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Module 2

ELECTROCHEMICAL ENERGY SYSTEMS


(Electrode potential& Cells) Lectures: 10hrs

Overview
The lesion plan for the module 2 consist of 10 lectures : we will discuss the topic as follows

Lecture 1 : Single electrode potential ,Standard electrode potential-definition -definition,


Origin of electrode potential, cell notation and sign conventions.
Lecture 2: . Construction of Galvani ccell.classification
Primary, secondary and concentration cells,
Lecture 3 : EMFofacelldefinition,notationandconventions.Referenceelectrodes
Calomel electrode, Ag/AgCl electrode. Derivation of Nernsts equation.
Lecture 4: Measurement of standard electrode potential.Numerical problems on electrode potentials and
EMF.
Lecture 5: Ion-selective electrode-glass electrode, determination of pH using glass electrode
Lecture 6: Electrochemical Energy Conversion and Storage: Battery technology and fuel cells: Basic
concepts, battery characteristics. Classification of batteriesprimary, secondary and reserve
batteries
Lecture 7 .State of heart BatteriesConstruction working and applications of ZnMnO 2, Lithium-
MnO2
Lecture 8:, Zn-air lead-acid, Nickel-Metal hydride and Lithiumion batteries,
Lecture 9 Fuel Cells Introduction, types of fuel cells Alkaline, Phosphoric acid and Molten carbonate
fuel cells. Solid polymer electrolyte and solid oxide fuel cells.

Lecture 10 : Construction and working of H2O2 and Methanol-Oxygen fuel cell.

TEXT BOOKS :
T1. Engineering Chemistry, Mahesh B,,Roopashree B,Suba Ramesh,Jayanna B K., 1 st edition , 2010
T2. Chemistry for Engineering Students, Jai Prakash B S, Venugopal, R,Shivakumariah, Pushpa Iyengar,2013

REFERENCE BOOKS :
R1. Engg.Chemistry by M.M.Uppal, Khanna publishers,Sixth edition ,2001
R2. A text book of Engg .Chemistry by Jain and jain , Dhanpat rai Publications, New -Delhi.
R4. Principles of Physical Chemistry , by Puri , Sharma, Pathania, VPC publications,1962

Video links :
http://ocw.mit.edu/courses/chemistry/5-111-principles-of-chemical-science-fall-
2008/video-lectures/lecture-25/

https://www.youtube.com/watch?v=0oSqPDD2rMA

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Objectives
The 10 lectures of electrochemical energy systems (Electrode potential& Cells) will make you
to understand clearly about the following points
how the electric current generate in galvanic cell through redox reaction ,
what is emf and how it created in cell,
what is the use of Nernest equation and its derivation
How to measure the pH of solution using cell potential concept

Introduction
Electrochemistry: It is a branch of chemistry which deals with the study of transformation of
chemical energy into electrical energy and vice versa

Electrochemical cells:An electrochemical cell is a device which converts chemical energy into
electrical energy or electrical energy into chemical energy

Galvanic Cell:It is an electrochemical cell which converts chemical energy into electrical energy
spontaneously.
Example-Dry cell, Lead-acid cell, Ni-Cd cell etc.

Electrolytic Cell:It is an electrochemical cell which converts electrical energy into chemical
energy.

Lecture 1 :
Single electrode potential-definition, origin, sign conventions.

Objectives

By the end of this lecture, you will be able to understand:


The definition of single and standard electrode potential, origin of electrode potential.
How a redox reaction produces an electric current in a galvanic cell?
How emf arises in a cell?

Introduction:
In this lecture you will be introduced to importance of electro chemistry, definition and
origin of
single electrode potential, standard electrode potential- sign conventions.

SINGLE ELECTRODE POTENTIAL (E):


It can be defined as the potential developed at the interface between the metal and solution,
when it is in contact with a solution of its own ions
OR

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Single electrode potential is a measure of tendency of a given half-cell reaction to occur as
reduction, when it is in equilibrium with the other half cell

Standard reduction potential (Eo):


Standard electrode potential is the electrode potential when the electrode is in contact with a
solution of unit concentration; at 298K.If the electrode involves a gas then the gas at one
atmosphere pressure

Origin of single electrode potential:

M M

+ - - +
+ - - +
+ - - +
+ - - +
- +

Electrical double layer or Helmohltz double layer

When a metal rod is in contact with a solution of its ions, two types of reactions are possible. The
metal shows the tendency to go into the solution as metal ion by losing electrons
M Mn+ +ne-
Simultaneously, ions from the solution tend to deposited as metal atoms.
Mn+ +ne- M
These two opposite tendencies will result in an equilibrium represented by the equation.
Mn+ +ne- M

There are two possibilities for the position of equilibrium.

i).Suppose at equilibrium the forward reaction has occurred to a greater extent than the backward
reaction. As a result the electrode surface develops a layer of +ve charges, which attracts a layer
of vely charged ions at the interface developing an electrical double layer or Helmholtz double
layer.
ii).If the backward reaction has occurred to a greater extent than the forward reaction at
equilibrium electrode develops a layer of ve charges, which attracts a layer of +vely charged
ions at the interface, again establishing an electrical double layer or Helmholtz double layer.
Formation of Helmholtz double layer gives rise to a potential difference across the layer. This
potential difference between the metal and the solution at the interface is the single electrode
potential

Sign Convention of Cell Potential:

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When a electrode is connected to the Std. Hydrogen electrode to form a cell, if the electrode
potential is equal to the

1) Negative sign on the cell potential, then it indicates that the electrode acts as anode by
releasing electrons to the hydrogen electrode.
2) Positive sign on the cell potential, then it indicates that the electrode acts as cathode
and accepts the electrons from the hydrogen electrode.

Summery

Electrochemical cells are those, which convert chemical energy into electrical energy and vice
versa. These cells are classified as electrolytic and galvanic cell. Galvanic cell converts chemical
energy into electrical energy and further classified as primary, secondary and concentration cells.

End of Lecture

Lecture 2: .
Construction of Galvani ccell.classification Primary, secondary and
concentration cells

Objective

By the end of this lecture, you will be able to understand:


How a redox reaction produces an electric current in a galvanic cell?
How emf arises in a cell?
What are different types of electrochemical cell?
Introduction:
In this lecture you will be introduced to importance of electro chemistry, definition and
origin of electrode potential in galvanic cell

Galvanic cells: The Daniel cell is an example of a galvanic cell. It consists of a zinc rod
dipped in a 1M ZnSO4.This forms one half cell. A copper rod dipped in a 1M CuSO 4
constitutes the other half cell. These two electrodes are connected internally by salt
bridge and externally connected through a voltmeter. The Daniel cell is based on the
redox reaction.
e-

Salt bridge

+
- Copper
Zinc
Anode Cathode

ZnSO4 CuSO4
Solution Solutio

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Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
At the zinc electrode zinc goes into the solution as Zn 2+ ions liberating electrons i.e. at zinc
electrode oxidation takes place
Zn Zn2+ + 2e-

At copper electrode reduction of Cu2+ ions takes place with the deposition of metallic copper on
copper rod by gaining electrons, i.e. at copper electrode reduction takes place
Cu2+ + 2e- Cu

By IUPAC convention the electrode at which oxidation takes place is anode and the electrode
where the reduction occurs is cathode.
In Daniel cell, zinc electrode is anode and copper electrode is cathode

Classification of galvanic cells:

1. Primary galvanic cell- In which the cell reaction is not completely reversible i.e. irreversible.
Example:-Dry cell.
2. Secondary galvanic cell- In which the cell reaction is reversible i.e. theyare rechargeable.
Example:-Lead-acid battery, Ni-Cd battery etc.

3. Concentration cells:

It is a type of galvanic cell, consists of two identical electrodes in contact with its salt solution of
different concentration.
The cell potential is due to difference in the concentrations of the metal ions, hence called
concentration cell.
The electrode with lesser concentration of metal ions behaves as anode and with higher
concentration of metal ions acts as cathode.
Oxidation occurs at the electrode containing lower concentration of the electrolyte and reduction
occurs at the electrode having higher concentration of electrolyte. The driving force of these cells
is the difference in concentration.
There is no net chemical reaction in the concentration cell.

A concentration cell is an electrochemical cell in which electrode materials and electrolytes of


two half cells are composed of same material but the concentration of either of them is
different.
Ex- Zn/ Zn 2+ (M1) || Zn 2+ (M2)/ Zn

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Zn rods are dipped in silver nitrate solutions of concentrations C1 and C2
respectively, where C1< C2.
The cell may be represented as: Zn/ Zn 2+ (M1) || Zn 2+ (M2)/ Zn

The electrode reactions are:


At Anode:Zn(s) - Zn2+(C1) + 2e-
At Cathode: Zn2+(C2) + e- -
Zn(s)
The EMF of the above cell is:
Ecell = Ecathode - Eanode
2.303RT 2.303RT
Ecell log(C2 ) log(C1)
nF nF
2.303RT C
Ecell log 2
nF C1
0.0591 C
Or Ecell log 2
n C1
at 298 K

Summary

Electrochemical cells are those, which convert chemical energy into electrical energy and vice
versa. These cells are classified as electrolytic and galvanic cell. Galvanic cell converts chemical
energy into electrical energy and further classified as primary, secondary and concentration cells.

End of Lecture

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Lecture 3 :
EMFofacelldefinition,notationandconventions.Referenceelectrodes
Calomel electrode, Ag/AgCl electrode. Derivation of Nernsts equation

Objective
By the end of this lecture, you will be able to understand:
The quantitative relationship between free energy change and potential of an electrode.
The use of Nernst equation to calculate the potential of an electrode and reference
electrode
The different types of electrodes, reference electrode its limitations and need for
developing secondary reference electrode.

Introduction:
In this lecture we study the origin of electrode potential and we derive the Nernst
equation and explain how it is used to calculate the potential of an electrode
We will be introducing different types of electrodes and we define a reference electrode,
SHE, its limitations and need for secondary reference electrode.

EMF of a cell:Emf is the potential difference between the two electrodes of a galvanic cell,
which causes the flow of current from one electrode to other

Nernst equation for emf of cells:


0.0591 Species.at.Cathode
Ecell E 0 cell . log
n Species.at. Anode

Reference electrode: Reference electrode is an electrode whose potential is known and with
reference to that, the electrode potential of any electrode can be measured.
There are two types of reference electrodes. They are primary and secondary reference
electrodes.
Primary Reference Electrode: It is an electrode, whose potential is arbitrarily taken as zero at all
temperatures. Eg- Standard Hydrogen Electrode (SHE)
Secondary Reference Electrode: It is an electrode, whose potential is known with respect to SHE.
They have several advantages over SHE and it is commonly used for determining the electrode
potential of various electrodes.
Example- Calomel electrode and silver- silver chloride electrode.

Calomel electrode:
Construction:

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It consists of glass tube having a side tube at each end. A small amount of pure mercury is placed
at the bottom of the glass tube and covered by a calomel paste obtained by grinding together Hg,
Hg2Cl2 and either 0.1N KCl or 1NKCl or saturated KCl. The remaining portion is filled with
either 0.1N KCl or 1NKCl or saturated KCl solution. Platinum wire is dipped into the mercury
layer and is used for making electrical contact. The side tube is used for making electrical
contact with a salt bridge.

Calomel electrode canbe represented as,Hg| Hg2Cl2|Cl-.

Working:
Reactions: The electrode behaves either as anode or as cathode
When it behaves as anode, the electrode reaction is:
2Hg (l) + 2Cl- Hg2Cl2(s) + 2e
When it behaves as cathode, the electrode reaction is:
Hg2Cl2(s) + 2e2Hg (l) + 2Cl-
Net half cell reaction is represented as follows Hg 2Cl2 + 2e- 2Hg + 2Cl-
The electrode potential for the half cell is gven as
E = E0 2.303RT log [Hg]2[Cl-]2
nF [Hg2Cl2]
The concentration of Hg and Hg2Cl2 is unity. The no of moles of electrons involved in the
reaction is 2, so n = 2.
By substituting all these in the above equation,
E = E0 2.303RT log 1.[Cl-]2
2F 1
By substituting R, F and at Standard condition, the above equation becomes
E = E0 0.059 log[Cl-] at 298 K
(Nernst equation for calomel electrode)
Hence, the electrode potential of Calomel electrode is dependent on the concentration of chloride
ions and it is reversible with respect to chloride ions.
Concentration of KCl 0.1N 1.0N Saturated
Potential of Calomel Electrode 0.334 V 0.280 V 0.241 V
Advantages:

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It is very simple construction.
It can be used for long time without much attention.
Its electrode potential will not vary with temperature
It is used as referencee electrode

Silver- Silver Chloride electrode


electrode: Silver-Silver chloride is also a metal al-metal salt ion
electrode. It consists of a small sheet of platinum is first coated with silver by the electrolysis of
an argantocyanide solution. Silver is partially converted into AgCl by making it an anode in KCl
solution and passing a current of low density for 30 minutes and it is dipped in a solution of KCl.
A drop of AgNO3 is added to the electrode to avoid the stripping of AgCl from the electrode

Ag/AgCl Electrode can be cell represented as, Ag|AgCl|Cl -

Net half cell reaction is

AgCl + e- Ag + C
Cl-
Electrode Potential E EO
0 . 0591
n

. log M n
E E0
0 . 0591
n

. log Cl Where n 1

E E 0 . 0591 log( Cl ) At 298 K


O

( Nernst Equatation for Ag / AgCl electrode )


Hence, the electrode potential is dependent on the concentration of chloride ions and it is
reversible with respect to chloride ions
ions.
Concentration of KCl 1.0N Saturated
Potential of Ag/AgCl Electrode At 298 K 0.223V 0.199V

Advantages:
Used as a reference electrode in ion
ion-selective
selective electrode such as glass electrode.
Used in determining the uniformity of potential distribution in ships hulls and
underground pipelines.

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Derivation of Nernst equation:
Nernst equation gives a relationship between single electrode potential and standard electrode
potential through concentration of metal ions at a particular temperature.

The decrease in free energy (-G) represents the maximum amount of work that can be obtained
from a chemical cell reaction.
-G = Wmax
Wmax = n F E
Where, n= No of electrons, E=Electrode potential & F= Faraday constant and

At standard condition; -Go= n F Eo


Where, -Go=Decrease in free energy under standard condition, Eo=Standard electrode potential

Consider a reversible electrode reaction of the type,


Mn+ + ne M
The decrease in free energy (G) and its equilibrium constant (K) are interrelated by vant Hoff
isotherm equation as
G G 0 RT . ln K c
Where, Kc= Equilibrium constants = [products] [reactants]

M
Substitute the value of Kc, we have

G G 0 RT . ln
M n

M
Substitute the value of -G &-Go

nFE nFE 0 RT . ln
M n

M
Divide the above equation by nF


RT
E E0 . ln
nF M n
For a solid metal concentration is unity, so that [M]=1


RT 1
Then, we have E E . ln
0

nF M n
E E0
RT
nF

. ln M n


Converting natural logarithm to the base 10 and the equation becomes as
2.303 RT
E E0 . log M n ..1
nF
Substitute the value of R=8.314J/K/mol, T=298K, F=96500C/mol to the equation (1)

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E E0
2.303 X 8.314 X 298
nX 96500

. log M n
E= E
0 0.0591
n

. log M n
This is the expression for Nernst equation for single electrode at 298k
Summary
The potential difference between the two electrodes is the emf of the cell Nernst equation
is derived, which gives a quantitative relation between electrode potential and
concentration of the electrolyte species involved. And this equation helps to determine
the magnitude of the electrode potential. Cells involve different types of electrodes
depending upon the purpose for which they are used. Reference electrode is those
electrode whose potentials is known.As SHE has its own limitations, secondary reference
electrodes such as calomel and silver-silver chloride electrode are used as reference
electrodes.

End of Lecture

Lecture 4:
Measurement of standard electrode potential. Numerical problems on electrode potentials
and EMF.

Objective
By the end of this lecture, you will be able to understand:
The quantitative relationship between free energy change and potential of an electrode.
The use of Nernst equation to calculate the potential of an electrode.
Introduction:
In this lecture we study the origin of electrode potential and we derive the Nernst
equation and explain how it is used to calculate the potential of an electrode.

Measurement of electrode potential: The absolute electrode potential of single electrode cant
be determined. This is because a single electrode of a cell works only when it is coupled with
another single electrode and doesnt work independently.
Therefore, the electrode potential of a single electrode can be measured by using some reference
electrode whose electrode potential is known. Commonly used reference electrodes are standard
hydrogen electrode, Calomel electrode & Ag-AgCl electrode.In order to measure the electrode
potential of given electrode, it is coupled with reference electrode internally through salt bridge
and externally through electronic voltmeter. Then the valve of emf of cell, E cell is measured
using electronic voltmeter.
Determination of electrode potential Using Calomel electrode:
To measure the electrode potential of any metal, the metal is dipped is in a solution containing its
own ions and connected to the calomel electrode through a salt bridge internally and by
electronic voltmeter externally. Emf of the cell is obtained from electronic voltmeter.

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For example to determine the Std. electrode potential of Zn, the Zn electrode is immersed in 1M
ZnSO4 solution and coupled with saturated calomel electrode as shown below.
Ecell = ERHE ELHE = ECalomel E0Zn2+/Zn
E0Zn2+/Zn = ECalomel Ecell

Net Rxn: Zn + Hg2Cl2 Zn2+ + 2Hg


Note: Similarly the electrode potential of Cu electrode can be determined, where Cu electrode
acts as cathode and Sat. Calomel electrode acts as anode.
Summary

Single electrode potential is measured using SHE as reference electrode and in the alternate
method calomel electrode is used as reference.

Note : Solved problems at the end of module

End of Lecture

Lecture 5:
Ion-selective electrode-glass electrode, determination of pH using glass electrode

Objective
By the end of this lecture, you will be able to understand:
Ion selective electrodes definition we study glass electrode in detail and then determine
the pH of a solution using glass electrode.
Introduction:
In this lecture we discuss ion selective electrode, its definition taking glass electrode as example
its construction, working, electrode reaction, advantages and limitation are studied in detail and
glass electrode is used to determine the pH of a solution

Ion selective electrode: They are the electrode which consists of a thin membrane that is
highly sensitive to specific ions present in the mixture and a potential is developed across the
membrane w.r.t that species in a mixture and ignoring the other ions totally.

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For example: Glass electrode:
Construction: The glass electrode consists of a glass bulb made up of special type of glass
which has low melting point and relatively high electrical conductivity. The glass bulb is filled
with a solution of constant pH (0.1MHCl)and insert with a Ag-AgCl electrode, which is the
Internal reference electrode and also serves for the external electrical contact.

0.1 M Hcl

Ag-AgCl electrode

H+ Ion Solution

Glass electrode

The electrode is representation as, Glass|0.1M HCl|Ag-AgCl

The potential of glass electrode when dipped in a solution containing H + ions, is given by
EG= EGo- 0.0591pH (Since n = 1)

Determination of glass electrode potential:

Principle: When a thin glass membrane is placed between two solutions of different pH values,
a potential difference arises across the membrane, called as boundary potential E b.

The potential difference varies as the pH of these solutions varies. In practice, pH of one of these
solutions is kept constant and therefore the boundary potential depends on pH of the other
solution i.e. experimental solution.

Working: The membrane undergoes an ion exchange reaction, the Na+ ions in the glass
membrane are exchanged for H+ ions in the solution.
H+ + Na+Gl- Na+ + H +Gl-
Solution membrane Solution membrane
Let us consider the glass electrode is filled with HCl solution of concentration C 1, and dipped in
a solution of concentration C2 w.r.t H+ ions, i.e. experimental solution.

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Gel layer of
the glass
Internal solution, memebrane
Conc C1
Glass bulb
External solution, H+ Ion
Conc C2 Solution
E1 E2
E b= E 2- E 1

Then the boundary potential arising across the membrane is given as,
Eb = E2-E1
where E2 and E1 are the potentials outside and inside the membrane respectively.
According to Nernst,
Eb = 2.303RTlog C2
nF C1
Eb = 2.303RTlog C2-2.303RTlog C1
nF nF
Since the HCl solution filled inside the glass membrane is usually 0.1M HCl (C 1) and n is 1, the
above equation at Std temp gets reduced as
Eb = 0.059log C2+ constant
Since C2 is the concentration w.r.t H ions outside the membrane,
+

Eb = 0.059log [H+] + constant, Since pH = -log [H+]


Eb = constant-0.059pH
(Boundary potential for glass electrode)
The glass electrode potential(EG) depends upon three factors 1)boundary potential 2) internal
reference electrode potential (Ag-AgCl) and 3) Asymmetry potential.
EG = Eb + EAg-AgCl + EAsy
Asymmetry potential arises due to the strain involved in the inner and outer surface of the glass
membrane.By substituting the Eb in the above equation, we obtain
EG = constant-0.059pH+ EAg-AgCl + EAsy
Since EAg-AgCl is known and EAsy is constant for a glass electrode, the above equation becomes
EG =EG-0.059pH
where EG (constant value) = constant+ EAg-AgCl + EAsy

Determination of pH using glass electrode:

Procedure: To determine the pH of the given solution the glass electrode is dipped into the
solution. It is combined with a reference electrode such as a calomel electrode through a salt
bridge internally and by electronic voltmeter or potentiometer externally.

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PotentioMeter

Glass
Calomel electrode
electrode

Solution of
unknown pH

The cell assembly is represented as,


Hg| Hg2Cl2|Cl-||Solution of unknown pH|glass|0.1M HCl|Ag+|AgCl
The emf of this cell is determined using potentiometer. The emf of the cell is given by

E cell=Ecathode-Eanode
E cell =Eglass- ESCE 1
E cell = EG- 0.0591 pH -ESCE ----2 (since EG=EGo- 0.0591 pH)
By Rearranging the above equation we obtain,
0.0591 pH = EG- Ecell ESCE ---3
pH = EG- E cell ESCE -------4
0.0591
pH= EG- E cell 0.244
0.0591

Summary
Ion-selective electrode consists of a thin membrane in contact with ionic solution and the electrode
respond to only on specific ion. pH of a solution can be determined using glass electrode as indicator
electrode and calomel electrode as reference electrode.

End of Lecture

Lecture 6:
Electrochemical Energy Conversion and Storage: Battery technology and fuel cells: Basic
concepts, battery characteristics. Classification of batteriesprimary, secondary and reserve
batteries

Objectives
By the end of this lecture, you will be able to understand:
The importance of battery and its basic concepts.
The operation of a battery during discharge and charge.
Introduction:
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In this lecture you will be introduced to battery, which is a galvanic cell and we study
principal components of a battery and we also discuss the operation of a battery during
charging and discharging.

CELL: A cell designates a single unit. The conversion of chemical energy into electrical energy
is a function of cells or batteries.

BATTERY: 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.

Uses: Batteries are used in calculators, watches and pacemakers for heart hearing aids,
computers, car engines, stand by power supplies, emergency lightning in hospitals, electroplating
industrial tractions and military and space applications.

Batteries have revolutionized the telecommunication system and are ushering a new era of
transportation with the possible replacement of petrol driven automobiles by the electrical
powered ones. In modern days portability of electronic equipments in the form of handsets has
been made possible by batteries.

Note: The size of the batteries ranges from a fraction of a cubic centimeter to several cubic
decimeters.

Basic concept; the spontaneous redox reaction, which forms the basis of batteries.

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 : The electrolyte must have good ionic conductivity but not be electrically
conductive. AS this would cause internal short circuiting. Electrolyte should be non reactive with
the electrode materials.
4.Containers: Must be resistance to corrosion from both inside and outside the cell.

OPERATION OF A BATTERY DURING DISCHARGE AND CHARGE.

DURING DISCHARGING: The Battery acts as voltaic cell i.e. oxidation takes place at the
negative electrode (anode) and reduction takes place at the positive electrode (cathode).
During charging the Battery acts as an electrolytic cell. The current flow is reversed and
oxidation takes place at the positive electrode (anode) and reduction takes place at the negative
electrode (cathode).

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COMMERCIAL CELLS: A useful commercial cell should meet the following basic
requirements.
1.portability.
2.Should be compact and lightweight.
3.Should provide economically priced, continuous electric supply.
4.Should be capable of recharging.
5.should have long shelf life.

BATTERY CHARACTERSTICS: The performance characteristics of commercial batteries are


given below.

VOLTAGE: According to Nernst equation at 298k


ECELL=Eocell - 2.303RT/ nF log Q
Where Q= [PRODUCT]/[REACTANT]
The emf of the battery depends on the following factors EOCELL, temperature and the
concentration ratio given by Q.
1.The e.m.f of a battery largely depends on E0CELL i.e E0R E0L the difference in the standard
electrode potentials of the two electrodes. As E0CELL increase the e.m.f also increases for a given
value of Q at constant temperature. In other words, the magnitude of e.m.f is large if the
electrodes used in the cell are far apart in the e.m.f series.
2.Increase in the value of Q marginally decrease the e.m.f . This is because Q decrease
when[products] decreases i.e when current is drawn from the cell.
3.The voltage of the battery depends on the free energy change in the overall cell reaction.
However the Nernst equation is applicable only to reversible systems. A condition for
thermodynamic reversibility is that the system should always be in equilibrium with its
surroundings. Therefore chemical cell behaves reversibly only when the current passing is small.
The system may not behave as a reversible cell if large current are passed since the cell will not
be in a state of equilibrium. The cell reaction selected should have a high negative free energy
change to get a high cell potential. The electrode should be fast and the cell should be designed
with a low internal resistance using high conductivity electrolyte to drive maximum voltage from
the cell.

2.CAPACITY: The capacity is the charge that may be obtained from the battery.It is expressed
in ampere hours and it depends on the size of the battery.
According to faradays law

Capacity C=WnF/M

Where w=weight of the active material.


M=molecular weight of the active material.

It is measured by finding, for a fixed current discharge, the time t taken for the battery to reach a
minimum voltage ,when the cell is said to be dead. A plot of voltage against time at a fixed
current discharge is shown in the fig. The variation of the battery voltage during discharge is
shown by the flatness of the curve. The length of the flat portion of the curve is a measure of the
capacity of the battery. Flatter and longer the curve better is the capacity.

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CURRENT: Current is the rate at which the battery is discharging. For an efficient working of
the cell there must be a large quantity of electro active species that help rapid electron transfer
reaction.
4.Power Density: It is the rate at which the storer is able to release the energy per unit weight.
Power density decreases during discharge.
5.Energy efficiency: Energy efficiency for the storage batteries is given by

energy released on discharge


% of energy efficiency= x 100
energy required for charge

Batteries should have high energy efficiency.


6.Cycle life: is the number of charge and discharge cycles that are possible before failure occurs.
Some of the factors which cause the failure are 1.for a secondary battery it is essential to
charge and discharge cycle to reform the active material in a suitable state for further discharge.
The cycle life depends upon how effectively this is achieved.2.Also depends upon the depth of
each discharge attempts to discharge totally damaging to the electrodes.
The most common form includes corrosion of containers at the contact points.
Shedding of the active materials from the plates.
7.Energy density: This refers to the energy that may be extracted from a given weight of a
substance or device per unit weight.

26.8nv
Energy density=K watt hours/kg
M

8.Electricity storage density: This is a measure of the total current which can be withdrawn
from the unit weight of a substance when it undergoes an electrochemical reaction.
In other words it is the capacity per unit weight i.e. electricity storage density is the amount of
electricity per unit weight which the accumulator can hold. In addition to the above
requirements, the commercial batteries should have long shelf lives, tolerance to different service
conditions such as temperature, vibration and shock.

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.
Egs; dry cell or Zn-MnO2 Cell

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

18
Egs. 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.
Egs: Magnesium water activated batteries, zinc silver oxide batteries etc.

NOTE: the type of activating medium or mechanism that is involved in the activation can
classify the reserve batteries.
1.Water activated batteries: activated by fresh or seawater.
2.Electrolyte activated batteries: activation by the complete electrolyte or with the electrolyte
solvent.
3.Gas activated batteries: activation by introducing a gas into the cell. The gas can be either the
active cathode material or part of the electrolyte.
4.Heat activated batteries: A solid salt electrolyte is heated to the molten condition and becomes
ionically conductive, this activating the cell.
NOTE: In electrolyte cell cathode is negative and anode is positive.
In galvanic cell cathode is positive and anode is negative.

Summary

Battery is a device consisting of two or more galvanic cells it can be used as a source of portable
electrical energy we have discussed the principal components of a battery and the operation of a
battery during charge and discharge.

End of Lecture

Lecture 7
.State of heart BatteriesConstruction working and applications of ZnMnO 2, Lithium-
MnO2

Objectives
By the end of this lecture, you will be able to understand:
The classification of a battery as primary, secondary and reserve batteries with examples.
We study the construction, working and applications of ZnMnO2, Lithium-
MnO2
.
Introduction:
We have classified the battery system as primary, secondary and reserve battery. Primary batteries are
those in which the reactions are not reversible and it cannot be recharged. Secondary batteries are those
in which the reactions are reversible and are rechargeable. Reserve batteries have one of the vital
component is separated from the rest of the battery prior to activation. We are studying in detail the
construction, working and application of a ZnMnO2, Lithium- MnO2

19
CLASSICAL BATTERIES:

PRIMARY CELL:

DRY CELL OR LACLANCHE CELL OR Zn-MnO2:

Zn/ZnCl2, NH4Cl /MnO2, C+


-

The cell consists of a zinc anode shaped as a container for the electrolyte and a carbon cathode
surrounded by MnO2 and a paste of ammonium chloride and zinc chloride as an electrolyte.
Manganese dioxide acts as a
Cathodic depolarizer and facilitates the H+ ion discharge reaction by removing the adsorbed
hydrogen atoms.
Carbon is added to increase the conductivity of manganese dioxide. Ammonium chloride is
added to zinc chloride to ensure high rate performance.

The primary reaction at the anode is


Zn Zn2+ +2e-

The overall cathodic reaction is


MnO2+ H2O+2e- Mn2O3 +2OH-
The net cell reaction is

2MnO2+H2O+Zn Mn2O3 +Zn2+ +2OH-


Some of the secondary reactions are

2NH4Cl +2OH- 2NH3 +2Cl-+2H2O

Zn2+ +2NH3 +2Cl- [Zn(NH3)2]Cl2 OR ZnCl2 .2NH3

20
The voltage of the cell, which is due to primary reactions is about 1.5V.The secondary reactions
consumes the Zn2+ and OH- ions and once the cell has discharged it cannot be charged again.

CELL PERFORMANCE: 1.This cell gives almost constant voltage for small discharge currents.
2.about 80% of the charge stored can be drawn.
3.Though the cell has a long shelf life, natural deterioration sets in.
4.Low temperature will increase the shelf life but the performance efficiency decreases.
5.for higher capacity and longer service life a high % of depolarizer is required, where as for
delivering large current in a short time as in photoflash, a high % of carbon is desirable.

DISADVANTAGES: 1.When current is drawn rapidly from it, products build up on the
electrodes thereby causing drop in voltage.
2. Since the electrolytic medium is acidic, so zinc metal dissolves slowly, thereby the cell
run down slowly, even it is not in use
3. These batteries are not chargeable.
4. Not intended for heavy duty.

Uses: dry cell finds applications in flashlights, transistors, radios, calculators, tape
recorders and similar electronic devices where small amount of current is required.

21
LITHIUM CELLS: Lithium metal is attractive as a battery anode material because of its
lightweight, high voltage, high electrical equivalence and good conductivity. Because of
these outstanding features, the use of lithium has predominated in the development of high
performance primary and secondary batteries.

ADVANTAGES OF LITHIUM CELLS:


1. High voltage.
2. High energy density.
3. Operation over a wide range of temperature. Many of the lithium cells will perform over
a temperature range from about 70-40oC.
4. Good power density.
5. Flat discharge characteristics.
6. Superior shelf life.

CLASSIFICATIONS OF LITHIUM PRIMARY CELLS:

Lithium primary cells can be classified into several categories, based on the type of
electrolyte or solvent and cathode material used.
1.Soluble cathode cells: These cells use liquid or gaseous cathode material, such as sulphur
dioxide or thionyl chloride, that dissolves in the electrolyte or are the electrolyte solvent.
2. Solid cathode cells: Uses solid material for the cathode such as MnO 2, CuS and V2O5
ETC.
3. Solid electrolyte cells: This type of cells use electrolytes in the solid form itself as the
cathode.PbI2, PbS etc

LITHIUM MANGANESE DIOXIDE CELL: Fig. shows the illustration of a typical coin
cell. The manganese dioxide pellet faces the lithium anode disk and is separated by a non-
woven polypropylene separator impregnated with the electrolyte. The cell is seald with the
can serving as the positive terminal and the cap as the negative terminal. The Li/MnO 2 cell
uses lithium for the anode, an electrolyte containing lithium salts in a mixed organic
solvent (propylene carbonate and 1,2-dimethoxyethane) and a specially prepared heat-
treated form of MnO2 for the active cathode material.

The cell reactions for the system are

Anode: Li Li+ + e-

Cathode: MnO2 + Li+ + e- LiMnO2

The overall reaction is Li + MnO2 LiMnO2

Manganese dioxide is reduced from the tetravalent to the trivalent state by lithium. LiMnO 2
signifies that the Li+ ion enters into the MnO2 crystal lattice. The theoretical voltage of the
total cell reaction is about 3.5V.

22
APPLICATIONS: Used as long -term memory backup, safety and security devices,
cameras, lighting equipment and many consumer electronic devices.

Summary

We have classified the batteries as primary, secondary and reserve batteries. Secondary batteries are
storage batteries in which the reactions are reversible and rechargeable. In detail we have discussed the
construction, working and applications of of ZnMnO2, Lithium- MnO2

End of lecture

Lecture 8
lead-acid, Nickel-Metal hydride and Zn-air batteries,

Objectives
By the end of this lecture, you will be able to understand:
The construction, working and applications of classical batteries like lead-acid ,Ni-
Metal hydride battery.
The importance of modern battery and in detail Zn-air battery.
Introduction:
We are studying in detail the construction, working and application of lead-acid
Ni-Metal hydride battery.which is an example of secondary battery. And we also
discuss the importance of modern battery. With modernization, and advancement in
science, engineering and technology the modern battery came into existence. The
modern batteries fulfill the improved performance and advanced characteristics.

23
SECONDARY BATTERIES:

LEAD-ACID BATTERY:

Pb/PbSO4, H2SO4// PbSO4/PbO2/Pb


(s) (s) (s)

It consists of a spongy lead anode and a grid of lead antimony alloy coated with lead
dioxide, as cathode. Both electrodes are dipped in H2SO4 having density 1.25-1.30g/cm3
which is the electrolyte. Additives such as graphite powder, lignin sulphonate and barium
sulphate are added. Graphite powder increases the conductivity and barium sulphate
prevents the reduction in surface area of the lead.

The electrode reactions that occur during the discharge of the cell, i.e when current is
drawn from the cell are

Anode:

Pb Pb2+ + 2e-

Pb2+ + SO42- PbSO4

Pb + SO42 PbSO4 + 2e-

Cathode:

PbO2 +SO42- +4H+ +2e- PbSO4 + 2H20

The net cell reaction is

Pb + PbO2 + 2H2SO4 2 PbSO4 + 2H20


The lead sulphate formed gets precipitated on the cathode and in the solution.
CHARGING: When anode and cathode becomes covered with lead sulphate the cell ceases
to function as a voltaic cell. To re charge a lead storage cell the reactions taking place
during discharge are reversed by passing an external e.m.f greater than 2v from a
generator. The cell acts as an electrolytic cell.

The following reactions takes place are

Reaction at the negative terminal [cathode]

PbSO4 +2e- Pb +SO42-

Reaction at the positive terminal [anode]

24
PbSO4 +2H2O PbO2 +SO42- +4H+ +2e-

Hence the net reaction during charging is

2PbSO4 + 2H20 Pb(s)+ PbO2 (s)+2H2SO4(aq)

The net reaction during charging and discharging can be represented as follows.
Discharging
Pb(s) + PbO2(S) + 2H2SO4 2PbSO4(S) + 2H2O(l)
Charging

During the discharge process the consumption of sulphuric acid is replaced by an


equivalent quantity of water and so as the cell produces electric current the sulpuric acid
concentration decreases. However on charging the reverse reaction takes place. Sulphuric
acid being generated and water consumed. Hence the original acid strength is restored.

CELL PERFORMANCE: These batteries deteriorate during the idle storage due to
shedding of active materials like lead dioxide and lead sulphate. The corrosion of the grid
also occur. This deterioration can be minimized by frequently charging the battery. The
voltage of the cell depends on the concentration of sulphuric acid. The lead sulphate
cloges the pores in the plates and decrease the penetration of the acid. Overcharging leads
to non adhesion and shedding of active materials. Similarly over discharge leads to the

25
formation of hard crystalline lead sulphate, which is non conducting and clogs pores. At
low temperature the rates of electrochemical reactions decrease and the capacity of the
battery to deliver current also decreases.

APPLICATIONS: The lead storage batteries are extensively used in automobiles to start
the engine. They are also used for supplying current for electrical vehicles, gas engine
ignition, in telephone exchanges, railway trains, in laboratories, hospitals, broadcasting
stations, UPS, power stations etc.

ALKALINE STORAGE BATTERY:

NICKLE CADMIUM BATTERY:

It can be represented as
Cd/CdO/KOH(6M)//Ni(OH)3/Ni(OH)2/Ni

Nickle cadmium cell consists of a cell cup made up of steel coated with nickel acts as
cathode and a cell cap in contact with action anodic materials acts as the anode. The active
materials of the anode are spongy Cd with 78% Cd(OH)2 , 18% Fe, 1% Ni and 1% graphite
which are pressed into a tablet form and wrapped in nickel wire gauge. The cathode
contains a mixture of 80% Ni(OH)2 and Ni(OH)3 , 2% Co(OH)2, 18% graphite and traces
of barium compound to increase the efficiency of active materials.

The cell reactions are

At anode: Cd(s) + 2OH-(aq) Cd(OH)2(s) + 2e-

cathode: 2Ni(OH)3 +2e- 2Ni(OH)2 + 2OH-


(s)
The overall reaction is

Cd(s) +2Ni(OH)3 Cd(OH)2 +2Ni(OH)2


(s) (s)

The reaction can be readily reversed because the reaction products Ni(OH)2 and Cd(OH)2
adhere to the electrode surfaces.
Ni-Cd battery is a portable, rechargeable cell and its cell voltage is fairly constant (1.4v). It
can be left for long periods of time without any appreciable deterioration, since no gases
are produced during discharging or charging.

26
USES: It is used in electronic calculators, electronic flash units, cordless electronic shavers,
transistors and other battery powered small tools. Phones, alarms systems, transmitters,
receivers, computers, emergency lighting, hearing aids, telemeter etc.

MODERN BATTERIES:

Zinc air battery:

It is a metal air battery, which use oxygen directly from the atmosphere to produce
electrochemical energy. The air diffuses into the cell, as it is needed. The air cathode acts
only as a reaction site and is not consumed. The zinc air cell consists of an anode, made up
of loose granulated powder of zinc mixed with electrolyte [KOH] and a gelling agent to
immobilize the composite and to ensure adequate electrolyte contact with zinc granules.
The structure includes the separators, catalyst layer, metallic mesh diffusion membrane,
air distribution layer. The catalyst layer contains carbon blended with oxides of manganese
to form a conducting medium. The outer metal acts as the cathode of the battery and a
plastic gasket insulates the anode active materials and the cathode. An air access hole on
the positive terminal of a zinc air cell provides a path for oxygen to enter the cell and
diffuse to the cathode catalyst site. A schematic representation of a typical zinc air cell is
given in fig.

Electrode reaction:

At the anode: Zn Zn2+ +2e-


27
Zn2+ +2OH- Zn(OH)2

Zn(OH)2 ZnO +H2O

Overall reaction: Zn +2OH- ZnO +H2O +2e-

At the cathode: O2+ H2O + 2e- 2OH-

cell reaction : Zn + O2 ZnO

The cell produces an open circuit potential of 1.4v.

ADVANTAGES: 1.High energy density.


2.Flat discharge voltage.
3.Long shelf life.
4.No ecological problems.
5.Low cost.
6.Capacity independent of load and temperature when within operating
range.

DISADVANTAGES: 1.Not independent of environmental conditions.


2.Drying out limits shelf life once opened to air.
3.Short activated life.
4.Flooding limits power output.

28
APLLICATIONS: 1. As a power source for hearing aids, electronic pagers, telemetry
(voice transmitters) portable battery charges, used in medical devices. It is served as a
portable power source for the wireless crew communicator system used by astronauts
aboard the space shuttle.

Nickle metal hydride batteries: 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.
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-

At the cathode: NiOOH + H2O +e- Ni(OH)2 + OH-

The overall reaction on discharge is,

MH +NiOOH M +Ni(OH)2

The process is reversed during charge.


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

ADVANTAGES. 1. Higher capacity than nickel cadmium batteries.


2.No maintenance required.
3. Rapid recharge capabilities.
5. Cadmium free, minimal environmental problems.
6. 5. Long cycle life.
7. 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.

29
APPLICATIONS: 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.

Summary
We have studied in detail the construction, working and applications of Nickel metal
hydride and lead acid battery, which is a secondary battery. We have also discuss about
the importance of modern battery and we have studied in detail the construction, working
and applications of Zincair battery

Lecture 9
Fuel Cells Introduction, types of fuel cells Alkaline, Phosphoric acid and Molten carbonate fuel
cells. Solid polymer electrolyte and solid oxide fuel cells.

Objectives
By the end of this lecture, you will be able to understand:
The importance of fuel cell, the difference between the battery and fuel cell
and types of fuel cells.

Introduction:
At present, motor vehicles account for about one half of the total hydrocarbon and nitrogen oxide
pollution at the global level. The hydrocarbons and oxides of nitrogen combine to form
photochemical smog that pollutes the atmosphere in many towns and cities. Storage batteries were
used to power cars. The large scale manufacture of storage batteries such as Ni-Cd and lead
accumulators lead to the discharges of many toxic chemicals. An electric car equipped with a fuel
cell is the only option to reduce the pollution caused by battery operated motor cars.
Usage of fuel cell reduces oil consumption. Fuel cells are about three times more effective than
any other method of providing electricity on board and hence are used as auxiliary power
generators in space vehicles and this helps to reduce our pollution too.
Fuel cell is defined as a galvanic cell in which electrical energy is directly derived by the
combustion of chemical fuels supplied continuously. A fuel cell differs from a conventional
battery in the following aspects.

FUELS CELLS:
DEFINITION: A fuel cell is an electrochemical device, which can continuously convert
the chemical energy of a reducing agent and an oxidant fuel stored externally by a process
involving an essentially invariant electrode electrolyte system.
A fuel cell consists of two electrodes and an electrolyte. However, the fuel and the
oxidizing agents are continuously and separately supplied to the two electrodes of the cell,
at which they undergo reactions. These cells are capable of supplying current as long as
they are supplied with the reactants.

A fuel cell may be represented as

30
Fuel/electrode/electrolyte/electrode/oxidant

At the anode fuel undergoes oxidation and at the cathode oxidant undergoes reduction.

ADVANTAGES OF FUEL CELL SYSTEM:


1.Savings in fossil fuels due to the high efficiency of electrochemical energy conversion.
2.Low pollution level, no noxious exhaust gases formed.
3.Production of water of drinking quality in hydrogen-oxygen system.
4.only a small number of moving parts.
5.Low noise level.
6.Low maintenance, exchangeable parts.
7.No need of charging.

DISADVANTAGES:
1.High initial cost of the system (catalyst, membranes etc).
2.Large weight and volume of gas fuel storage systems.
3.High price of clean hydrogen.
4.Lifetimes of the cells are estimated but not accurately known (40,000hrs for acidic and
10,000hrs for alkaline cells).
5.Present lack of infrastructure to distribute hydrogen.

Classification of fuel cells:


They are classified as
1.Indirect fuel cells: use organic fuels or biochemical substance, which is decomposed by
using enzymes to a simple fuel like hydrogen.
Egs. Reformer fuel cells and biochemical fuel cells.

2.Direct fuel cells: The products of the reaction are discarded.

Direct fuel cells are classified as


1.Low temperature fuel cell: egs H2-O2, N2 compound O2 and Metal-oxygen fuel cells etc
[<100oc]
2.Intermediate temperature fuel cell: egs. Organic compound - O 2 and H2-O2 fuel cells etc
[100-500oc]
3.High temperature fuel cell: egs. H2-O2, CO-O2 fuel cells etc [500-1000oc]
4.Very high temperature fuel cell: egs, H2-O2, CO-O2 fuel cells etc [> 1000oc]

Classification based on the electrolyte used:

TYPE ELECTROLYTE USED TEMPERATURE


OPERATION OF

1.ALKALINE FUEL Aq. KOH solution 60-120oc


CELL
[AFC]

31
2.POLYMER polymer membrane 60-120oc
ELECTROLYTE
MEMBRANE FUEL
CELL
[PEMFC]
mixture of molten
3.MOLTEN carbonates
CARBONATE FUEL 60-650oc
CELL [MCFC]

4.PHOSPHORIC ACID
FUEL CELL [PAFC] concentrated 180-220oc
phosphoric acid

5.SOLID OXIDE FUEL ceramic solid ZrO2 900-1000oc


CELL (Y2O3)
[SOFC]

ALKALINE FUEL CELL [AFC]: Alkaline fuel cell uses aqueous solution of KOH or
NaOH as electrolyte. Pure oxygen or air is used as the oxidant. The fuels of the cells are
hydrogen or any hydrocarbons. The cell and electrodes can be built from low cost carbon
and plastic.

Reaction: At anode H2 + 2OH- 2H2O + 2e-

At cathode O2 + H2O + 2e- 2OH-

H 2 + O 2 + H2 O 2H2O

Disadvantage: Carbonation of electrolyte by CO2, poisoning of catalyst by CO2.

Advantages: AFC offer the best prospect for usage of non-noble metals catalysts such as
raney Ni and raney Ag etc.

Polymer electrolyte membrane fuel cell [PEMFC]: The cell employs a thin cation-
exchange membrane [polystyrene sulphonic acid mixed with triflouroethylene resin as
plasticizer] as electrolyte. A Ti screen coated with a pt catalyst covers each side of the
rectangular membrane. The electrodes used in this type of cells are typical gas diffusion
electrodes, made of porous carbon and impregnated with platinum catalyst. Hydrogen gas
is supplied at anode and oxygen at cathode.

32
Reaction takes place are
At anode 2H2 4H+ + 4e-

At cathode O2 + 4H+ + 4e- 2H2O

2H2 + O2 2H20

A storage system built of these cells having an average power of 900W and a maximum
power of 2KW was used in the first two mars Gemini spacecraft.

DISADVANTAGES:

1.The water balance is considered to be the main problem.


2.Dehydration of the membrane is a problem therefore complicated cooling systems have
to be used in addition to humidification of feed gases.
3.Reactant gases should be free from CO, as it is a catalytic poison.

ADVANTAGES:
1.Long life.
2.Simple to fabricate the cell.
3.No free corrosive liquid in the cell.
4.Able to withstand large pressure.

MOLTEN CARBONATE FUEL CELL [MCFC]:

Here instead of pure hydrogen and oxygen, CO or natural gas largely methane (as source of
hydrogen) and air (as source of oxygen) are used. Mixed with steam methane is reformed
into hydrogen and carbon monoxide with a Ni catalyst heated to 600-750 oc. The electrolyte
in the form of a paste with MgO is a molten mixture of Li2CO3, Na2CO3 and K2CO3.Mg is
added to increase the conductivity and hold the mixture in the form of paste. A thin layer of
porous Ni is the anode while a finely divided Ag constitutes the cathode.

Reaction:
At anode: CO + CO32- 2CO2 + 2e-

H2 + CO32- CO2 + H2O +2e-

At cathode: 2CO2 + O2 + 4e- 2 CO32-

Single cells are able to sustain current density of 100mA Cm 2 at 0.6-0.7v for continuous
periods of more than one year.

33
ADVANTAGE: Reduction of polarization of oxygen cathode due to high temperature.
However electrode lifetime is short due to high temperature corrosion.

PHOSPHORIC ACID FUEL CELL [PAFC]:

This is based on the immobilized phosphoric acid electrolyte. The cell operated to 180-
220oc and uses air for the source of oxygen. Hydrogen is used as a fuel. The most desirable
fuel system is one, which operates on hydrocarbons directly because of the low cost of the
hydrocarbon fuel. The most important property required for an electrolyte in a cell is that it
must be able to withstand temperature above 100oc. It must posses good electronic
conductivity. It must support complete electrochemical oxidation of carbon containing fuel
cell and it must not contain anion, which must adsorbed on the electrode and block the
reaction site. The electrolyte, which satisfies several of these criteria, is concentrated
phosphoric acid. Each cell consists of two Teflon bonded gas diffusion electrodes on a
porous conducting support. Pt is deposited on both the electrodes which acts as catalyst.

ADVANTAGES:
1.Excellent thermal, chemical and electrochemical stability.
2.Low volatility of phosphoric acid above 150oc.
3.Simple construction.

DISADVANTAGE: Only Pt catalyst can be used.

SOLID OXIDE FUEL CELL [SOFC]:

It uses a solid electrolyte (ZrO2) 0.85 (CaO) 0.15 or (ZrO2) 0.9 (Y2O3) 0.1

The electrolyte is an impervious ceramic and its electronic conductivity is very high at
temperature above 1000oc
The current carriers in the electrolyte are oxide ion. The single cell is fabricated by
applying a porous Pt electrode on both sides of a sharp cylindrical electrolyte segment. The
fuel gas (H2) passes through the tube and the outer surface is exposed to air. The anode is
CO-ZrO2 or Ni-ZrO2 cermet and the cathode is Sr doped LaMnO3.

Reaction: The oxygen from the air reduced at the cathode O 2 + 4e- 2O2-

The oxide ions formed migrate through the electrolyte and reach the anode (inner surface)
where they are reconverted to oxygen. The oxygen then combines with hydrogen the
reaction being catalyzed by Pt to form H2O.

2O2- O2 + 4e-

34
O2 + 2H2 2H2O

Open circuit voltage is 1.15 V.

ADVANTAGE: SOFC do not suffer from the poisoning, leakage or evaporation problems
experienced by other fuel cell system.

DISADVANTAGE: The main problems are brittleness, thermal expansion and corrosion of
the cell intermediates.

Summary
Fuel cell is a galvanic cell in which electrical energy is directly obtained by the combustion
of the fuels and based on the types of electrolyte used, fuel cells are classified.

End of Lecture

Lecture 10 :
Construction and working of H2O2 and Methanol-Oxygen fuel cell.

Objectives
By the end of this lecture, you will be able to understand:
Construction, working and application of HydrogenOxygen fuel cell and
Methanol oxygen fuel cell and how it is more useful.
Introduction:
In fuel cells, we are using the fuel such as hydrogen, methanol and oxidant like
oxygen. These cells work continuously as long as we supply the fuel and the
oxidant regularly. These cells are
mainly used in space vehicles and it helps in reducing the pollution.

H2 O2 FUEL CELL: The cell consists of a porous carbon impregnated with Ni/Pt catalyst
as anode. The cathode is also a porous carbon impregnated with silver catalyst. The
electrolyte is an aqueous solution of KOH.
In this cell there are three comportments separated from one another by porous electrodes.
The hydrogen gas is fed into another comportment. These gases diffuse through the
electrodes and react with an electrolyte solution in the center comportment.

At the cathode the oxygen undergoes reduction, producing OH - ions.

O2 (g) + 2H2O (l) + 4e- 4OH-(aq)

At the anode, hydroxide ions react with hydrogen gas by the equation

2H2 (g) + 4OH- (aq) 4H2O (l) + 4e-

The net cell reaction is 2H2 (g) + O2 (g) 2H2O (l)

35
The fuel cell is operated at high temperature, so the water that is produced is removed as
steam.
H2- O2 fuel cell was used as the primary source of electrical energy on the Appolomoon
flights. A secondary advantage is that the water produced as a product of the cell reaction
can be condensed and used as drinking water for the astronauts.

36
METHYLALCOHOL FUEL CELL: It is an egs. of a liquid fuel cell. Platinised porous
carbon acts as anode and hollow porous carbon tube impregnated with mixed oxides of Ag,
Co and Al acts as cathode. Methanol dissolved in potassium hydroxide acts as a fuel. The
oxidant is the oxygen or air. Electrolyte is alkaline KOH.

The electrode reactions are

At anode CH3OH + 6OH- CO2 + 5H2O + 6e- X 2

At cathode O2 + 2H2O + 4e- 4OH- X3

Net reaction 2 CH3OH + 3 O2 2 CO2 + 4 H2O

The use of alkali as electrolyte presents problems. The carbon dioxide is absorbed by the
electrolyte and the electrolyte is gradually converted into carbonate. This decreases the cell
efficiency because of the increasing concentration polarization at the electrode surface and
the decreasing conductivity of the electrolyte.

Summary

We have studied in detail the construction, working and importance of HydrogenOxygen fuel
cell and Methanol Oxygen fuel cell and how we can avoid pollution.

Solution for Problems


1.Calculate the potential of Daniel cell at 250 C, given the electrode potentials of Cu and Zn are 0.34V and
0.76V respectively.

Given: E0Zn = -0.76V; E0Cu= 0.34V


w.k.t Ecell = Ecathode -Eanode
Ecell = 0.34-(-0.76)
Ecell = 1.1 V
2. Calculate the voltage of the cell Mg(s)Mg+2(1M) Cd+2(7x10-11M) Cd(s), where E0cell=1.97V.
Given:E0cell = 1.97V
[Mg+2] =1M
[Cd+2] = 7x10-11M
0.0591 [Cd 2 ]
E cell E o
log
n [ Mg 2 ]
cell

0.0591
E cell 1.97 log 7 X 10 11 1.6699 V
2
3. Write the half cell and net cell reactions for the cell

37
Cd(s)Cd+2(0.01M)Cu+2(0.5M) Cu(s)
The standard reduction potentials of Cd and Cu are 0.4V and 0.34V respectively. Calculate the emf of
the cell.
Given: E0Cd = -0.4V; E0Cu= 0.34V; [Cd+2] =0.01M; [Cu+2] = 0.5M

At anode: Cd Cd2+ +2e-


At cathode Cu2+ + 2e- Cu

Net cell reaction Cd + Cu2+ Cd2+ + Cu

E o Cell E Cathode E Anode 0.34 ( 0.40) 0.74 V


0.0591 [Cu 2 ]
E cell E 0 Cell log
n Cd 2

0.0591 0 .5
E cell 0.74 log 0.7902 V
2 0.01

4. A cell is constructed by coupling Zn electrode dipped in 0.5 M ZnSO4 and Ni electrode dipped in
0.05M NiSO4. Write the cell representation, cell reaction & calculate emf of the cell, given SRPs of
Zn and Ni as -0.76 & -0.25 v respectively. [July/Aug 02]
Zn(s)Zn+2(0.5M)Ni+2(0.05M) Ni(s)

At anode: Zn Zn2+ +2e-


At cathode Ni2+ + 2e- Ni

Net cell reaction Zn + Ni2+ Zn2+ + Ni


E o Cell E Cathode E Anode 0.25 ( 0.76 ) 0.51V


0.0591 [ Ni 2 ]
E cell E o Cell log
n Zn 2
0.0591 0.05
E cell 0.51 log 0.4804 V
2 0 .5

5. What voltage will be generated by a cell that consists of an iron rod immersed in 1.0M FeSO 4
solutionand a manganese rod immersed in 0.1M MnSO4solution at 298K? Given E0Fe2+/Fe = -0.44V;
E0Mn2+/Mn = -1.18V[March 01]
Mn(s)Mn+2(0.1M)Fe+2(1.0M) Fe(s)

E o Cell E Cathode E Anode 0.44 ( 1.18) 0.74 V


0.0591 [ Fe 2 ]
E cell E 0 Cell log
n Mn 2

38
0.0591 1
E cell 0.74 log 0.7696 V
2 0 .1
6. Calculate the potential of Ag-Zn cell at 298 K, if the concentration of Ag+ and Zn +2 are 5.2x10-6M
and 1.3x10-3M respectively. E0 of the cell at 298K is 1.5V given: T=298K; E0cell = 1.5V.
[Ag+] =5.2x10-6M[Zn+2] = 1.3x10-3M


0.0591 [ Ag ] 2
E cell E 0 Cell log
n Zn 2
0.0591 (5.2 x10 ) 6 2
E cell 1.5 log 1.27 V
2 1.3 x10 3

7. An electrochemical cell consists of iron electrode dipped in 0.1M FeSO 4 and silver electrode in 0.05M
AgNO3. Write the cell representation, cell reaction and calculate the emf of the cell at 298K.
(The standard reduction potentials of iron and silver are 0.44V and 0.8V respectively).
Given: T=298K; E0Fe = -0.44V; E0Ag= 0.8V
[Fe+2] =0.1M
[Ag+] = 0.05M
cell representation: Fe(s) FeSO4(0.1M) AgNO3(0.05M) Ag(s)

E o Cell E Cathode E Anode 0.8 ( 0.44) 0.36 V


0.0591 [ Ag ] 2
E cell E 0 Cell log
n Fe 2
0.0591 [0.05]
2
E cell 0.36 1.19 V
0.1
log
2

8.Calculate the emf of the cell Fe(s)FeSO4(0.01M) AgNO3(0.1M) Ag(s) at 298 K, if SRPs of Fe and
Ag are -0.44 Vand 0.8 V respectively(Jan/Feb 03: Dec 07/Jan 08)

E 0 Cell ECathode E Anode 0.8 (0.44) 0.36V


0.0591 [ Ag ]
2

ECell E 0
log
n
Cell
Fe 2
0.0591 [0.1]
2
E cell 0.36 1.24 V
0.01
log
2

9. An Electrochemical cell consists of a copper electrode dipped in 0.5 M CuSO4 and silver electrode
dipped in 0.25 M AgNO3. Write the cell scheme, half cell and net cell reactions. Also, calculate the emf.
Given, SRPs of Cu & Ag are 0.34 and 0.8V respectively.
cell representation: Cu(s) CuSO4(0.5M) AgNO3(0.25M) Ag(s)

39
At anode: Cu Cu2+ +2e-
At cathode 2Ag+ + 2e- 2Ag

Net cell reaction Cu + 2Ag+ Cu2+ + 2Ag

E 0 Cell ECathode E Anode 0.8 (0.34) 0.46V


0.0591 [ Ag ]
2

ECell E 0
log
n
Cell
Cu 2

E cell 0.46
0.0591
log
0.25 0.433 V
2

2 0 .5

10.Calculate the cell potential of a cell containing Ag+/Ag & Cu/Cu2+ if the concentrations
of Ag+ and Cu2+ ions are 4.2 X 10-6 and 1.3 X 10-3 respectively. Given E0Ag+/Ag=0.8V,
E0Cu2+/Cu = 0.34V

E 0 Cell ECathode E Anode 0.8 (0.34) 0.46V


0.0591 [ Ag ]
2

ECell E 0
log
n
Cell
Cu 2

E cell 0.46
0.0591
log

4.2 X 10 6
2

0.2275V
2 1.3 X 10 3

11. Calculate single electrode potential of Zn electrode when [ Zn2+] =0.1M Given EoZn2+/Zn=-0.76V
(July/Aug05)
0.0591 [H ]
E cell E cell log
0

n [ Zn 2 ]
0.0591 [1]
E cell .076 log 0.7895V
n [0.1]

12. Calculate the electrode potential at a copper electrode dipped in a 0.1M solution of
Copper sulphate at 298K, assuming copper sulphate to be completely dissociated. The standard electrode
potential of Cu+2/Cu is 0.34V at 298KGiven: T=298K; E0Cu= 0.34V
[Cu+2] =0.1M
logCu 2
0.0591
E Cu 2 E0 at 298 K
Cu n
0.0591
E Cu 2 0.34 log(0.1)
2
0.34 0.0296
Cu

E Cu 2
Cu

40
E Cu 2 0.3105 V
Cu

13. Calculate the standard electrode potential of Cu2+/Cu if its electrode potential at 25oC
0.296V when [Cu2+]= 0.015M(June-July 08)

Ecell Ecell
0 0.0591
n
log Cu 2
0.0591
E0 E log 0.015
2

0.0591
E 0 0.296 log 0.015
2
E0 =0.349V
14.Write the electrode reactions and Calculate the EMF of the given cell at 298K, Ag(s)AgNO3
(0.018M) AgNO3 (1.2M)Ag(s).

At anode Ag(s) Ag+ + e-

At cathode Ag+ + e- Ag(s)

0.0591 C 2
. w.k.t E cell log at 298K
n C1
1 .2
E cell 0.0591 log (n=1)
0.018
Ecell = 0.1078 V.
15. Calculate the emf of Copper concentration cell at 25 0 C, where the copper ions ratio in the
cell is 10.
[Cu 2 ] cathode C 2
Given: 10
[Cu 2 ] anode C1
0.0591 C 2
w.k.t E cell log ; at 298 K
n C1
0.0591
E cell log(10)
2
Ecell = 0.0296 V.

16.A concentration cell was constructed by immersing two silver electrode in 0.05M and 1M
AgNO3 solution. Write the cell representation, cell reactions and calculate the EMF of the cell.
(July-06)
Cell representation: Ag(s) AgNO3(0.05M) AgNO3(1M) Ag(s)

41
At anode: Ag(0.05M) Ag+(0.05M) +e-
At cathode Ag+ (1M) + e- Ag (1M)

0.0591 C 2
Net cell reaction Ag(0.05M) + Ag+ Ag+ (0.05M)+ Ag
E cell log
n C1

0.0591 1
Ecell log
0.05

Ecell = 0.0768V

17. A concentration cell was constructed by immersing two silver electrode in 0.01M and
10M AgNO3 solution. Write the cell representation, cell reactions and calculate the emf of
the cell. (July-Aug 05)
Cell representation: Ag(s) AgNO3(0.01M) AgNO3(10M) Ag(s)
At anode: Ag(0.01M) Ag+(0.01M) +e-
At cathode Ag+ (10M) + e- Ag (10M)

0.0591 C 2
Net cell reaction Ag(0.01M) + Ag+ Ag+ (0.01M)+ Ag
E cell log
n C1

0.0591 10
Ecell log
0.01

Ecell = 0.1773V

18. The spontaneous galvanic cell Tin/Tin ion(0.024M)//Tin ion(0.064M) /Tin develop an
emf of 0.0126 V at 25OC, Calculate the Valency of Tin.(Jan-06)
0.0591 C 2
E cell log
n C1

0.0591 C2
n log
Ecell C1
0.0591 0.064
n log
0.0126 0.024
n =2(Valency of tin)

19. Claculate the potential of the Zn-Cu Daniel cell at 298K, if the free energy change of the cell
reaction is -212.3kJmol-1, Faraday constant, F=96.5kJV-1mol-1.

-Go= nFEo

42
G o 212.3
E cell 1.10 V
nF 2 X 96.5
20. In the daniell cell

a) Calculate the cell potential if the Zn2+ and Cu2+ concentrations are 0.1 M and 1.0X10-9M
respectively at 298K?

b) Calculate G and Go for the reduction of 1.0 mol of Cu2+ by Zn at 298K.


EoCell=1.10V.


0.0591 [Cu 2 ]
E cell E cathode
0
E anode
0
log
n Zn 2
0.0591 [1.0 X 10 9 ]
E cell 0.34 ( 0.76) 0.8636 V
0.1
log
2
G nFE 2 X 96.5 X 0.8636 166.7 kJmol 1

G o nFE o 2 X 96.5 X 1.10 212.3 kJmol 1

21. The EMF of the cell Cu/CuSO4)(0.01M) //CuSO4(XM)/Cu is 0.0295V at 25OC. Find the value
of X.
0.0591 C 2
E cell log
n C1
0.0591 X

0.0295 log
2 0.01

Ans: 0.09964M

22. Represent the cell formed by the coupling of two electrodes immersed in CuSO4 solution
concentration of cupric ions in one electrode system is 100 times more concentration than other.
Write the cell reaction and calculate the potential at 300K.(July 07)

Cu(s) CuSO4(1M) CuSO4(100M) Cu(s)Possibility 10/0.1=100 or 5/0.05 or 5/0.05=100

0.0591 C 2 0.0591 10
Ecell log Ecell log
n C
1 2 0.1
ECell=0.0595V

43
Model Questions:
1. What is single electrode potential? Derive the Nernst equation for single electrode potential.
2. Discuss the origin of electrode potential.
3. Define concentration cells?
4. Explain the construction of Ag/AgCl electrode. Give the half-cell reaction.
5. Write a note on Calomel electrode.
6. What is an ion selective electrode? Explain its principle and working.
7. Write a note on glass electrode.
8. Explain how glass electrode can be used in the determination of a P H of a solution.
9. Explain the determination of electrode potential by using reference electrode.
10. What are ion selective electrodes? Discuss the construction of glass electrode and derive an
expression relating glass electrode potential and pH.

44