Engineering Chemistry Notes (21CHE12/22)

MODULE 1: Electrochemistry and Energy storage systems

Structure: Electrochemistry Energy storage systems
Introduction Determination of pH using glass electrode
Single electrode potential Batteries: Introduction
Nernst equation Classification of Batteries:
Reference Electrodes Lithium Batteries:
Calomel electrode Advantages of lithium-ion batteries in electric
Ion-selective electrode vehicles
Glass Electrode Recycling of lithium-ion batteries:

Electrochemistry
1.1 INTRODUCTION
Electrochemistry is a branch of chemistry that deals with the relationship between
chemical energy and electrical energy and their inter conversions by means of redox
reaction.
Electrochemical cells
These are devices that convert chemical energy into electrical energy by redox
chemical reactions. They are also called Galvanic cells or Voltaic cells.
Ex: Example for Galvanic cell is Daniel cell.
EMF of the cell
The cell electromotive force (emf) of the cell is the potential difference
between the two electrodes,
When no current is flow through the cell.
Free energy or Gibbs’s energy
Gibbs free energy is the energy available in a substance to do work. It refers
to the 'chemical work' involved in chemical reactions
It is defined by the equation: G = H – TS
G=Gibbs’s energy H=Enthalpy S=Entropy T=Temperature
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 Engineering Chemistry Notes (21CHE12/22)

SINGLE ELECTRODE POTENTIAL

“Single electrode potential is defined as the potential generated when the metal is
dipped in the solution consisting of its own ions, at the interphase between solution
and metal”
 The potential arises at single electrode due to reduction.
 The half-cell having lower reduction potential undergoes oxidation.
 The half-cell having higher reduction potential undergoes reduction.
The EMF of the cell is due to the difference between the potentials of the cathode
and the anode.
𝐸𝑀𝐹𝑐𝑒𝑙𝑙 = 𝐸𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒 − 𝐸𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒
𝑬𝑴𝑭 𝒄𝒆𝒍𝒍 = 𝑬𝒄𝒂𝒕𝒉𝒐𝒅𝒆 − 𝑬𝒂𝒏𝒐𝒅𝒆
NERNST EQUATION

Nernst equation is a thermodynamic equation which relates the cell potential

with concentrations Mn+ using standard free energy equation.
The decrease in free energy change (-∆G) is given by the maximum amount of work
done by an electrochemical cell.
−∆𝐺 = 𝑊𝑚𝑎𝑥 − −−→ 1
The maximum work done by the electrochemical cell depends on, Number of
coulombs that flow and the energy available per coulomb.
𝑊𝑚𝑎𝑥 = 𝑁𝑜 𝑜𝑓𝑐𝑜𝑙𝑜𝑚𝑏𝑠 𝑋 𝐸𝑛𝑒𝑟𝑔𝑦 𝑎𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒 𝑝𝑒𝑟 𝐶𝑜𝑢𝑙𝑜𝑚𝑏
The number of coulombs that flow is equal to the number of moles of electrons (n)
and the faraday (F).
∴ 𝑁𝑜 𝑜𝑓𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 = 𝑛𝐹
Energy available per coulomb is the emf of the cell E.
The maximum work done for an electrochemical cell is given by
𝑊𝑚𝑎𝑥 = 𝑛𝐹𝑋𝐸 ------- 2

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 Engineering Chemistry Notes (21CHE12/22)

Substituting equation 2, in 1 we have,

∆𝑮 = −𝒏𝑭𝑬 − −−→ 3
When the concentrations of all species is unity at 25 0C the standard free
energy change ∆𝐺0 is given as
∆𝑮𝟎 = −𝒏𝑭𝑬𝟎 − −−→ 4
Where E0 is the standard electrode potential
“Standard electrode potential is the potential when a metal is dipped in 1M
solution of its ions or when an inert electrode is in contact with a gas at temperature
at 298K”
Consider a red-ox reaction involved in an electrochemical
cell,
The equilibrium constant K c is given by change in free energy by the equation,
[𝑀]
∆𝐺 = ∆𝐺0 + 𝑅𝑇𝑙𝑛𝐾𝑐 𝑤ℎ𝑒𝑟𝑒 𝐾𝑐 =
[𝑀 𝑛+ ]

Therefore, the above equation becomes,

[𝑀]
∆𝐺 = ∆𝐺 0 + 𝑅𝑇𝑙𝑛
[𝑀 𝑛+ ]
∆𝐺 = ∆𝐺 0 + 𝑅𝑇𝑙𝑛[𝑀] − 𝑅𝑇𝑙𝑛[𝑀 𝑛+ ] − −−→ 5
Substituting equations 3 and 4 in equation 5 we have,
−𝑛𝐹𝐸 = −𝑛𝐹𝐸 0 + 𝑅𝑇𝑙𝑛[𝑀] − 𝑅𝑇𝑙𝑛[𝑀 𝑛+ ]
Dividing throughout by –nF, and under standard conditions M=1. Hence the above
equation becomes,
𝑹𝑻
∴ 𝑬 = 𝑬𝟎 + 𝒍𝒏[𝑴𝒏+ ]
𝒏𝑭
Where E= electrode E0 = std. electrode R = gas constant = 8.314
potential, potential, j/k/mole,
T= temperature, F= Faraday = 96500 n= no. of electron involved in
coulombs, the

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 Engineering Chemistry Notes (21CHE12/22)

reaction

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 Engineering Chemistry Notes (21CHE12/22)

Nernst equation at 298K and converting natural log to the base 10 is,
2.303 𝑋 8.314 𝑋 298
𝐸 = 𝐸0 + log[𝑀 𝑛+ ]
𝑛𝑋 96500
𝑬. 𝑬𝑬𝑬𝑬
𝑬 = 𝑬𝑬 + 𝑬𝑬𝑬[𝑬𝑬+ ]
𝑬
This is the Nernst equation for single electrode potential
Nernst equation for cell potential:
𝑬 = 𝑬𝟎 +
𝟎.𝟎𝟓𝟗𝟏
𝒍𝒐𝒈
[𝒔𝒑𝒆𝒄𝒊𝒆𝒔 𝒂𝒕 𝒄𝒂𝒕𝒉𝒐𝒅𝒆]
𝒄𝒆𝒍𝒍 𝒄𝒆𝒍𝒍 𝒏 [𝒔𝒑𝒆𝒄𝒊𝒆𝒔 𝒂𝒕 𝒂𝒏𝒐𝒅𝒆]

REFERENCE ELECTRODE
A Reference electrode is an electrode whose electrode potential is known and
remains constant. Reference electrodes are of two types
Primary reference electrodes: The electrodes whose potential is arbitrarily taken as

zero, for example Hydrogen electrode. It is used to measure potential of all other

electrodes.

Secondary reference electrodes: The electrodes whose potential is known w.r.t SHE

and it is used to measure potential of other electrodes. Ex; Calomel, Ag-AgCl

electrode etc.

 It is simple to construct.

 The cell potential is reproducible and constant for long period.

 The cell potential does not vary with temperature.

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 Engineering Chemistry Notes (21CHE12/22)

CALOMEL ELECTRODE
Construction:
Calomel Electrode is a Secondary Reference
electrode. It consists of a drop of mercury at the
bot- tom, over which a paste of mercury-
mercurous chloride is placed. A solution of
saturated solution of potassium chloride is filled
inside the glass tube. A platinum wire sealed to the
bottom of glass tube is taken out for making the
electrical contact. This reference electrode is
connected to other electrode system by the help of
the side tube which serves as salt bridge.
Working: It is a reversible electrode. It undergoes both oxidation and reduction
depending upon the other electrode (Half-cell) in contact. If it acts as anode,
undergoes oxidation add vice versa.
It is represented as KCl(satd)│ Hg2Cl2(satd)│ Hg
Half-cell for Calomel Electrode:
The net reaction involving both anode and cathode is,

Figure 1.1 Standard Calomel

Electrode
The potential of the calomel electrode depends upon the concentration of the
potassium chloride solution. The reduction potentials of the calomel electrodes on
hydrogen scale at 298K are as follows: Saturated KCl 0.2415 V1.0N, KC1 0.2800 V&
0.1NKCl 0.3338 V.
Advantages:
 Simple to Construct.

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 Engineering Chemistry Notes (21CHE12/22)

 Electrode potential is reproducible and constant for long period.

 Used as reference electrode to measure pH.

ION – SELECTIVE ELECTRODES

“The electrodes that are selectively sensitive to certain ions and develop
potential proportional to the concentration of ions”.
An ion selective membrane electrode consists of generally a membrane which
is capable of exchanging the ions with solutions with which it is in contact.
Some of the ion selective membranes are,
1. Glass membranes 2. Solid state membranes 3. Heterogeneous membranes
Application of Ion selective electrodes
1. Concentration of several cations such as H +, Na+, Li+, K+, Ag+ etc.,
2. Concentration of some anions such as NO3-, CN- etc.,
3. pH of a solution using glass electrode.

GLASS ELECTRODE
Principle
Thin-walled glass bulb containing an acid is
immersed in another solution as shown in figure
1.4. A potential is developed across the glass
membrane. This is called boundary potential Eb.
The potential is due to the difference in
potential (E1-E2) developed between the two
liquids across the layer of the glass membrane.
Glass Electrode showing boundary
potential due to different concentration of H +
ion
Eb gives the difference in the hydrogen ion concentration of the two solutions and is
given by the relation.
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 Engineering Chemistry Notes (21CHE12/22)

𝐸 = 𝐸 − 𝐸 = 𝑅𝑇 𝑙𝑜𝑔 𝐶2
𝑏 1 2 10
𝐹 𝐶1
Where, C1& C2 are the concentrations of H+ ions of the acid solution inside and
outside the glass bulb respectively.
The concentration of H+ (C1) ions inside the solution is constant
∴ 𝑬𝒃 = 𝑳 + 𝟎. 𝟎𝟓𝟗𝟏𝒍𝒐𝒈 𝟏𝟎 𝑪𝟐
Where L is constant, since 𝑝 𝐻 = −𝑙𝑜𝑔10 [𝐻 + ]
∴ 𝑬𝒃 = 𝑳 − 𝟎. 𝟎𝟓𝟗𝟏𝒑𝑯
1.7.1 CONSTRUCTION OF GLASS ELECTRODE:
Glass electrode is pH sensitive electrode which can
selectively detect and measures H+ ions in a system. Thus, it
is widely used for pH measurements.
Glass electrode consists of a long glass tube with a thin-
walled glass bulb at one end as shown in figure 1.6. The bulb
contains 0.1M HCl. Ag/AgCl electrode (internal reference
electrode) is placed in the solution and connected by a
platinum wire for external contact.
The electrode is represented as,
Ag│ AgCl │ 0.1 M HCl │ Glass membrane
Working of glass electrode
When the glass electrode is dipped in the test solution (xM), the Na + ions of
the glass membrane are exchanged for H + ions of the solution inside & outside. The
reaction is ion-exchange.
+ + - + + -
H + Na Gl Na + H Gl
solution membrane solution membrane

The boundary potential Eb is established due to the above reaction. The glass
electrode potential EG is given by.

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 Engineering Chemistry Notes (21CHE12/22)

𝐸𝐺 = 𝐸𝑏 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙
When Eb=o, when C1=C2, But even when C1=C2 a small potential is developed called as
asymmetric potential (Easy).
𝐸𝐺 = 𝐸𝑏 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + Easy
WKT 𝑬𝒃 = 𝑳 − 𝟎. 𝟎𝟓𝟗𝟏𝒑𝑯
EG = L-0.0591pH + EAg/AgCl + Easy
EG = L1 - 0.0591pH
Where L1 = L- EAg/AgCl + Easy
DETERMINATION OF PH USING GLASS ELECTRODE

The glass electrode is immersed in

the solution whose pH is to be
determined. It is combined with external
reference electrode such as calomel
electrode through a salt bridge to
complete the cell. The emf is determined
using pH meter as shown in figure.

The cell is represented as,

Ecell is the difference between EG and the calomel electrode ESCE.

𝐸𝑐𝑒𝑙𝑙 = 𝐸𝐺 − 𝐸𝑆𝐶𝐸
Conventionally, glass electrode always acts as cathode
W. K. T, 𝐸𝐺 = 𝐿 − 0.0591𝑝 𝐻
∴ 𝐸𝑐𝑒𝑙𝑙 = 𝐿 − 0.0591𝑝 𝐻 − 𝐸𝑆𝐶𝐸
𝑳 − 𝑬𝑺𝑪𝑬 − 𝑬𝒄𝒆𝒍𝒍
𝒑𝑯 =
𝟎. 𝟎𝟓𝟗𝟏

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 Engineering Chemistry Notes (21CHE12/22)

The above equation may be written by replacing the constants L-ESCE by

another term K, called electrode assembly constant.
𝑲 − 𝑬𝒄𝒆𝒍𝒍
𝒑𝑯 =
𝟎. 𝟎𝟓𝟗𝟏
In order to calculate K, a known pH of solution is used and the potential of the cell is
measured.
Application of Ion selective electrodes
 Concentration of a number of cations such as H +, Na+, Li+, K+, Ag+ etc.,
 Concentration of some anions such as NO3-, CN- etc.,
 pH of a solution using glass electrode.

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 Engineering Chemistry Notes (21CHE12/22)

Energy storage systems

1.9 Batteries: Introduction
Battery is an electrochemical device which converts stored chemical energy into electrical
energy.
Classification of Batteries:
Batteries are classified as primary (non-rechargeable), secondary
(rechargeable) and reserve (inactive until activated):
Primary batteries Secondary batteries Reserve batteries
→Primary batteries are →Secondary batteries →Reserve batteries are special
those which cannot be are those which can be purpose primary batteries designed
recharged. recharged. for emergency use and for long term
→The net cell →Net cell reaction storage.
reaction is not is reversible. →The vital part of the battery is stored
reversible. →Example: Lead separately
→Primary batteries are acid, Li-Ion batteries →The battery is only activated when it
relatively inexpensive. etc is needed.
→Example: Dry cell. →Used in cell →Self-Discharge is eliminated.
phones, laptops etc →Example: Magnesium-AgCl
batteries, zinc-silver oxide batteries,
etc.
→Used in Missiles, space ships, etc.

Lithium Batteries:
Lithium metal is an attractive anode material because of its lightweight, high voltage,
very low electrode potential, high electrical equivalence and good conductivity. A
lithium cell can produce voltage from 1.5 V to 3.5 V based on the types of materials
used. There are two types of lithium-based batteries are available. Schematic
diagram of Lithium Metal Battery is shown

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 Engineering Chemistry Notes (21CHE12/22)

in Figure 1.11 and Lithium-ion Battery is shown in Figure 1. 12.

Construction and working of Li-Ion Batteries:

The cell is represented as, C, Li+│Li+│ LiMn2O4
It consists of
 Anode: is made of graphite (C6)
 Cathode: The cathode material is made of intercalated lithium compound, such as
multi layered lithium cobalt oxide (LiCoO2), lithium iron phosphate (LiFePO4),
lithium manganese oxide (LiMn 2O4) etc.
 Electrolyte: A non-coordinating electrolyte salt such as LiPF6 or lithium
hexafluoroarsenate monohydrate (LiAsF6) or lithium tetrafluoroborate (LiBF4) is
dissolved in an organic solvent like ethylene carbonate or diethyl carbonate etc.
Since lithium reacts violently with water, a non-aqueous electrolyte must be
used.
 Separator: Polypropylene soaked with electrolyte.
Working:
During charging; an external load forces the Li+ ions to travel from cathode (lithium
compound of LiMn2O4) to anode and accumulates on the surface of graphite. During
discharge, Li+ spontaneously starts migrating back to lithium compound (LiMn 2O4)
at
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 Engineering Chemistry Notes (21CHE12/22)

cathode and electrons flow through the external circuit. The probable cell reactions
are given below,

Anode LixC6→ xLi+ + 6C + xe-

Cathode Mn2O4 + xLi+ +xe- LixMn2O4

Overall reaction LixC6 + Mn2O4 → LixMn2O4 + 6C

Overall charging and discharging,
Dischargin
LixC6 + Mn2O4 g LixMn2O4 + 6C
Charging

Advantages
1. They have high energy density than other rechargeable batteries
2. They are less weight
3. They produce high voltage out about 4 V as compared with other batteries.
4. They have improved safety, i.e., more resistance to overcharge.
5. No liquid electrolyte means they are immune from leaking.
6. Fast charge and discharge rate

Disadvantage:
1. They are expensive
2. They are not available in standard cell types.
Applications:
 Light weight and compact, low maintenance
 High voltage and high energy density
 Used in mobile phones, tabs, laptops, wireless communication devices etc.
 Used in medical devices, electric cars, auto mobiles etc.
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Advantages of lithium-ion batteries in electric vehicles: -

A Lithium-ion (Li-ion) battery is a type of rechargeable battery used in
electric vehicles and a number of portable electronics. Compared to lead-acid
and other lithium batteries have several advantages. Some important
advantages of Li-
Ion batteries in electric vehicles are listed below.
1. Safety: Inherently safe chemistry. BMS provides extra protection.
2. Light weight: 50-60% less weight than lead-acid equivalent.
3. Longest Life: Up to 10X longer cycle life than lead-acid equivalent.
4. More Usable Capacity: 25-50% more capacity than lead-acid equivalent.
5. Constant Power: Full power available throughout discharge. Voltage does
not drop like lead-acid.
6. Temperature Tolerant: 2.5X more efficient operation at low temperatures.
Safely operational up to 149°F (65°C). Lithium is the logical choice for
applications that will exhaust the batteries or run-in extreme weather.
7. Charging - Fast & Safe: Highly efficient charging. Can fully charge in 1-3
hours. Built-in overcharge protection.
8. Long Shelf Life: Low self-discharge so the battery maintains state of charge.
9. Maintenance Free: Plug, play and charge. No watering.
10. Non-Hazardous: No gasses emitted.
Expected Questions
Electrochemistry
1. Derive Nernst equation for single electrode potential.
2. Explain the construction and working of a. Calomel electrode
3. What are ion selective electrodes? Explain the construction and working of
Glass electrode.
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4. Write a note on concentration cells?

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Battery Technology & Fuel Cells

1. Explain the construction and working of Ni-MH battery.
2. Explain the construction and working of Lithium-Ion.
3. Give the advantages of Li-Ion in electric vehicles
4. Write a note on recycling of Li-Ion batteries.
Module Outcome
1. Students acquire the knowledge of Electrochemistry and Batteries.
2. Students will be able to know the basics like electrode potential, Electrode
systems, Battery terminologies. Primary and secondary battery working
principle.
3. Students can analyse the need of developing new batteries for future
development.
1.14 Further Studies
1. https://en.wikipedia.org/wiki/Electrochemistry
2. https://www.corrosionpedia.com/definition/206/calomel-electrode
3. www.horiba.com/application/.../measuring-ph-using-a-glass-electrode/

4. https://www.batterystuff.com/kb/articles/battery-articles/battery-basics.html
5. batteryuniversity.com/learn/archive/understanding_lithium_ion

6. https://www.myprivatetutor.com/questions/details/8065/discuss-the-
construction- and-working-of-methanol-oxygen-fuel

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