ENGINEERING CHEMISTRY (18CHE12/22)

MODULE-I

ELECTROCHEMISTRY AND ENERGY STORAGE SYSTEM

Use of free energy in chemical equilibria

Thermodynamic functions: (Terminologies)

Thermodynamics:

Thermodynamics is the branch of physical sciences concerned with heat and temperature and
their relation to energy and work.

State function:

A thermodynamic quantity that has definite values for given states of a system, such
as entropy, enthalpy, free energy, etc

In thermodynamics, a state function or function of state is a function defined for a system

relating several state variables or state quantities that depends only on the current
equilibrium state of the system.

Example: a gas, a liquid, a solid, crystal, or emulsion.

Path function:

In thermodynamics, a quantity that is well defined so as to describe the path of a process

through the equilibrium state space of a thermodynamic system is termed a process
function or alternatively, a process quantity or a path function.

Example: mechanical work and heat are process functions because they describe
quantitatively the transition between equilibrium states of a thermodynamic system.

Path functions depend on the path taken to reach one state from another. Different routes give
different quantities.

Free energy:

A thermodynamic quantity is the difference between the internal energy of a system and the
product of its absolute temperature and entropy. (The capacity of a system to do work)

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 2

 ENGINEERING CHEMISTRY (18CHE12/22)

Helmholtz free energy: The Helmholtz free energy is a thermodynamic potential that
measures the useful work obtainable from a closed thermodynamic system at a constant
temperature and volume

The Helmholtz energy is given by

A = U - TS

Where

A is the Helmholtz free energy

U is the internal energy of the system
T is the absolute temperature (kelvins) of the surroundings, modelled as a heat bath,
S is the entropy of the system

Gibbs free energy:

The Gibbs free energy also known as free enthalpy is a thermodynamic potential that can be
used to calculate the maximum of reversible work that may be performed by a
thermodynamic system at a constant temperature and pressure

Gibbs free energy is given by

G (p,T) = U+ pV – TS

OR

G (p,T) = H – TS

Where:
p is pressure

V is volume
T is the temperature
S is the entropy
H is the enthalpy
U is the internal energy

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 3

 ENGINEERING CHEMISTRY (18CHE12/22)

Enthalpy: A thermodynamic quantity equivalent to the total heat content of a system. It is

equal to the internal energy of the system plus the product of pressure and volume.

Entropy: A thermodynamic quantity representing the unavailability of a system's thermal

energy for conversion into mechanical work, often interpreted as the degree of disorder or
randomness in the system.

The relation between Entropy and Gibbs free energy, ΔG = ΔH - TΔS

Laws of thermodynamics:

First law of thermodynamics (law of conservation of energy): the first law of

thermodynamic states that the total energy of an isolates system is constant. Energy can
transfer from one form to another form, but can neither be created nor be destroyed.

Second law of thermodynamics: The second law of thermodynamics states that the
total entropy of an isolated system can never decrease over time. The total entropy of a
system and its surroundings can remain constant in ideal cases where the system is
in thermodynamic equilibrium

Third law of thermodynamics: The third law of thermodynamics is sometimes stated as

follows, regarding the properties of closed systems in thermodynamic equilibrium.
The entropy of a system approaches a constant value as its temperature approaches absolute
zero.

Electrochemistry: It is the branch of chemistry, which deals with the study of inter
conversion of electrical energy into chemical energy that takes place through oxidation-
reduction reactions.

Electrochemical cell: The device which converts chemical energy into electrical energy and
electrical energy into chemical energy are called electrochemical cells.

Cell potential (Ecell): The cell potential is the measure of the potential difference between
two half cells in an electrochemical cell. The potential difference is caused by the ability of
electrons to flow from one half cell to the other.

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 4

 ENGINEERING CHEMISTRY (18CHE12/22)

Derivation of Nernst equation for single electrode potential:

The equation for single electrode potential was developed by Nernst in the year 1889 and is
called Nernst equation.

Nernst equation relates the electrode potential of the metal to the concentration of metal ions,
standard reduction potential and temperature. It is derived on the basis of thermodynamic
principles.

If we consider the metal M immersed in the salt solution of concentration 𝑀𝑛+

For the reversible reaction 𝑀𝑛+ + 𝑛𝑒 − → 𝑀

The change in free energy is given by the Vant Hoff’s reaction isotherm as

∆𝑮 = ∆𝑮𝟎 + 𝑹𝑻 𝒍𝒏𝑲 … … … … … … … . . (𝟏)

Where G –Free energy change, Go – Standard free energy change

R - Universal gas constant, T - Temperature

K – Reaction quotient

Product of molar concentration of products [𝑀]

𝐾= = 𝑛+
Product of molar concentration of reactants [𝑀 ]

Decrease in free energy represents the maximum work done.

−∆𝐺 = (𝑊𝑜𝑟𝑘 𝑑𝑜𝑛𝑒)𝑚𝑎𝑥𝑖𝑚𝑢𝑚

Work done = Total electrical energy

=Energy available per Coulomb x total charge in coulomb

𝑊𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 = 𝐸 × 𝑛 𝐹

−∆𝐺 = 𝑤𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 = 𝑛 𝐹 𝐸

−∆𝐺 = 𝑛 𝐹 𝐸

Under standard conditions

−∆𝐺 0 = 𝑛 𝐹 𝐸 0

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 5

 ENGINEERING CHEMISTRY (18CHE12/22)

Equation (1) can be written as

−𝑛𝐹𝐸 = −𝑛𝐹𝐸 0 + 𝑅𝑇 ln 𝐾

𝑅𝑇
𝐸 = 𝐸 0 − 𝑛𝐹 ln 𝐾 (Divide by –nF)

2.303𝑅𝑇
𝐸 = 𝐸0 − log10 𝐾 … … … … (2)
𝑛𝐹
[𝑀]
But 𝐾 = [𝑀𝑛+]

Substitute the value of K in eqn (2)

2.303𝑅𝑇 [𝑀]
𝐸 = 𝐸0 − log10 𝑛+
𝑛𝐹 [𝑀 ]

M is a metal & [M] =1

2.303𝑅𝑇 1
𝐸 = 𝐸0 − log10 𝑛+
𝑛𝐹 [𝑀 ]

𝟐. 𝟑𝟎𝟑𝑹𝑻
𝑬 = 𝑬𝟎 + 𝐥𝐨𝐠 𝟏𝟎 [𝑴𝒏+ ] … … … … … … … (3)
𝒏𝑭

Substitute the standard value of T, R and F in the equation (3)

T = 298k, R = 8.314J/k/mol, F = 96,500C

2.303𝑅𝑇 2.303 × 298 × 8.314

=
𝐹 96,500

= 0.0591

𝟎.𝟎𝟓𝟗𝟏
Equation (3) becomes 𝑬 = 𝑬𝟎 + 𝐥𝐨𝐠 𝟏𝟎 [𝑴𝒏+ ]………….(4)
𝒏

Equation (4) is called Nernst’s equation for single electrode potential

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 6

 ENGINEERING CHEMISTRY (18CHE12/22)

Numerical problems on E, E0, and Ecell:

1) The standard reduction electrode potential , E0 of copper is 0.34 V and the concentration of
Cu2+ ion is 0.015 M. find (i) reduction electrode potential E of copper and (ii) free energy
change of electrode reaction.

Given data:

E0 Cu2+/ Cu = 0.34 V

[Cu2+] = 0.015M

The reduction electrode reaction: Cu2+ + 2e- → Cu

0.0591
E = E0 + log10 [Cu2+]
n

0.0591
E = 0.34 + log10 [0.015]
2

Ecell = 0.296 V

∆𝑮 = −𝒏 𝑭 𝑬
n = 2 mol, E = 0.296 V, F = 96500 C/mol

∆G = −[2 X 96500 X 0.296]

∆𝐆 = −𝟓𝟕. 𝟏𝟑𝐤 𝐉/𝐦𝐨𝐥

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 7

 ENGINEERING CHEMISTRY (18CHE12/22)

2) The EMF of cell, Cd / Cd++ (0.01 M) // Cu++ (0.5M) / Cu is 0.79 V. determine the
standard reduction potential of Cd electrode , if the standard electrode potential of Cu
is 0.34 V

Given data:

E0 Cu++/Cu = 0.34 V

E = 0.79 V

[Cd] = 0.01

[Cu] = 0.5

0.0591 M n+ at anode
E = E0 + log10 [ n+ ]
n M at cathode

0.0591 [Cd]
E = E0 + log10 [ ]
n [Cu]

0.0591 [0.01]
E = 1.22 + log10 [ ]
2 [0.5]

= 0.79 – 0.05

= 0.74 V.

E0cell = E0 cathode – E 0 anode

E0cell = E 0 Cu++ /Cu – E 0 Cd++/Cd

E 0 Cd++/Cd = 0.34 – 0.74

= -0.40 V.

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 8

 ENGINEERING CHEMISTRY (18CHE12/22)

3) Calculate the reduction electrode potential of copper when it is contact with 0.5M
copper sulphate solution at 298 K. The E0 value of copper is 0.34V

Given data:

E0 Cu++/Cu = 0.34 V

[Cu] = 0.5M

The reduction electrode reaction of copper

Cu2+ + 2e- → Cu

0.0591
E = E0 + log10 [Cu2+]
n

0.0591
E = 0.34 + log10 [0.5]
2

= 0.34+0.002

= 0.342V

4) A cell is fprmed by dipping a nickel rod in 0.01M nickel sulphate solution and lead
rod in 0.5M lead sulphate solution. The standard electrode potential of Ni and Pb are -
0.24V and -0.13V respectively. Write the cell representation, cell reaction and
calculate the EMF of the cell. If E0 Pb++/Pb > E0 Ni++/Ni
Given data:

E0 Ni++/Ni = -0.24 V

E0 Pb++/Pb = -0.13 V

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 9

 ENGINEERING CHEMISTRY (18CHE12/22)

[Ni] = 0.01M

[Pb] = 0.5M

Cell representation: Ni / Ni++ (0.01 M) // Pb++ (0.5M) / Pb

Cell reaction: At anode: Ni → Ni2+ + 2e-

At cathode: Pb2+ + 2e- → Pb

E0cell = E0 cathode – E 0 anode

E0cell = E 0 Pb++/ Pb – E 0 Ni++/ Ni

E 0 Cd++/Cd = -0.13 – [-0.24]

= 0.11V.

0.0591
0
M n+ at anode
E=E + log10 [ n+ ]
n M at cathode

0.0591 [Ni]
E = E0 + log10 [ ]
n [Pb]

0.0591 [0.01]
E = 0.11 + log10 [ ]
2 [0.5]

= 0.11- [-0.00922]
= 0.12 V

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 10

 ENGINEERING CHEMISTRY (18CHE12/22)

Electrochemical system:
Reference electrode: These are the electrodes whose potentials are known and are used for
the determination of potentials of other electrodes.

Types of reference electrodes

Reference electrodes are of two types

1) Primary reference electrodes 2) Secondary reference electrodes.

Primary reference electrodes: These are the electrodes whose potential is arbitrarily taken
as zero and used to measure the potential of another electrode.

Example: Standard hydrogen electrode (SHE)

Limitations of Primary Reference Electrode

1) It is difficult to maintain H+ ion concentration as 1M.

2) It is difficult to maintain hydrogen gas at 1 atmosphere at the interface of platinum
electrode.
3) Impurities present in hydrogen gas may poison the platinum electrode which alters the
potential values.
4) It cannot be used in the presence of oxidizing agent.

Secondary reference electrodes: whose potential with respect to SHE are known and are
commonly used for determination of the electrode potentials of the other electrodes.

Example: Calomel electrode and Ag/AgCl electrode.

Construction and working of calomel electrode:

Platinum w ire

Salt bridge

Saturated KCl solution

Hg 2Cl 2 + Hg paste
Mercury (Hg)

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 11

 ENGINEERING CHEMISTRY (18CHE12/22)

• The calomel electrode consist of narrow glass tube

• The bottom of which as a layer of mercury followed by a paste of Hg and Hg2Cl2
• The remaining portion of glass tube is filled with saturated KCl solution
• A platinum wire is dipped into the mercury layer for electrical contact
• The calomel electrode is represented as Hg Hg 2Cl 2 . KCl (aq)

The calomel electrode can act as anode or cathode depending on the nature of the other
electrode of the cell

When it acts as anode the electrode reaction is

2+ -
2Hg Hg 2 + 2e
2+ -
Hg 2 + 2 Cl Hg 2Cl 2
2Hg + 2Cl- Hg 2Cl 2 + 2e
-

When it acts as cathode the electrode reaction is

2+ -
Hg 2 + 2e 2Hg
2+ -
Hg 2Cl 2 Hg 2 + 2 Cl
- -
Hg 2Cl 2 + 2e 2Hg + 2 Cl
The electrode potential is given by

0.0591
𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙 = 𝐸 0 − log[𝐶𝑙 − ]2
𝑛

0.0591
𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙 = 𝐸 0 − 2 log[Cl− ]
2

𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙 = 𝐸 0 − 0.0591 log[Cl− ]

The potential of the calomel electrode depends on the concentration of the KCl solution.

Concentration of KCl E0 Calomel

0.1M 0.33V
1M 0.281V
Saturated 0242V

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 12

 ENGINEERING CHEMISTRY (18CHE12/22)

Application:

1) It is used as secondary reference electrode in the determination of electrode potential

2) Used as reference electrode in potentiometric determination
3) Used as reference electrode in PH determination

Advantages

➢ It is simple to operate.
➢ The cell potential is reproducible and constant over a long period.
➢ The cell potential does not vary with temperature.

Ion selective electrode:

Definition: Ion selective electrodes are the electrodes that respond to certain specific ions
present in solution containing mixture of ions and they develop potential due to the presence
of these specific ions by ignoring the presence of other ions in the solution.

Uses:

➢ Determination of concentration of number of cations such as K+, Ca2+, Mg2+, Ag+, Cd2+,
Pb2+,Cu2+.
➢ Concentration of anions such as NO3-, CN-, S2- & halide ions.
➢ Determination of pH of a solution.
➢ Concentration of gas using gas sensing electrodes.
Glass electrode:

Principle:

glass bulb Gel lay er of the

glass membrane

External solution
Internal solution
concentration (C2) concentration (C1)

E2 E1

E b= E 2 -E 1

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 13

 ENGINEERING CHEMISTRY (18CHE12/22)

A thin walled glass bulb containing an acid is immersed in another solution as shown in the
figure. A potential is developed across the glass membrane. This is called boundary potential
(Eb). The potential is due to the difference in potential (E2-E1) developed across the gel layer
of the glass membrane between two liquids.

𝐸𝑏 = 𝐸2 − 𝐸1

𝑅𝑇 𝑅𝑇
𝐸𝑏 = 𝑙𝑛𝐶2 − 𝑙𝑛𝐶1 … … … … … (1)
𝐹 𝐹

Where C1 & C2 are the concentration of H+ ions of the acid solution inside and outside the
glass bulb respectively.

The concentration C1 of the solution inside the bulb is constant. Hence second term on the
right hand side of the equation (1) is constant.

𝑅𝑇
𝐸𝑏 = 𝑙𝑛𝐶2 + 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝐹

𝑅𝑇 𝑅𝑇
𝐸𝑏 = 𝑙𝑛𝐶2 + 𝐾 𝑊ℎ𝑒𝑟𝑒 𝐾 = − 𝑙𝑛𝐶1 𝑖𝑠 𝑎 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝐹 𝐹

𝑅𝑇
𝐸𝑏 = 𝐾 + 𝑙𝑛𝐶2
𝐹

𝐸𝑏 = 𝐾 + 0.0591 𝑙𝑜𝑔𝐶2

K is a constant which depends upon the pH of the solution taken in the bulb and glass
electrode assembly.

Since C2 = [H+] of the solution.

−log[𝐻 + ] = 𝑃𝐻

𝐸𝑏 = 𝐾 − 0.0591log[𝐻 + ]

𝐸𝑏 = 𝐾 − 0.0591𝑃𝐻

Construction of Glass electrode

The glass electrode consists of a long glass tube with a thin walled bulb at one end of the
glass electrode as shown fig. The composition of the glass used in glass electrode is Na2O
22%, CaO 6% & SiO2 72%. It has low m.p, high electrical conductance & can sense
hydrogen ions up to pH 9. The bulb contains 0.1M HCl. An Ag/AgCl electrode (internal

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 14

 ENGINEERING CHEMISTRY (18CHE12/22)

reference electrode) is placed in the solution and connected by a platinum wire for electrical
contact.

The electrode is represented as

Ag AgCl . KCl (aq) HCl glass

(0.1M)

0.1M HCl Ag / AgCl

Glass membrane

Working of Glass Electrode

When the glass electrode is dipped in the test solution, the Na+ ions of the glass membrane
are exchanged for H+ ions of the test solution.
+ + - + + -
H + Na Gl Na + H Gl
solution glass solution glass membrane
membrane

The boundary potential established due to the above reaction is mainly responsible for the
glass electrode potential EG. The potential of the glass electrode is given by

𝐸𝐺 = 𝐸𝑏 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙

When two solutions are of the same concentration then C1=C2, Eb=0. However it has
observed that even when C1=C2 a small potential is developed this is called asymmetric
potential (Easy). Hence above equation can be written as

𝐸𝐺 = 𝐸𝑏 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝑎𝑠𝑦

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 15

 ENGINEERING CHEMISTRY (18CHE12/22)

𝐸𝐺 = 𝐾 − 0.0591𝑃𝐻 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝑎𝑠𝑦

EG = E0G – 0.0591PH

Where, E0G = k+ 𝐸𝐴𝑔 + 𝐸𝑎𝑠𝑦

𝐴𝑔𝐶𝑙

Advantages:
➢ Glass electrode can be used in the presence of strong oxidizing or reducing agents or
metal ions.
➢ Not poisoned easily.
➢ Simple to operate
➢ Can be used in portable instruments.

Determination of PH of a Solution Using Glass Electrode:

The glass electrode is immersed in the solution whose PH is to be determined. It is combined

with a reference electrode such as a calomel electrode through salt bridge.

The cell assembly is represented as

H
Hg HgCl 2 KCl(aq) solution of unknow n P glass HCl AgCl /Ag
(0.1M)

The emf of a given cell is measured using an electronic voltmeter.

It does not function satisfactorily in pure alcohol

Emf of the cell is given by

Ecell = EG − ESCE

Ecell = L1 − 0.0591P H − ESCE

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 16

 ENGINEERING CHEMISTRY (18CHE12/22)
L1 − ESCE −Ecell
PH = 0.0591

𝐊−𝐄𝐜𝐞𝐥𝐥
𝐏𝐇 = … … … … . . (𝟏)
𝟎.𝟎𝟓𝟗𝟏

Where K is another constant is equal to L1-ESCE called glass electrode assembly constant.

In order to evaluate K, a solution of known PH is used & the potential of cell is measured.

H
P meter

Glass
calomel
elec trode
elec trode

Buf f er solut ion

or
Test s olution

Electrolyte concentration cell:

Definition: A concentration cell is an electrochemical cell in which both anode & cathode are
made up of the same element in contact with solution of the same electrolyte but of different
concentrations.
Ex: A cell in which both the electrodes are made up of copper metal dipped in copper
sulphate solution of different concentrations.
- -
e e
-
- e
e voltmeter
Anode (-) (+)Cathode
Copper rod
Copper rod saturated KCl sol n
+
Ag ar ag ar
g el Salt bridge

2+ 2+
[Cu ] =C1 [Cu ] =C2

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 17

 ENGINEERING CHEMISTRY (18CHE12/22)

The cell notation is given by

Cu(s)/Cu2+ (C1)//Cu2+ (C2)/Cu
Where C1 and C2 are the molar concentrations of Cu2+ ions in the two half cells.
The half cell reactions are
The net cell reaction is obtained by adding the two half cell reactions

2+ 2+
Cu Cu
(C 2) (C 1 )

2+ -
At anode Cu(s) Cu + 2e (oxidation)
(C 1)
2+
At cathode Cu Cu (reduction)
(s)
(C 2)

Emf of the cell is given by

Ecell = ER − EL

0.0591 0.0591
Ecell = [E 0 + logC2 ] − [E 0 + logC1 ]
n n

0.0591 0.0591
Ecell = [ logC2 − logC1 ]
n n

𝟎. 𝟎𝟓𝟗𝟏 𝐂𝟐
𝐄𝐜𝐞𝐥𝐥 = 𝐥𝐨𝐠
𝐧 𝐂𝟏

It may be noted that the term Eo does not appear in the final equation. The following
conclusions are drawn from the equation.
1) When the two solutions are of the same concentration log C2/C1=0 and hence no
current flows through the cell.
2) When C2>C1 then logC2/C1 = +ve & hence E is positive, thus the direction of the
spontaneous reaction is from the more concentrated solution (C2) to less concentrated
solution (C1).
3) Higher the ratio of C2/C1 higher the value of cell potential.

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 18

 ENGINEERING CHEMISTRY (18CHE12/22)

Numerical problems:

1) Calculate emf of the following concentration cell at 250 C Ni (S) / Ni++ ( 0.01M) //
Ni++ ( 0.1M) / Ni (S)
Where, (M2) > (M1)

0.0591 C2
Ecell = log
n C1

0.0591 Mn + at cathode
Ecell = log
2 Mn + at anode

0.0591 0.1
Ecell = log
n 0.01

= 0.02955V
2) Calculate emf of the following concentration cell at 250 C Cu (S) / Cu++ (0.05M)
//Cu++ (5M) / Cu (S)
Where, (M2) > (M1)

0.0591 C2
Ecell = log
n C1

0.0591 5
Ecell = log
n 0.05

= 0.0591V

3) The emf of cell, Cu / Cu2+(0.01M) / Cu2+(X) / Cu, is 0.0595V. Determine the value of
X
Given, Ecell = 0.0595
n= 2
C1= 0.01
C2 = X

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 19

 ENGINEERING CHEMISTRY (18CHE12/22)

0.0591 C2
Ecell = log
n C1

0.0591 X
Ecell = log
n 0.01

0.0591 X
0.0595 = log
2 0.01

0.0595= 0.02955 log [ X / 0.001]

0.0595/ 0.02955= log [ X / 0.001]

2.0135= log [ X / 0.001]

Antilog (2.0135) = X / 0.001

X= 0.103M

Energy storage system:

Introduction:

With all the new applications to which have developed over the past few decades, the market
for consumer batteries in the form of energy storage system has grown correspondingly.
Many of these batteries are of advanced design and construction, giving greatly improved
performance as a result of developments in the field of material science and technology.

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 20

 ENGINEERING CHEMISTRY (18CHE12/22)

Battery:

Definition: “A Battery is an electrochemical cell or often several electrochemical cells

connected in series that can be used as a source of direct electric current at a constant
voltage.”

Components of Battery: The cell consists of three major components.

1.The anode: The anode selected with the following properties in mind; efficiency as a
reducing agent, high coulombic output (Ah/g) good conductivity , stability ease of fabrication
and low cost .

2. The Cathode: The cathode must be an efficient oxidizing agent, be stable when in contact
with the electrolyte and have a useful working voltage.

3. Electrolyte: It provides the medium for transfer of ions inside the cell between the anode
and cathode. The electrolyte must have good ionic conductivity.

The battery itself can be built in many shapes and configuration: cylindrical, button and flat.

CLASSIFICATION OF BATTERIES.

The batteries are classified as

1.Primary battery or primary cells: A primary cell is the one in which electrical energy can be
obtained at the expense of chemical energy only as long as the active materials are still
present . i.e cells in which the cell reaction is not completely reversible. These are not
rechargeable and once discharged have no further electrical use.

Ex: dry cell or Zn-MnO2 Cell

2. Secondary battery: The cell reaction occurring in secondary cells is reversible and these are
rechargeable. They are also referred to as storage cells.

Ex: Lead storage cell and nickel cadmium cell.

3. Reserve Batteries: In these batteries, a key component is separated from the rest of the
battery prior to activation. Usually the electrolyte is the component that is isolated. In this
condition, chemical deterioration or self- discharge is essentially eliminated and the battery is
capable of long- term storage.

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 21

 ENGINEERING CHEMISTRY (18CHE12/22)

Ex: Magnesium water activated batteries, zinc –silver oxide batteries etc.

NICKEL-METALHYDRIDE BATTERY:

The rechargeable sealed nickel metal hydride battery is similar to those of the nickel –
cadmium battery. The principal difference is that the nickel –metal hydride battery uses
hydrogen, adsorbed in a metal alloy for the active negative material in place the cadmium
used in the nickel-cadmium battery.

The active material at the cathode of the nickel –metal hydride battery, is nickel
oxyhydroxide and at the anode is hydrogen in the form of a metal hydride. This metal alloy is
capable of undergoing a reversible hydrogen adsorbing, desorbing reaction as the battery is
charged and discharged.

Anode: Hydrogen in the form of a MH

Cathode: Nickel oxyhydroxide

Electrolyte: KOH

An aqueous solution of potassium hydroxide is the major component of the electrolyte.

The cathode in the cylindrical nickel –metal hydride cell is a highly porous sintered, or felt
nickel substrate into which the nickel compounds are impregnated or pasted and converted
into the active material by electrode deposition. The anode is highly porous structure using a
perforated nickel foil or grid onto which the plastic bonded active hydrogen storage alloy is
coated. The electrodes are separated with a synthetic non -woven material, which serves as an
insulator between the two electrodes and as a medium for absorbing the electrolyte.

Electrode reactions that occurs during discharge are,

At the anode: MH +OH- M +H2O +e-

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 22

 ENGINEERING CHEMISTRY (18CHE12/22)

At the cathode: NiO[OH] + H2O +e- Ni(OH)2 + OH-

The overall reaction on discharge is,

MH +NiO (OH) M +Ni(OH)2

The process is reversed during charge.

The open circuit potential of the cell ranges from 1.25-1.35V.

Application: Used in computers, cellular phones and other portable and consumer electronic
applications where the higher specific energy is desired. They also used in electronic vehicles
Etc.

Advantages:

1. Higher capacity than nickel cadmium batteries.

2. No maintenance required

3. Rapid recharge capabilities.

4. Cadmium free, minimal environmental problems.

5. Long cycle life.

6. Long shelf life.

Disadvantages:

1. High rate performance not as good as with nickel cadmium batteries.

2. Moderate memory effect.

3. Poor charge retention.

Lithium ion battery:

Cathode: A cathode is made up of lithium liberating compounds like Lithium cobaltous oxide
Anode: The anode consist of lithium intercalated graphite

Electrolyte: electrolyte consist of lithium salt in an organic solvent (salt includes LiPF6,
LiBF4 and organic solvents are ethylene carbonate, diethyl carbonate etc)

Seperator: polypropylene

A non-aquoes electrolyte is used because lithium is highly reactive in water.

RASHMI B N/DEP. OF CHEMISTRY/EWCE Page 23