FALLSEM2024-25 BCHY101L TH VL2024250106763 2024-09-09 Reference-Material-I

Engineering Chemistry (BCHY101L)
Module 4; Energy Devices

▪ Electrochemical and electrolytic cells
Electrochemical cell- Daniel cell, numerical (Nernst relation) Types of cells/battery
(primary- secondary- fuels cells), chemistry of Li ion secondary batteries, Fuel cells:
H2-O2 and solid oxide fuel cell (SOFC),
Solar cells: Solar spectrum, types of silicon, types of semiconductors Disadvantages
of Photovoltaic Solar Cells, dye-sensitized cells.
Dr. A. A. NAPOLEON, M. Pharm., Ph.D.

Professor,
Chemistry Division, SAS,
VIT University, Vellore – 14.
Contents…. (6 hours)
▪ Electrochemical and electrolytic cells
Electrode materials with examples
• Semi-conductors
▪ Chemistry of Li ion secondary batteries
▪ Fuel cells: H2-O2 and solid oxide fuel cell (SOFC)

▪ Solar cells: Photovoltaic cells (silicon based),
▪ Photoelectrochemical cells, Dye- sensitized cells.
A fuel cell is a device that converts chemical energy (by combining hydrogen
and oxygen) into electrical energy, water and heat through electrochemical reactions.
Fuel + O2 ------ Oxidation products + Electricity.
Module 4 -Energy Devices (Contents…. (6 hrs)
(4a). Electrochemical and electrolytic cells The Electrolysis of Molten NaCl

• Electrode materials with examples Electrolytic Decomposition of Water.
• Electrode-electrolyte interface
 The Nobel Prize in Chemistry 2019 is awarded to John B.
Goodenough, M. Stanley Whittingham and Akira Yoshino.
(4b). Secondary Batteries and Fuel Cells:

• Chemistry of Li ion secondary batteries
• H2-O2 Fuel Cell (HOFC) and Solid Oxide Fuel Cell (SOFC)
(4c). Semiconductors and Solar Cells:

• Semiconductor types  Lithium-ion battery is a secondary battery.
• Photoelectric Cell
 Lithium ion battery technology was first proposed in the
• Silicon-based Photo-voltaic Cell
1970s by M Whittingham who used titanium sulphide for
• Dye-sensitized Solar Cell (DSSC)
the cathode and lithium metal for the anode.
 The movement of lithium ions are responsible for charging
& discharging.
1. Electrochemical Cell
▪ A device that Converts Chemical energy into electrical energy used to generate electricity
from a spontaneous redox reaction.
▪ An electrochemical cell typically consists of

• Two electronic conductors (also called electrodes >> anode and cathode)
• An ionic conductor (called an electrolyte)
• the electron conductor used to link the electrodes is often a metal wire, such as
copper wiring
The electrochemical cells are broadly classified into two types:

• Galvanic or voltaic cell: Converts the energy released by a spontaneous chemical
reaction to electrical energy. ΔG < 0
• Electrolytic cell: Consumes electrical energy from an external source to drive a non-
spontaneous chemical reaction. ΔG > 0
Galvanic or voltaic cell
▪ A galvanic cell uses the energy released during a spontaneous redox reaction (ΔG < 0) to generate
electricity.
▪ This type of electrochemical cell is also called a voltaic cell after its inventor, the Italian physicist
Alessandro Volta.
▪ Anode is written on the left-hand side >> oxidation occurs
▪ Cathode is written on the right-hand side >> reduction occurs.
Electrode on the left Electrode on the right

Metal (or solid phase)| Electrolyte (whole formula Electrolyte (whole formula or ion) | Metal (or
or ion) solid phase)
Zn|Zn(NO3)2 (1M) Cu(NO3)2 (1M)|Cu
Oxidation: M1 → M1n+ + n e- Reduction: M2n+ + n e- → M2

Eg; Zn → Zn2+ + 2 e- Eg; Cu2+ + 2 e- → Cu
Overall representation of Galvanic cell
M1 | M1n+ (C1) ║ M2n+ (C2) | M2
Daniel Cell
▪ Invented by British chemist John Frederic Daniel.
▪ Zn Electrode dipped in ZnSO4 solution:
• Oxidation: Zn → Zn2+ + 2 e-
▪ Cu Electrode dipped in CuSO4 solution:

• Reduction: Cu2+ + 2 e- → Cu
▪ Each electrode is referred to as half cell which are

connected through a salt bridge
▪ Salt bridge: KCl or NH4Cl in a gelatine form

▪ Maintains the charge balance in the two half cells
▪ Minimizes or eliminates the liquid junction potential
▪ Cell emf = 1.1 V
EMF of Electrochemical Cell- Nernst Equation
▪ The electromotive force (EMF): Maximum potential difference between two electrodes of
a galvanic or voltaic cell.
▪ This quantity is related to the tendency for an element, a compound or an ion to acquire
(i.e. gain) or release (lose) electrons.
▪ Cell reaction is feasible when Ecell has positive value.
▪ Cell EMF in terms of Nernst Equation:
Anode
Anode
▪ For equimolar solution of electrolytes corresponding to M1 and M2:
EMF of Electrochemical Cell using Nernst Equation- Numerical
1. Write the half cell reaction, the net reaction and cell EMF of the following cell:
Cd|Cd2+ (0.01 M)║Cu2+ (0.5 M)|Cu
The standard reduction potentials are ̶ 0.40 V and 0.34 V respectively.
(a)Calculate the EMF of the cell: Zn|Zn2+ (0.02 M)║Cu2+ (0.05 M)|Cu. The standard reduction
potentials of the electrodes used herein are ̶ 0.76 V and 0.34 V, respectively.
Ans: EMF of the cell = 1.1117V
E Cell = 0.34 –(-0.76) + 0.059 /2 log10 [0.05] / [ 0.02]
E Cell = 0.34 + 0.76) + 0.059 /2 {0.979)

= 1.1 + 0.01173
= 1.11173 V
Electrolysis
Electrolysis is a process by which electric current is passed through a substance to effect a chemical
change.
The chemical change is one in which the substance loses or gains an electron (oxidn or redn.)
Also refers to the decomposition of a substance by an electric current.
1. The Electrolysis of Molten NaCl

When the current is passed through the molten sodium chloride, sodium and chlorine are
deposited at different electrodes. Thus, sodium chloride is decomposed into sodium and chlorine.
2 NaCl (l) → 2 Na (l) + Cl2 (g)
2. Electrolytic Decomposition of Water

Electrolysis of Water:
Electrolysis is the process of using electricity to split water into hydrogen and oxygen.
This reaction takes place in a unit called an electrolyzer.
2 H2O → O2(g) + 2 H2(g)
The major applications of the electrolysis are given below.

Extraction of Metal from their Ores. ...
Refining of Metals. ...-- Purification
Manufacturing of Chemicals. ...
Electroplating. ...– Coating on the surface of materials / Metals
1. The Electrolysis of Molten NaCl (Davy process- industrial production of sodium metal)
▪ Here Na+ ions gain electrons and are reduced to Anode
Na at the cathode.
▪ As Na+ ions near the cathode are depleted,
additional Na+ ions migrate in.
▪ Similarly, there is net movement of Cl- ions to
the anode where they are oxidized to Cl2. (g)
Cathode
▪ Positive terminal is connected to the anode.
▪ The negative terminal is connected to the cathode which

forces electrons to move from the anode to the cathode.
▪ Electrolysis is performed at ~ 801 °C.
▪ Here inert electrodes- Graphite are used.
Cathode: 2 Na+ (l) + 2 e- → 2 Na (l)

Anode: 2 Cl ̶ (l) → Cl2 (g) + 2 e- Overall: 2 NaCl (l) → 2 Na (l) + Cl2 (g)
CaCl2 acts as flux material, decreasing the melting point, in the
Davy process for the industrial production of sodium metal.
2. Electrolytic Decomposition of Water
▪ A pair of inert electrodes are dipped into the solution
and applying a voltage between them results in the rapid
evolution of bubbles of H2 and O2. Anode Cathode
▪ Due to very poor electrical conductivity of pure water, a

small amount of an ionic solute (such as H2SO4 or
Na2SO4) is added to increase its electrical conductivity.
▪ The electrolytes are chosen such a way that the ions that
are harder to oxidize or reduce than water:
Cathode: 4 H+(aq) + 4 e- → 2 H2(g)
Anode: 2 H2O → O2(g) + 4 H+ + 4 e-
Overall: 2 H2O → O2(g) + 2 H2(g)

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Engineering Chemistry (BCHY101L)

Module 4; Energy Devices

Dr. A. A. NAPOLEON, M. Pharm., Ph.D.

▪ Fuel cells: H2-O2 and solid oxide fuel cell (SOFC)

(4a). Electrochemical and electrolytic cells The Electrolysis of Molten NaCl

(4b). Secondary Batteries and Fuel Cells:

(4c). Semiconductors and Solar Cells:

▪ An electrochemical cell typically consists of

The electrochemical cells are broadly classified into two types:

Electrode on the left Electrode on the right

Oxidation: M1 → M1n+ + n e- Reduction: M2n+ + n e- → M2

▪ Cu Electrode dipped in CuSO4 solution:

▪ Each electrode is referred to as half cell which are

▪ Salt bridge: KCl or NH4Cl in a gelatine form

Ans: EMF of the cell = 1.1117V

E Cell = 0.34 –(-0.76) + 0.059 /2 log10 [0.05] / [ 0.02]

E Cell = 0.34 + 0.76) + 0.059 /2 {0.979)

1. The Electrolysis of Molten NaCl

2. Electrolytic Decomposition of Water

The major applications of the electrolysis are given below.

▪ The negative terminal is connected to the cathode which

Cathode: 2 Na+ (l) + 2 e- → 2 Na (l)

▪ Due to very poor electrical conductivity of pure water, a

Overall: 2 H2O → O2(g) + 2 H2(g)

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