Engineering Chemistry 18CHE12/22

Module – 1
MODULE- I: Electrochemistry and Energy storage systems

Use of free energy in chemical equilibria: Thermodynamic functions: Definitions of free

energy and entropy. Cell potential, derivation of Nernst equation for single electrode potential,
numerical problems on E, E0, and Ecell.

Electrochemical Systems: Reference electrodes: Introduction, construction, working and

applications of Calomel electrode. Ion-selective electrode – Definition, construction and
principle of Glass electrode, and determination of pH using glass electrode. Electrolyte
concentration cells, numerical problems.

Energy storage systems: Introduction, classification - primary, secondary and reserve batteries.
Construction, working and applications of Ni-MH and Li-ion batteries.
(RBT Levels: L3)

ELECTROCHEMISTRY & ENERGY STORAGE SYSTEMS

Introduction:

A part of a total energy of a system is converted in to work and the rest is unavailable. Any
kind of work which is converted into useful work is called as available energy. Energy which
cannot be converted into useful work is known as unavailable energy which is represented as
Entropy function. Isothermally available energy of a system is known as free energy (Gibb‘s
Free energy)

Entropy, the measure of a system‘s thermal energy per unit temperature that is unavailable
for doing useful work.
OR
The amount of entropy is also a measure of the molecular disorder, or randomness, of a
system. (Because work is obtained from ordered molecular motion)

dS=dQ/T

dS= Change in entropy, dQ=change in energy & T is the temperature.

∆S= 0 for reversible process

∆S>0 for irreversible process

Entropy change depends on system and surrounding. To study the above system a new
thermodynamic function is introduced- which is free energy. Free energy is a point function.

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Free energy is a composite function that balances the influence of energy vs. entropy.

The Gibbs free energy G: G = H – TS ------------------1

Where G= Gibbs free energy, H= Enthalpy, T= Constant Temp, S= Entropy

Consider a change A B

GA, HA, and SA are Gibb‘s free energy, Enthalpy and Entropy of reactant A respectively.

GB, HB, and SB are Gibb‘s free energy, Enthalpy and Entropy of product B respectively.

Calculation of change in free energy during a chemical change is given as follows:

∆G= GB-GA = (HB-HA) – T(SB-SA)

∆G=∆H-T∆S

Above change continue till equilibrium is attained. At equilibrium, the second Law states that

dQ= TdS

Under Constant temperature and pressure dH= TdS

For a finite change ∆H=T∆S

At Equilibrium ∆G=∆H-T∆S=0

Significance of Free Energy

∆G= 0 Reaction at equilibrium

∆G= -ve spontaneous reaction

∆G= +ve non-spontaneous reaction

∆G= -nEF for work done in a redox reaction at a given temp

∆G˚= -nE˚F for work done in a redox reaction at 298˚ K

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ELECTROCHEMISTRY
On passing electric current through an electrolytic solution causes chemical reaction to take
place. The reverse is also true i.e,.generation of electric current takes place by chemical reaction.
Depending up on these two types of electrochemical processes there are two types of cells such
as

1) Electrolytic cell: is the cell that converts electrical energy into chemical energy.
2) Galvanic cell or Electrochemical Cell: is the cell that converts chemical energy into electrical
energy.

Red-ox (Reduction-Oxidation) reactions are the basis for electrochemical cells. An

electrochemical cell consists of two electrodes; each electrode is referred as ‘Half Cell’ or
‘Single Electrode’ connected by a metallic wire and electric current flows of as a result
spontaneous red-ox reaction.

Difference between an electrolytic cell and a galvanic cell

Electrochemical cell or Galvanic Cell Electrolytic cell

A Galvanic cell converts chemical energy into An electrolytic cell converts electrical
electrical energy. energy into chemical energy.
The redox reaction is non spontaneous and
The redox reaction is spontaneous and is
electrical energy has to be supplied to initiate
responsible for the production of electrical energy.
the reaction.
The two half-cells are set up in different containers Both the electrodes are placed in a same
being connected through the salt bridge or porous container in the solution of molten
partition. electrolyte.
The anode is negative and cathode is the positive The anode is positive and cathode is the
electrode. negative electrode.
The electrons are supplied by the species being The external battery supplies the electrons.
oxidized. They move from anode to the cathode in They enter through the cathode and come out
the external circuit. through the anode.
The electrodes may be of same metal or
The electrodes are of different metal.
different metal.

ELECTROCHEMICAL CONVENSIONS

1.Representation of Electrode:

It oxidation reaction takes place at anode,then the electrode is represented as M/Mn+

It reduction reaction takes place at the cathode then the electrode is represented as M n+/M
The vertical lines indicated the contact between metal electrodes and metalions.

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2.Representation of Cell:

The following points have to be noted to represent an electrochemical cell

a>Anode is always written to LHS.
b>Cathode of the cell is written to RHS of the anode.
c>The two vertical lines denotes the salt bridge and interface between the two electrodes.
Cell notation is given by M / Mn+ // Mn+ / M
Ex.Zn(s) / Zn+2//Cu+2/Cu(s)

3.Calculation of emf of the cell:

According to electro chemical application
Ecell = Ecathode – Eanode.
If the EMF value is + ve then the reaction is spontaneous & if It is –ve the reaction is
nonspontaeous.

SINGLE ELECTRODE POTENTIAL(E)

Single electrode potential is defined as the potential developed at the interface between the metal
and electrolytic solution,when it is contact with solution of its own ions.
0
STANDARD ELECTRODE POTENTIAL(E )

It is the potential measured, when the electrode is in contact with solution of unit concentration
at 298K.If the electrode involves gas,then gas is at1atmpressure.

EMF OF THECELL(Ecell)

The potential difference between the two electrodes of the galvanic cell which causes the flow
of current from one electrode (higher potential) to the other (lower potential) is know as EMF
of the cell.
EMF = E0Cathode - E0Anode

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Nernst Equation:

Nernst derived a equation to establish relationship between electrode potential and concentration
of metal ion.
The decrease in free energy represents maximum amount of work.
i.e. –Δg = Wmax (1)

Wmax for an electrochemical cell is given by the equation

Wmax = nFE (2)
On comparing eqn (1) & (2) we have
-ΔG = nFE OR ΔG = -nFE

Under standard conditions the free energy ΔG is given by the equation

ΔG° = -nFE°
E° is a constant called standard reduction potential.

Consider a reduction reaction:

Mn+ + ne- M

For spontaneous reaction, the change in the free energy depends on the concentration of reacting
species.
ΔG = ΔG° + RT lnKc (3)

Where Kc = [Products]
[Reactants]

Substituting for Kc in (3) we get

ΔG = ΔG° + RT ln [Product]
[Reactant]

ΔG = ΔG° + RT ln [M] (4)

[Mn+]

Substitute for ΔG and ΔG° in eqn (4)

-nFE = -nFE° + RT ln [M] – ln [Mn+]

Under standard conditions [M] = 1

Hence, -nFE = -nFE° – ln [Mn+] (5)

Dividing eq-(5) by –nF we get

E = E° + RTln [Mn+]
nF

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Converting ln to log we get

E = E° + 2.303RT log [Mn+] (6)

nF

Substituting for RT and F in eqn (6) we get

E = E° + 0.05918 log [Mn+] (7) (For reduction reaction)
n
E = E° - 0.05918 log [Mn+] (7) (For oxidation reaction)
n
Nernst equation can also be applied for the calculation of emf of a chemical cell by using the
following equations:

1) E = E° + 0.05918 log [species at cathode]

n [species at anode]
2) E = E° + 0.05918 log [Product]
n [Reactant]

Reference electrode:

Reference electrode is the electrodes whose potentials are known and are used for
determination of potentials of other electrodes.
Types of reference electrodes:
1) Primary reference electrode
2) Secondary reference electrode

Primary reference electrode: Standard hydrogen electrode (SHE) is used as primary electrode.
SHE – whose potential is arbitrarily taken as zero at all temperatures.

Limitations of SHE:

1) Difficulty in setting up of the electrode

2) It is difficult to maintain the pressure of hydrogen gas at 1atm uniformly.
3) It is difficult to maintain one atm pressure of H2 gas uniformly for a long time.
4) Platinum foil gets poisoned easily by the adsorption of impurity in the solution.
5) The equilibrium between H+ ions and hydrogen gas gets disturbed due to adsorption of
impurities.
6) The hydrogen electrode cannot be used in the presence of oxidizing agents. (As H 2 gas a
reducing agent and it reacts with oxidizing agent)

Secondary reference electrode: Whose potential with respect to SHE are known. Secondary
reference electrodes have several advantages over SHE. These electrodes are commonly used for
determining the electrode potentials.
The two commonly used secondary reference electrodes are calomel electrode and silver-
silver electrode.

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Calomel Electrode:

It is very convenient secondary reference electrode. The Calomel

electrode consists of solid mercury in contact with a sparingly soluble KCl
Hg2Cl2 and dipped in KCl solution. solution
Calomel electrode consists of solid mercury placed at the bottom of the
tube, which is covered with the paste of calomel (Hg2Cl2), over which the Pt
potassium chloride solution is introduced. A platinum wire dipped into
the mercury gives external electrical contact. The electrode is represented Hg2Cl2
as: Cl- / Hg2Cl2 /Hg
Hg

The potential of a calomel electrode depends on the concentration of KCl used.

The Potential developed for:
- 0.1 M KCl solution is +0.334 V.
- 1 M KCl solution it is +0.281 V
- Saturated KCL solution it is +0.242 V

Calomel electrode behaves as anode or cathode depending upon the nature of other electrode.
The net cell reaction when it acts as an anode is

When it acts as anode, the electrode reaction is,

2Hg Hg22+ + 2e-

Hg22+ + 2Cl-
Hg2Cl2
2Hg + 2Cl-
Hg2Cl2 + 2e-

When it acts as cathode, the electrode reaction is,

Hg22+ + 2e- 2Hg

Hg2Cl2 Hg22+ + 2Cl-
Hg2Cl2 + 2e- 2Hg + 2Cl-
The net cell reversible electrode reaction is,

The net cell reaction when it acts as a cathode is

Hg2Cl2(s) + 2e- 2Hg(l) + 2Cl-

The Nernst equation is given by,

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Uses: is used as a secondary reference electrode in the measurement of single electrode potential.

Advantages:

1) Easy to constructed
2) Highly reproducible
3) Stable for long period
4) Temperature invariant

Applications:

1.It is used as secondary reference electrode in the measurement of single electrode.

2. It is used as reference electrode in all potentiometer determinations
3. It is used as a secondary reference electrode in place of calomel electrode / glass electrode /
ion selective electrodes.
4. Used in determining whether the potential distribution is uniform or not in ship hulls
and old pipelines protected by cathodic protection.
5. As a portable reference electrode for measuring the different depths of oil rigs
anplatforms, submerged oil pipelines etc. usually such probe is powered by Ni – Cd
battery and can operate up to a depth of 300-400m with precision of ±1mv.

Ion-selective electrodes:

The electrode, which responds to a specific ion in a mixture by ignoring other ion, known
as ion selective electrode. It consists of a thin membrane in contact with ion solution. It has the
ability to respond to a specific ion and develop a potential on membrane. In ion selective
electrode, the membrane will be in contact with an analyte solution on one side and internal
reference solution on the other side and internal reference electrode dipped in internal reference
solution, schematically represented as
Membrane
Solution to be Internal Internal
analysed (C1) Standard Solution (C2) Reference Electrode

The potential developed across the membrane is due to the difference in concentration of analyte
solution and internal standard solution. By convention
Ecell= RT log C2 - RT log C1
nF nF
Ecell= RT log C2
nF C1
Uses:
1)used in the determination of cations such as H+, Li+, K+, etc and anions such as CN-, NO3-, F-,
etc.
2) used in determination of pH by using H+ ion selective electrode.
3) Used to determine the concentration of gas in presence of gas-sensing electrode.

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Glass Electrode:

Ag-AgCl electrode

Ag/AgCl
0.1 M HCl [H+]=C2

H+ ion [H+]=C1

Cell representation: Ag / AgCl / HCl (0.1M) / Glass.

Glass membrane selectively responses to hydrogen ions.

This electrode works on the principle that when a thin and low resistivity glass membrane is in
contact with a solution containing H+ ions, a potential develops between the membrane and the
solution. Potential developed depends on the concentration of hydrogen ions in the solution.

When the concentration of hydrogen ions is different on either side of the glass membrane, the
potential develops across the membrane.

Construction:
A long glass tube with a thin walled glass bulb (sense H+ ions up to pH-9) contains 0.1 M HCl.
An Ag/AgCl electrode placed in the solution connected by a platinum wire for electrical contact.
The electrode containing H+ ions of concentration C1 is dipped in another solution of
concentration C2. A change in H+ ion concentration causes a change in the composition of glass,
due to exchange of ions by inner membrane and outer membrane resulting in a boundary
potential Eb.

At Equilibrium, Na+(glass) + H+(aq)⇔ Na+(aq) + H+(glass)

Membrane
Solution to be Internal Internal
Analyzed (C2) Standard Solution (C1) Reference Electrode
(H+ ions) (0.1 M HCl) (Ag/AgCl electrode)
E1 E2

Eb= E1-E2 (E1& E2 is the potential developed at outer and inner membrane respectively)
Where E1= 0.0591/n logC2 and E2= 0.0591/n logC1
Then boundary potential
Eb= E1-E2= 0.0591logC2 - 0.0591logC1 (n= [H+] =1)

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C1 is constant due to known electrolyte taken in bulb,
Then -0.0591logC1=constant=L
+
C2 = [H ] ions in outer membrane then,
Eb= L+ 0.0591 log [H+]
Eb= L - 0.0591 pH (pH = -log[H+])

Advantages: Disadvantages:
1) It is used in both oxidizing and reducing 1) Cannot be used for acids having pH < 1.
agents. 2) Cannot be used in the presence of fluoride
2) It is simple to operate. ions.
3) It provides accurate results. 3) Cannot be used in alcohol and some organic
4) It is not poisoned easily. solvents.
5) It is used to determine the pH of a solution
in the range 0-10

Determination of pH of a Solution using Glass Electrode:

The potential of a glass electrode depends on the concentration of H+ ions. Hence, pH of

a solution can be determined by using glass electrode and calomel electrode assembly. The cell
assembly is represented as

Cl-/Hg2Cl2/Cl- // solution of unknown PH / glass/0.1 M HCl / AgCl / Ag

The emf of a cell is determined by using high impedance voltmeter.

Ecell is the difference b/w glass electrode potential EG and the calomel electrode potential ESCE

Ecell = EG - ESCE = L1 – 0.0591pH – ESCE

PH = L1 - ESCE - Ecell
0.0591

L1 – a constant K can replace ESCE

PH = K - ESCE
0.0591

In order to evaluate K, a solution of known pH is used and the potential of the cell is measured

Electrolyte Concentration cells:

“Electrolyte Concentration cell is an electrochemical cell in which the electrode material and the
solution in both the electrodes are composed of the same substances but only the concentrations
of the two solutions (electrolyte) are different”.
A typical example of Copper concentration cell is shown below.

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Concentration Cells:

When two electrodes of a same material are introduced into a solution of same
electrolyte, having same concentration the potential developed is 0. Hence, current does not flow
through the circuit. When electrodes of same material are dipped in a solution of different
concentrations, the potential is developed. Such cells are called concentration cells.

Construction of a cell in which the emf is produced by difference in concentration of

solution.
Consider a cell in which both the electrodes are made up of copper metal dipped in
CuSO4 solution of different concentration.

Voltmeter
V

- +

Cu Anode Cu Cathode

SaltBridge

[Cu2+] = M1
[Cu2+] = M2

Cell Notation: Cu | Cu2+ (M1) || Cu2+ (M2) | Cu

Where M1 and M2 are the molar concentration of the Cu2+ in the two, half cells. The copper
electrode, which is in contact with a solution of higher concentration acts as cathode and that
with lower concentration, acts as anode.
The half-cell reactions are:
Cu Cu2+ (M1) + 2e (anode)
2+
Cu (M2) + 2e Cu (cathode)
The net cell reaction is:

Cu2+ (M2) Cu2+ (M1)

The current flow is due to change in concentration. This takes place until the concentration in the
two half-cells become equal.

Ecell = ER - EL (R – Right & L – Left)

=
E° + 0.0591 log M2 E° + 0.0591 log M1
n n

Ecell= 0.0591 log M2

n M1

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ENERGY STORAGE SYSTEMS

Introduction
● A battery is a portable energy source with three basic components-an anode (the negative
part), a cathode (the positive part), and an electrolyte. As current is drawn from the battery,
electrons start to flow from the anode through the electrolyte, to the cathode.
● A device enables the energy liberated in a chemical reaction to be converted directly into
electricity.
● The term battery originally implied a group of cells in a series or parallel arrangement, but
now it is either a single cell or group of cells.
● Examples: It ranges from small button cells used in electric watches to the lead acid batteries
used for starting, lighting and ignition in vehicles with internal combustion engines.
● The batteries are of great importance based on the ability of some electrochemical systems to
store electrical energy supplied by the external source. Such batteries may be used for
emergency power supplies, for driving electric vehicles, etc.
● For the commercial exploitation, it is important that a battery should provide a higher energy,
power density along with long shelf life, low cost and compatible rechargeable units.

Battery: It is a device consisting of two or more galvanic cells connected in series or parallel or
both.

Principle components of a battery are:

1. An anode where oxidation occurs.
2. A cathode where reduction occurs.
3. An electrolyte, which is ionically conducting.
4. A separator to separate anode and cathode compartments.

Classification of batteries:
1. Primary batteries: In these batteries the cell reaction is not reversible after discharging cannot
be rechargeable. e.g. Zn-MnO2 dry cell.
2. Secondary batteries: In this battery the cell reaction is completely reversible after discharging
can easily rechargeable. e.g. Lead-acid battery, Ni-MH battery.
3. Reserve batteries: In these batteries, one of the active components (e.g. electrolyte) of the
battery is separated from the rest of the components. It is assembled just before the use. e.g. Mg-
water activated the battery.

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Nickel-metal hydride battery (Ni-MH)

Nickel metal hydride (metal hydride is a binary compound formed by the union of hydrogen and
other elements) batteries are similar to Ni-Cd battery, but are less toxic and offer higher
capacities. Ni-MH batteries have a high self-discharge rate and are relatively expensive to
purchase.

Construction:

● In a Ni-MH cell, a hydrogen storage metal alloy behaves as anode and nickel oxy hydroxide
cathode.
● At cathode (a highly porous substrate) nickel oxy hydroxide is impregnated.
● The electrolyte is an aqueous potassium hydroxide solution.
● Synthetic non-woven material used as a separator that separates the two electrodes and
behaves as a medium for absorbing the electrolyte.
● Electrode reactions are:
At anode: MH + OH-—> M + H2O + e-
At cathode: NiO(OH) + H2O + e- —> Ni(OH)2 + OH-
Over all reaction: NiO(OH) + MH —> Ni(OH)2 + M
● The open circuit voltage is 1.35V.
● During recharging of the battery the above cell reaction is reversed.

● Advantages Disadvantages: Uses:

● Higher capacity ● Limited service life ● Cellular phones

● Long shelf life ● Limited discharge ● Emergency
● Simple storage and current ● Power tools
transportation ● High self-discharge ● Portable electric
● Environmentally friendly ● High maintenance vehicles

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Lithium-ion battery (Li-ion Battery)

1.Li-ion batteries are secondary batteries.

2.The battery consists of a anode of Lithium, dissolved as ions, into a carbon.
3.The cathode material is made up from Lithium liberating compounds, typically the three
electro-active oxide materials,

Principle

1. During the charge and discharge processes, lithium ions are inserted or extracted from
interstitial space between atomic layers within the active material of the battery.
2. Simply, the Li-ion is transfers between anode and cathode through lithium Electrolyte.
.Since that of a Lithium metal battery

These batteries with high energy density, high energy efficiency, high voltage and long life
cycle. Lithium has the following characteristics.
(i) It is light weight. (ii) It has high electrochemical equivalence (3.86 Ah g-1). (iii) It has good
electrical conductivity. (iv) It has high standard electrode potential (-3.05V).

construction and working:

A conventional lithium ion battery consists of and a metal oxide such as carbon (graphite) forms
the anode and lithium cobalt oxide (LiCoO2) as a cathode. The electrolyte consists of a lithium
salt in an organic solvent. The salts include lithium hexafluorophosphate LiPF6, lithium
tetrafluoroborate LiBF4 and lithium perchlorate LiClO4. The solvents used are ethylene
carbonate, dimethyl carbonate, and diethyl carbonate. The cell delivers an emf of 4V.

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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
1. The Li-ion batteries are used in cameras, calculators.
2. They are used in cardiac pacemakers and other implantable device.
3. They are used in telecommunication equipment, instruments, portable radios and TVs,
pagers. They are used to operate laptop computers and mobile phones and aerospace
application.

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Most probable Questions
1. Define single electrode potential. Derive the Nernst equation for single electrode
potential. (L1)
2. Define the following: a) Free energy b) Entropy (L1)
3. What are concentration cells? Explain the construction and working of a copper
concentration cell. ( L2)
4. Define reference electrode. Explain the construction and working of Calomel electrode. (L2)
5. What is an ion selective electrode? Construct the Glass electrode and explain the principle
and working of Glass electrode. (L3)
6. Explain the construction and working of Glass electrode? (L2)
Illustrate how a glass electrode can be used in the determination of a P H of a
solution. (L3)
7. Explain the determination of electrode potential by using Calomel electrode. (L1)
An electrochemical cell consists of metallic zinc immersed in 0.1 M Zn(NO3)2
solution and metallic copper immersed in 0.2 M CuSO4 solution. Calculate emf of
the cell at 250C and change in free energy of the cell reaction E0cell = 1.1 V. (L3)

8. Emf of the cell Ag/AgNO3(C1) // (C2 = 0.2) AgNO3 /Ag is 0.8 V. Calculate C1 of
the cell. (L3)
9. Define Battery? Explain the classification of batteries with suitable example. (L2)
Explain the construction, working and applications of a Ni-Metal hydride
Battery (L2)
10. Discuss the construction and working of a Li-ion battery. (L3)
11. Lithium batteries are more advantageous over other batteries. Explain. (L2)

Note: Refer the Numerical problems which are solved in the class.

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