ELECTROCHEMISTRY

ECU 102 ENG. DOROTHY MAINA

1. Introduction
2. Galvanic Cells
3. Standard Reduction potentials
4. Electromotive force (emf) of a cell:
5. Corrosion
 INTRODUCTION
• Electrochemistry is the branch of chemistry that deals with the
relationship between electricity and chemical reactions.

• Electrochemical processes are redox (oxidation-reduction) reactions in

which the energy released by a spontaneous reaction is converted to
electricity or in which electrical energy is used to cause spontaneous
reaction to occur (Electrolysis).
 Types of cells

Voltaic (galvanic) cells:

a spontaneous reaction generates electrical energy

Electrolytic cells:
absorb free energy from an electrical source to
drive a nonspontaneous reaction
 COMMON COMPONENTS OF A GALVANIC CELL
• Electrodes:
conduct electricity between cell and surroundings

• Electrolyte:
mixture of ions involved in reaction or carrying charge

• Salt bridge:
completes circuit (provides charge balance)
 Electrodes
Anode:
Oxidation occurs at the anode

Cathode:
Reduction occurs at the cathode

Active electrodes: participate in redox

 Voltaic (Galvanic) Cells

A device in which chemical energy

is changed to electrical energy.

Uses a spontaneous reaction.

A zinc bar is immersed in a 𝑍𝑛𝑆𝑂4 solution, and a copper bar is
immersed in a 𝐶𝑢𝑆𝑂4 solution.
 The cell operates on the principle that the oxidation of Zn to
𝑍𝑛2+ and the reduction of 𝐶𝑢2+ to Cu can take place
simultaneously in separate locations with the transfer of electrons
between them occurring through the an external wire.
 Zinc and copper bars are called electrodes
 The half reactions are:
 To complete the electrical circuit, the solutions must be connected
by a conducting medium thro’ which the cations and anions can
move from one electrode compartment to the other.

 This is done by a salt bridge with an inert electrolyte solution such

as KCl, KN𝑂3 or 𝑁𝐻4 𝑁𝑂3

 The salt bridge allows movement of ions: anions towards the

anode and cations towards the cathode.

 Conduction of electricity from one electrolyte solution to another-

occurs via migration of 𝐾 + from the bridge in one direction and
𝐶𝑙 − in the other
STANDARD REDUCTION POTENTIALS
 The electrical potential or voltage is denoted by 𝐸 ° .
• It is referred to as the standard as the standard electrode
potential which is the voltage associated with a reduction
reaction at the electrode when all solutes are 1M and all gases
are at 1 atm Standard reduction potential of SHE zero

• The driving force that allows electrons to flow is called the

electromotive force (emf) or the cell potential (Ecell).

 The unit of electrical potential is volt (V)

The hydrogen electrode is called the standard hydrogen electrode (SHE)
• The driving force that allows electrons to flow is called the
electromotive force (emf) or the cell potential (Ecell).
 The unit of electrical potential is volt (V)
 The standard emf of the cell, 𝐸 ° , which is composed of a contribution
from the anode and a contribution from the cathode, is given by:
∘ ∘ ∘
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒

 Where both 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒

∘
and 𝐸𝑎𝑛𝑜𝑑𝑒 ∘
are the standard potentials of the
electrodes.
 For the Zn-SHE cell, we write
Ecell  EH  / H  EZn2 / Zn
2
𝐻 + Τ𝐻2 𝑚𝑒𝑎𝑛𝑠 2H+ + 2𝑒 − → 𝐻2
0.76V  0  EZn2 / Zn 𝑍 𝑛2+ Τ𝑍 𝑛 means Zn2+ + 2𝑒 − → 𝑍𝑛
 The standard reduction potential table contains the half reactions and the
values of the standard potentials.
 Below the SHE, the negative standard potentials increase and above it, the
positive potentials increase
 For the calculations the following points are important:
1. The 𝐸 ° values apply to the half-cell reactions as read in the forward (left
to right) direction.
2. The more positive 𝐸 ° is the greater the tendency for the substance to be
reduced.
3. The half-cell reactions are reversible. Depending on the conditions, any
electrode can act either as anode or a cathode
4. Changing the stoichiometric coefficients of the half cell reaction does not
affect the value of the 𝐸 °
Example

1. A galvanic cell consistA galvanic cell consists of Mg electrode in a

1.0M Mg(NO3)2 solution and a Ag electrode in a 1.0M Ag(NO3)
solution. Calculate the standard emf of this cell at 25°С.
Practice exercise
What is the standard emf of a galvanic cell made of a Cd electrode in a
1.0M Cd(NO3)2 solution and a Cr electrode in a 1.0M Cr(NO3)3 solution
at 25°C?
 Corrosion
Some metals, such as copper, gold, silver and platinum, are
relatively difficult to oxidize.
These are often called noble metals.

What is Corrosion?
Corrosion is a gradual deterioration of metals upon interaction
with the environment as a result of chemical reactions between
them. Almost every metal is susceptible to degradation. Rusting
of iron is the most familiar example of corrosion.
What is Rust?
When iron is exposed to water or air over a period of time, the iron
reacts with oxygen in the presence of moisture to form a reddish-brown
chemical compound, iron oxide. This is referred to as rust. So chemically,
rust is hydrated iron(III) oxide or Fe2O3.nH2O. The chemical equation for
the same is given by:

4Fe(OH)2 + O2 + xH2O → 2Fe2O3.(x+4)H2O

Iron reacts very readily with oxygen. This is one of the reasons as to why
it is rare to find pure iron in nature.
Factors Affecting Rusting
• There are several factors that assist and accelerate the process of rusting.
Some of them are:

• Moisture: Iron exposed to rains is the most common reason.

• Acid: It accelerates rusting. When exposed to acid rains, iron rusts faster.
On the other hand, alkalis inhibit rusting.

• Salt: Iron tends to rust faster in sea, due to the presence of salt.

• Impurity: Pure iron rusts slower than the iron mass which contains a
mixture of metals.
Why Rust Prevention?
• Rusting makes iron flaky and friable and decreases its intended
usage period.

• A considerable amount of damage is done by rusting every year,

which includes damaging of cars, grills, buses, railings, sinking of
ships, falling of bridges, deterioration of statues, etc.

• Huge sums of money is spent for the replacement and repair of

these damages. Thus, it is important to take steps to prevent iron
from getting rusted.
Preventive Measures
Some effective measures used to prevent rusting are:
•Coating and painting: Iron surface is often painted with the coatings of
varnish or paint to isolate it from the environment. Window grills, bodies
of automobiles, iron bridges and rails are painted regularly to protect them
from rusting.
•Applying a layer of grease: Grease or a layer of oil is also applied to iron
surfaces, primarily on machines and industry tools. This serves dual
purpose of a lubricant reducing friction as well as rust prevention.
•Galvanisation: It is a process of depositing a thin layer of a non-reactive
metal like zinc on the surface of iron. This metallic layer prevents the iron
to come in contact with air and moisture. Buckets, drums, roofs, pipes etc.
are galvanized to prevent rusting.
 Galvanization of Iron
Cathodic Protection
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