emf).

 The electromotive force in a Galvanic cell comes from the redox reaction that pushes
electrons from the anode to a cathode through the external circuit.

 Electrical work ( W) is the product of the emf of the cell and the total charge (in
coulombs) that passes through the cell:
Wele = Q x E, where Q is the charge and E is electrical potential.

 By definition, Q = nF,
where n is moles of electrons that pass through the circuit and F, the Faraday constant,

1 F= 96,500 C/mol e–

What is Free energy change (∆G)?

The change in free energy ( ∆G) represents the maximum amount of useful work that can
be obtained from a reaction.
∆G = -nFEcell
• Under standard state condition,
∆Go = -nFEocell
• The standard free energy change, ∆G°, for a reaction is related to its equilibrium
constant, K, as follows.
∆Go = -RT ln K
• Let us summarize the relationships among ∆G°, K and Eocell and characterize the
spontaneity of a redox reaction.
 4.5.5 Dependence of Ecell (emf) on concentration

What is the effect of changing the concentration of reactants on cell potential?

• A change in concentration affects the change of cell potential which is a result of free
energy change. According to chemical thermodynamics
∆ G = ∆Go + RT ln Q Where,
Q is the reaction quotient, and was used to calculate the effect of concentration on ∆G.
• Since ∆ G = – nFEcell and ∆Go = – nFEo cell, the equation becomes

Nernst equation

The the relationship between the cell potential and the concentrations of the cell components
and is called the Nernst equation.
During the operation of a Galvanic cell, electrons flow from the anode to the cathode,
 resulting in product formation and a decrease in reactant concentration.
 Q increases, which means that Ecell decreases.
 At equilibrium, there is no net transfer of electrons,
so Ecell = 0 and Q = K , where K is the equilibrium constant.
Solution :
The half-cell reactions are
Anode (oxidation ) : Cd(s) → Cd2+ (aq) + 2e–
Cathode (reduction ) : Fe2+ (aq) + 2e– → Fe(s)
Using the standard reduction potentials in Table 4.2, the standard emf (Eocell) can be calculated,
Eocell = Eored (cathode) – Eored ( anode)
= Eored(Fe2+/Fe) – Eored (Cd2+/Cd)
= – 0.44 V – (– 0.41 V) = – 0.03 V
Using the Nernst equation:-
𝑪𝒅 𝟐+
𝟎. 𝟎𝟐𝟓𝟕 𝑽
𝑬𝑶
𝒄𝒆𝒍𝒍 = 𝑬𝑶
𝒄𝒆𝒍𝒍 − 𝒍𝒏
𝒏 𝑭𝒆𝟐+
𝟎. 𝟎𝟐𝟓𝟕 𝑽 𝟎. 𝟎𝟏
= −𝟎. 𝟎𝟑 𝑽 − 𝒍𝒏
𝟐 𝟎. 𝟔𝟎

= +0.013 V The reaction is spontaneous in the direction written.

 4.5.6 Application of Galvanic Cells

BATTERY FUEL CELLS

Learning Objectives
 Classification (or) Types of batteries

A. Primary battery (Primary cells)

• are not rechargeable are discarded after they run down when all the
chemicals are used up. .
• The entire cell reaction cannot be reversed on recharging
• When all the reactants have been completely converted to product, no more
electricity is produced and
• the battery is then dead and cannot be used again and again.
Example: Dry cell, Hg-cell

B. Secondary battery (secondary cells)

• In which cell reactions can be reversed by recharging.
• Secondary batteries are often called storage batteries, or rechargeable
batteries.
• Thus it can be used again and again.
Example: Lead-Acid Batteries, Nickel-Cadmium, Li-ion battery
 Dry Cell battery, LeClanchè Battery

Dry cell-History

• A French engineer Georges Leclanché in 1866 invented a

battery bears his name.
• Leclanché’s invention, which was quite heavy, was steadily
improved over the years.
• In slightly modified forms, the Leclanché battery, now called a
dray cell, is produced in great quantities and is widely used in
Georges Leclanché devices such as flashlights and portable radios.
 Parts Dry Cell

The dry cell is the modification of the wet Leclanché battery.

Commercial battery Figure 4.10 The interior section of a dry cell battery.
Chemical reaction Occur during discharging

 The Oxidation reaction at the Zn electrode

Zn (s) → Zn2+ (aq) + 2e–

 The Reduction reaction at the graphite anode

2MnO2 (s) + 2NH4+ (aq) + 2e– → Mn2O3 (s) + 2NH3 (aq) + H2O (l)

Overall reaction:
Zn (s) +2MnO2 (s) + 2NH4+ (aq) → Zn2+ (aq) + Mn2O3 (s) + 2NH3 (aq) + H2O (l)

 This dry cell produce a voltage about 1.5 volts.

 Alkaline Dry Cell

• The chemistry of alkaline cells is quite similar to that of LeClanchè cells, except that the

material inside the cell is basic or alkaline.

• Alkaline cells use the oxidation of zinc and reduction of MnO2 to generate a current, but

NaOH or KOH is used in the cell instead of the acidic salt NH4Cl.

Anode reaction: Zn (s) + 2OH- (aq) → ZnO (s) + H2O (l) + 2e–

Cathode reaction: 2MnO2 (s) + H2O (l) + 2e– → Mn2O3 (s) + 2OH-(aq)

Overall reaction: Zn (s) +2MnO2 (s) → ZnO (s) + Mn2O3 (s)

The additional advantage of alkaline cells is that the cell potential does not decline under
high current loads, because no gases are formed.
 Mercury dry Cell Battery

This dry cell produces about 1.35 Volts.

The anode in a mercury cell is again metallic zinc, but the cathode is mercury (II)
oxide.

Anode reaction: Zn (s) + 2OH- (aq) → ZnO (s) + H2O (l) + 2e–
Cathode reaction: HgO (s) + H2O (l) + 2e– → Hg(s) + 2OH-(aq)
Overall reaction: Zn (s) + HgO (s) → ZnO (s) + Hg(s)

These cells are widely used in calculators, cameras, watches and other devices.

watches cameras Calculators

 Secondary Battery

1. The Lead Storage Battery

 commonly used in automobiles

 a secondary rechargeable cell.
 The reactions within the cell can be reversed.
 consists of six identical cells joined together in series

When a lead-storage battery is on discharge, the following reactions occur at the electrodes:

Anode reaction : Pb (s) + SO42- (aq) → PbSO4 (s) + 2e–

Cathode reaction: PbO2(s) + 4H+ (aq) + 2e– → PbSO4 (s) + 2H2O(l)
Overall reaction: Pb (s + PbO2 (s) + 4H+ (aq) + SO42- (aq) → 2PbSO4 (s) + 2H2O(l)

The reaction that takes place on recharging a lead storage battery is given by the following
equation.

2PbSO4 (s) + 2H2O(l) + electricity → Pb (s + PbO2 (s) + 4H+ (aq) + SO42- (aq)
 2. Nickel-Cadmium Battery

• The nickel-cadmium battery is rechargeable

• is used in portable computers.
• The cell gives an emf of 1.35 V.
• Ni-Cd cells are expensive.
• Electrolyte: aqueous solution of KOH.

The following reactions occur at the electrodes during discharging

Anode reaction: Cd(s) + 2OH – (aq) → Cd(OH)2 (s) + 2e-

Cathode reaction: NiO2 (s) + 2H2O (l) + 2e- → Ni(OH)2 + 2OH-(aq)
Overall reaction: Cd(s) + NiO2 (s) + 2H2O (l) ↔ Cd(OH)2 (s) + Ni(OH)2
 3. Fuel Cells

What makes a fuel cell different from other types of batteries?

• A fuel cell is a Galvanic cell that requires a continuous supply of reactants to keep
functioning.
• Unlike batteries, fuel cells do not store chemical energy. Reactants must be continuously
supplied, and products must be continuously removed from a fuel cell.
• Most common fuel cell is Hydrogen-Oxygen fuel cell, as shown in figure .
• a hydrogen-oxygen fuel cell consists of an electrolyte solution such as sodium hydroxide
solution, and two inert electrodes.
 4.5.7 Corrosion of Metals

What are the causes of corrosion?

• Corrosion is a galvanic process by which metals deteriorate through oxidation—usually but
not always to their oxides.

• Corrosion is the term usually applied to the deterioration of metals by an electrochemical

process.

• It causes enormous damage to buildings, bridges, ships, and cars.

• For nearly all metals, oxidation in air is a thermodynamically favourable process at room
temperature. If the oxidation process is not inhibited, it can be very destructive.

Rust is
a chemical reaction (oxidation) of iron that occurs over a period of time.
Is an iron oxide, usually red oxide formed by the redox reaction of iron and oxygen in the
presence of water or air moisture.
 Corrosion of Iron
• The most familiar example of corrosion is the rusting of iron.
• Oxygen gas and water must be present for iron to rust.

• The formation of rust requires iron, water and oxygen.

the First Step: Oxidation of Solid Iron

Fe(s) → Fe2+(aq) + 2e-

The electrons produced by this reaction combine with hydrogen ions
in the water as well as with dissolved oxygen to produce water

4e- + 4H+(aq) + O2(aq) → 2H2O(l)

These two reactions produce water and iron(II) ions,

The Second Step: Formation of Hydrated Iron Oxide (Rust)

Fe3+(aq) + 3OH-(aq) → Fe(OH)3

This compound dehydrates to become Fe2O3.H2O, which is the chemical formula for rust.
 Prevention of Corrosion

Iron and its alloys are widely used in the construction of many structures and in many
machines and objects.
Therefore, the prevention of the corrosion of iron is very important. Some preventive
methods are listed below.
1. Galvanization
2. Cathodic Protection
3. Coatings with paints
Galvanization is the process of applying a protective layer of zinc on a metal.
This can be done by dipping the metal to be protected in hot, molten zinc or by the process
of electroplaing.
It is a very common method of preventing the rusting of iron.
In this case, the iron serves as the cathode in the electrochemical corrosion, because zinc is
oxidized more readily than iron.
Therefore, the zinc serves as anode and is corroded instead of iron.

The reactions that occur under these conditions are as follows:

reduction at cathode O2(g) + 4e− +4H+(aq) → 2H2O(l)
Oxidation at anode Zn(s) → Zn2+(aq) + 2e−
overall reaction 2Zn(s) + O2(g) + 4H+(aq) → 2Zn2+(aq) + 2H2O(l)
,
 2. Cathodic Protection

• Protection of metal by making it as cathode in an electrochemical cell is known as

cathode protection.
• The metal that is oxidized while protecting the cathode is called as sacrificial anode.
• Underground pipelines are often protected against corrosion by making the pipeline
as the cathode of galvanic cell.
• Pieces of active metals, such as magnesium are buried along the pipeline and
connected to it by a wire, as shown in below.

Connecting a magnesium rod to an

underground steel pipeline protects the
pipeline from corrosion. Because
magnesium (E° = −2.37 V) is much more
easily oxidized than iron (E° = −0.45 V),
the Mg rod acts as the anode in a galvanic
cell.