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Introductory Chemistry I
(3 units)
(Electrochemistry)
– Part IV –

Dr. Osibote/Dr. Abayomi/Dr. Izunobi

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Electrochemistry
▪ Electrochemistry studies the conversion of
chemical to electrical energy and vice versa
▪ lt deals with oxidation/reduction reactions
that either produce or utilize electrical energy
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Oxidation/Reduction Reactions – Revision

▪ Oxidation and Reduction occur simultaneously

▪ Oxidation is the process of electron loss
▪ Reduction is the process of electron gain
▪ Oxidation leads to increase in oxidation no.
▪ Reduction leads to decrease in oxidation no.
▪ An oxidising agent is an acceptor of electrons
▪ A reducing agent is a donor of electrons
▪ An oxidising agent is reduced
▪ A reducing agent is oxidised
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Redox Reactions

▪ A redox reaction is the sum of two half

reactions – a reduction and an oxidation
▪ In a reduction half reaction, electrons are
gained
2H+( aq) + 2e– H2( g)
▪ In an oxidation half reaction, electrons are
lost
Zn(s) Zn2+(aq) + 2e–
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Redox Reactions

▪ The reduced and oxidised species in a half

reaction form a redox couple
▪ A redox couple is denoted Ox/Red e.g.,
H+/H2 or Zn2+/Zn
▪ That is, a couple is written with the oxidised
species before the reduced species
▪ H+ and Zn2+ are oxidised whereas H2 and Zn
are reduced
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Redox Reactions – Example

▪ When a piece of zinc is dropped into a

solution of copper (II) sulphate, a chemical
reaction occurs
▪ The deep blue colour of the copper (II)
sulphate solution grows lighter while the piece
of zinc grows smaller with the formation of
solid copper
Zn(s) + CuSO4(aq) → ZnSO4(aq) + Cu(s)
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Redox Reactions – Example

▪ Reaction:
Zn(s) + CuSO4(aq) → ZnSO4(aq) + Cu(s)
▪ Half Reactions:
Zn(s) → Zn2+(aq) + 2e– (oxidation)
Cu2+(aq) + 2e – → Cu(s) (reduction)
▪ Combined Half Reactions:
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
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Redox Reactions – Mneumonic

OIL RIG
▪ OIL – Oxidation Is Loss of electrons
▪ RIG – Reduction Is Gain of electrons
▪ Oxidation and reduction can not exist alone
▪ They occur simultaneously – at the same
time
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Electrolysis

▪ Electrolysis is the decomposition of a

compound – molten or in solution – by passing
an electric current
▪ In electrolysis, electrical energy is used to
produce chemical change
▪ Reduction occurs at the cathode while
oxidation occurs at the anode
▪ Cations (positive ions) migrate to the cathode
while anions (negative ions) move to the anode
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Electrochemical Cells

▪ The electrode is the metal strip or wire

(connected by an electrically conducting wire)
where reduction or oxidation occurs
▪ The anode is the negative electrode (where
oxidation occurs)
▪ The cathode is the positive electrode (where
reduction occurs)
▪ Electrons flow from anode to cathode
▪ The anode is placed on the left by convention
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Electrochemical Cells – Salt Bridge

▪ An electrolyte is a solution or molten that can

conduct electric current
▪ A salt bridge connects the electrolytes;
ensuring electrical contact between them
▪ It is made up of a gel permeated with the
solution of an inert electrolyte
▪ It prevents the electrolytes from mixing
▪ It maintains the electrical neutrality of the
half-cells as ions flow into and out of it
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Electrochemical Cells

▪A
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Electrochemical Cells – Batteries

▪ Spontaneous oxidation/reduction reactions

generate electric currents in a galvanic or
voltaic cell – in contrast to electrolysis
▪ Therefore, the processes in galvanic cells are
the reverse of those in electrolytic cells
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Electrochemical Cells – Batteries

▪ A battery has one or more galvanic cells,

which convert chemical energy into electrical
energy
▪ Single-cell batteries contain one galvanic cell
▪ Multi-cell batteries consist of several galvanic
cells linked in series to obtain the desired
voltage
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Electrochemical Cells – Batteries

▪ A galvanic cell is denoted thus:

anode/anode electrolyte//cathode electrolyte/cathode
- The single vertical lines indicate different phases but
with physical contact between species
- The double line indicates a salt bridge – a porous
divide permitting ion flow while preventing the
electrolytes from mixing
▪ Example: A zinc–copper cell would be written
as: 2+ 2+
Zn(s)/Zn (aq) //Cu (aq)/Cu(s)
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Electrochemical Cells – Batteries

▪ In a galvanic (or voltaic) cell, the cathode is

positive whereas the anode is negative
▪ In contrast, in an electrolytic cell
(electrolysis), the cathode is negative while the
anode is positive
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Electrochemical Cells – Batteries

▪ Types of batteries:
- Lead Storage Battery
- Zinc Dry Cell
- Alkaline Dry Cell
- Mercury Dry Cell
- Nickel–Cadmium Battery
- Nickel–Metal–Hydride (NiMH)
- Lithium Ion (Li-ion) Battery
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Electrochemical Cells – Batteries

▪ Lead Storage Battery (Car battery)

A typical 12-volt battery, which consists of six
individual cells connected in series
▪ Zinc Dry Cell (Leclanché Cell)
It uses a viscous paste rather than a liquid
solution
▪ Alkaline Dry Cell
It is a modified Leclanché cell, which replaces
NH4Cl with NaOH or KOH
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Electrochemical Cells – Batteries

▪ Mercury Dry Cell

It is a modified Leclanché cell, which replaces
MnO2 with HgO and uses a steel cathode
▪ Nickel–Cadmium Battery
It is a modified Leclanché cell with nickel as the
cathode and cadmium as the anode
- It is rechargeable (i.e., the reactions at the
anode and cathode are reversable)
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Electrochemical Cells – Batteries

▪ Nickel–Metal–Hydride (NiMH) Battery

The toxic cadmium (Cd) anode is replaced with
a hydrogen atom-impregnated ZrNi2 metal alloy
- It is rechargeable
▪ Lithium Ion (Li-ion) Battery
It is the newest rechargeable battery
- It is based on the migration of Li+ ions from
the anode and vice versa
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Electrochemical Cells – Standard Potentials

▪ The standard potential of any galvanic cell is

the sum of the standard half-cell potentials for
the oxidation and reduction half-cells, i.e.,
E°cell = E°oxidation + E°reduction
▪ Standard half-cell potentials are always
quoted as a reduction process. Therefore, the
sign must be changed for the oxidation process
▪ The cell potential (Ecell) is also known as the
electromotive force (emf) of the cell
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Electrochemical Cells – Standard Potentials

▪ The standard half-cell potentials are

determined from the difference between the
two electrodes
▪ The Standard Hydrogen Electrode (SHE) is the
reference point
▪ It consists of a platinum electrode in contact
with H2 gas (1 atm) and aqueous H+ ions (1 M)
▪ SHE is assigned an arbitrary value of exactly
0.00 V (zero volt) at all temperatures
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Electrochemical Cells – Standard Hydrogen

Electrode (SHE)

* The ° in E°cell
indicates standard
conditions of 25 oC,
1 atm. and 1 M for the
temperature, pressure
and molarity of the
solution, respectively
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Electrochemical Cells – SHE

▪ Zinc metal in dilute acid gives hydrogen gas

▪ When SHE is connected in a galvanic cell with
a Zn2+/Zn electrode, a spontaneous cell process
is obtained:
- Oxidation process: Zn(s) → Zn2+(aq) + 2e–
- Reduction process: H+(aq) + 2e – → H2(g)
E0 cell is 0.763V
E0 Zn2+/Zn = –0.763 V
* E0 Zn2+/Zn is –0.763 V (and not 0.763 V) because
Zn2+/Zn is an oxidation process
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Electrochemical Cells – SHE

▪ Similarly, for a cell with hydrogen and copper

electrodes:
- Anode (oxidation): H2(g) → 2H+(aq) + 2e–
- Cathode (reduction): Cu2+(aq) + 2e – → Cu(s)
E0 cell is +0.337V
E0 Cu/Cu2+= +0.337 V

* E0 Cu/Cu2+ is +0.337 V because Cu/Cu2+ is a

reduction process
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Electrochemical Cells – Standard Potentials

▪ The more negative value forms the oxidation

half-cell when selecting two half-cell reactions
▪ Consider the reaction between zinc and silver:
Ag+(aq) + e – → Ag(s) E° = 0.80 V
Zn2+(aq) + 2e – → Zn(s) E° = –0.76 V
▪ Zinc, therefore, forms the oxidation half-cell:
Zn(s) → Zn2+(aq) + 2e– E° = – (–0.76 V)
= +0.76 V
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Electrochemical Cells – Standard Potentials

▪ Consider a Zn–Cu couple:

Zn(s)/Zn2+(aq) //Cu2+(aq)/Cu(s)
- Anode (oxidation): Zn(s) → Zn2+(aq) + 2e–
- Cathode (reduction): Cu2+(aq) + 2e – → Cu(s)

- E0 Zn2+/Zn = –0.763 V
- E0 Cu/Cu2+= +0.337 V
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Electrochemical Cells – Standard Potentials

▪ Calculate using:
E°cell = E°oxidation + E°reduction
E°oxidation = –0.763 V (E0 Zn2+/Zn) = +0.763 V*
E°reduction = +0.337 V (E0 Cu/Cu2+)

E°Zn–Cu = 0.763 + 0.337

= 1.10 V
* E0 Zn2+/Zn is more negative than E0 Cu/Cu2+
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Standard Reduction Potentials (@ 25 oC)

▪ Prentice Hall, 2004 ©

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Corrosion

▪ Corrosion is defined as the oxidative

deterioration of metals
▪ It is commonly known as rusting (in iron)
▪ Rusting requires the presence of BOTH
oxygen and water
▪ Rusting results from tiny galvanic cells
formed by water droplets
▪ Iron and steel structures and products are
destroyed by corrosion
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Corrosion

Oxidation: Fe(s) → Fe2+(aq) + 2e–

Reduction: O2(g) + 4H+(aq) + 4e– → 2H2O(l)
Overall: 2Fe(s) + O2(g) + 4H+(aq) → 2Fe2+(aq) + 2H2O(l)
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Corrosion – Prevention

▪ Galvanization: is the coating of iron with zinc

- Zinc is more easily oxidized than iron
- Coating with zinc protects and reverses the
oxidation of the iron
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Corrosion – Prevention

▪ Cathodic Protection: is the protection of a

metal from corrosion by connecting it to a
metal – a sacrificial anode – which is more
easily oxidised
▪ All that is required for cathodic protection is
an electrical connection to the sacrificial anode
– usually magnesium or zinc
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Corrosion – Prevention

▪ Cathodic protection
with magnesium anode
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Corrosion – Prevention

▪ Alloying is also a method of preventing

corrosion