SVCE TIRUPATI

COURSE MATERIAL

CHEMISTRY(CH20ABS103)
SUBJECT

UNIT III

COURSE B.TECH

DEPARTMENT S&H

SEMESTER II

PREPARED BY Dr T Chandraiah, Associate Professor

(Faculty Name/s)

Version V-1

PREPARED / REVISED DATE 10-5-2021

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 TABLE OF CONTENTS – UNIT
3
S. NO CONTENTS PAGE NO.
1 COURSE OBJECTIVES 1
2 PREREQUISITES 1
3 SYLLABUS 1
4 COURSE OUTCOMES 1
5 CO - PO/PSO MAPPING 1
6 LESSON PLAN 2
7 ACTIVITY BASED LEARNING 2
8 LECTURE NOTES 2
3.1 Electro chemistry –Introduction 2

3.2 Electrode-Reference electrode 3

3.3 Electro chemical cell 5
3.4 Nernst equation 10
3.5 pH-metry, Potentiometry 15
3.6 Conductivity-conductometric titrations 16
3.7 Electro chemical sensors 20
3.8 Types of batteries 25
9 PRACTICE QUIZ 31
10 ASSIGNMENTS 32
11 PART A QUESTIONS & ANSWERS (2 MARKS QUESTIONS) 33
12 PART B QUESTIONS 34
13 PRESCRIBED TEXT BOOKS & REFERENCE BOOKS 35
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1. Course Objectives
The objectives of this course is to
 To impart the concept of soft and hard waters, softening methods of hard water
 To familiarize engineering chemistry and its applications
 To train the students on the principles and applications of electrochemistry
and polymers
 To introduce instrumental methods

2. Prerequisites
Students should have knowledge on
1. Types of batteries
2. Redox reactions
3. Nernst equation
4. EMF

3. Syllabus
UNIT III
Electrochemistry and Applications:
Electrodes – concepts, reference electrodes (Calomel electrode,
Ag/AgCl electrode and glass electrode); Electrochemical cell, Nernst
equation, cell potential calculations and numerical problems,
Potentiometry- potentiometric titrations (redox titrations), concept of
conductivity, conductivity cell, conduct metric titrations (acid-base
titrations).Electrochemical sensors – potentiometric sensors with
examples, amperometric sensors with examples.
Primary cells-Zinc-air battery, Secondary cells –Nickel-Cadmium
(NiCad),and lithium ion batteries- working of the batteries including cell
reactions; Fuel cells, hydrogen-oxygen, methanol fuel cells – working of
the cells.

4. Course outcomes
1. Apply Nernst equation to calculate the cell potential.
5. Co-PO / PSO Mapping
P P P
PO PO PO PO PO PO PO
CHE PO1 PO2 O O O PSO1 PSO2
5 6 7 8 10 11 12
3 4 9
CO3 3

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6. Lesson Plan
Lecture
Weeks Topics to be covered References
No.
1 Electro chemistry –INTRODUCTION T1
2 Electrode-Reference electrode TB1/RB2
1
3 Electro chemical cell ,Nernst equation TB1/RB2
4 Cell potential Problems TB1/RB2
5 pH metry, potentiometry TB1/RB2
6 Conductance, conductometric titrations TB1/RB2
2
7 Electro chemical sensors TB1/RB2
8 Potentiometric sensor TB1/RB2
9 Amoperometric sensor TB1/RB2
10 Primary batteries
3
11 Secondary batteries TB1/RB2
12 Fuel cells TB1/RB2

7. Activity Based Learning

1. Measurement of conductance in acids and bases
2. Determination of pH-of the samples
8. Lecture Notes
3.1 Electro chemistry: This is a branch of physical chemistry that deals with conversion
of chemical energy into electrical energy and vice versa.

Electrolyte:-A Substance, which decomposes as a result of passage of electric current,

is called “Electrolyte”.

Electrolysis:-The phenomenon of decomposition/ breakdown/ lysis of electrolyte by

passing electricity is called electrolysis.

Electric current:-The flow of electrons that are generated by a battery when the
circuit is complete is called electric current.

Electric conductor:-Any substance which allows or passes electric current through it is

called as ‘electric conductor’.

Anode: It is an electrode at which Oxidation occurs.

Cathode: It is an electrode at which Reduction occurs.

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Types of Electrolytes: Electrolytes may be classified into

1. Strong electrolytes
2. Weak electrolytes

1. Strong electrolytes: It is a substance that gives a solution in which almost all the
molecules are ionized and having increasing value of equivalent conductance at
low dilution.

Eg: Strong acids: HCl, H2SO4, HNO3, HBr etc

Strong bases : NaOH, KOH, Ca (OH2), Mg (OH2) etc.
Salts : NaCl, KCl, AgCl2

2. Weak electrolytes: The electrolytes which ionize to a small extent on dilution are
called weak electrolytes. They are poor conductors in solution.
Eg: Weak acids : All organic acids like Acetic acid, Propionic acid etc.
Weak bases : Alkyl amines, NH4OH
Weak salts : HgCl2 and Lead acetate.
Electrode potential:
- Metal ions have a tendency to go into solution as metal ions. This tendency is
called ‘electrode potential’ of that metal.
- Electrode potential can be defined as the tendency of metal atoms to go in
to solution in the form of metal ions.
- The electrode equilibrium is represented as

M(s) Oxidation Mn+ (aq) + ne-

Reduction

- Electric current flows between two electrodes if the contact is established

between two metals.
- The flow of current from one electrode to another electrode in a galvanic cell
indicates that the two electrodes have different potentials.
- The difference of potential which causes the flow of current from one
electrode which is at higher potential to another electrode which is at lower
potential is called “EMF of the cell”

Illustration of Electrode Potential

In order to understand the origin of electrode potential, the

following two examples are considered.

Example-1 Zn electrode dipped in ZnSO4 solution

When Zn electrode is dipped in ZnSO4 solution, Zn goes into the

solution as Zn2+ ions due to oxidation.

Zn >Zn2 + + 2e-

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 Now, the Zn electrode attains a negative charge, due to the
accumulation of valence electrons on the metal. The negative
charges developed on the electrode attract the positive ions
from solution. Due to this attraction the positive ions remain
close to the metal.

Electrode potential

Example -2 Cu electrode dipped in CuSO4 solution

When Cu electrode is dipped in CuSO4 solution, Cu2+ ions

from the solution deposit over the metal due to reduction.

Cu2+ 2e Cu

Now, the Cu electrode attains a positive charge, due to the

accumulation of Cu 2+ ions on the metal. The positive charges
developed on the electrode attract the negative ions from
solution. Due to this attraction, the negative ions remain close to
the metal.

Thus, a sort of layer (positive (or) negative ions) is formed all

around the metal. This layer is called Helmholtz electrical
double layer. This layer prevents further passing of the positive
ions from the solution or to the metal. A difference of potential is
consequently set up between the metal and the solution. At
equilibrium, the potential difference becomes a constant value,
which is known as the electrode potential of a metal.

Factors affecting electrode potential

The rate of the above reactions depend on

1. The nature of the metal.

2. The temperature.
3. The concentration of metal ions in solution.
Single electrode potential( E)

It is the measure of tendency of a metallic electrode to lose or gain electrons, when

it is in contact with a solution of its own salt.

Standard electrode potential (E0)

It is the measure of tendency of a metallic electrode to lose or gain

electrons, when it is in contact with a solution of its own salt of 1
molar concentration at 25 C.

Oxidation and Reduction Potentials

1.Oxidation potential

If oxidation occurs at the electrode, at equilibrium, the potential of

the electrode is oxidation potential.

Zn Zn2 2e

Thus, the tendency of an electrode to lose electrons is called the

oxidation potential.

2. Reduction potential

If reduction occurs at the electrode, at equilibrium, the potential of

the electrode is reduction potential.

Cu2 2e Cu

Thus, the tendency of an electrode to gain electrons is called the

reduction potential.

3.2 NERNST EQUATION FOR ELECTRODE AND CELL POTENTIAL:

Electrode potential for the electrode reaction,
Mn+(aq) + ne- M(s)
Relative to hydrogen electrode is given by a simple form of the Nernst equation as
𝑹𝑻
E Mn+ /M = Eo Mn+ /M + ln (Mn+)
𝒏𝑭

Here
Eo Mn+ /M = Standard electrode potential for a molar solution of a metal ion at 298oK

(This is determined by using the standard hydrogen electrode )

R= Universal gas constant (8.31 J/K/mol)
T= Temperature in Kelvin
n= Number of moles of electrons
F= Faraday (96500 C/mol)
In the Daniell cell,
(Left) Zn (s) +Cu2+ (aq) Zn2+ (aq) +Cu(s) (Right),
The electrode potential of the right hand electrode is written as:
𝑹𝑻
E Cu+2/ Cu = Eo Cu+2/ Cu + ln [Cu +2 (aq)]
𝒏𝑭

The electrode potential of the left hand electrode is written as:

𝑹𝑻
E Zn+2/ Zn = Eo Zn+2/ Zn+ ln [Zn+2 (aq)]
𝒏𝑭

∴ The cell potential E cell = Electrode potential of right hand electrode –

Electrode potential of left hand electrode
= E right - E left
∴E cell = { Eo Cu
+2
/ Cu + 𝑹𝑻 ln [Cu +2 (aq)]} – { Eo Zn
+2
/ Zn+ 𝑹𝑻 ln [Zn+2 (aq)]}
𝒏𝑭 𝒏𝑭

= (Eo E
- o +2 𝑹𝑻 [𝑪𝒖+𝟐
)(𝒂𝒒)]
+ ln
+2
Cu / Cu Zn /
Zn 𝒏𝑭 [𝒁𝒏+𝟐(𝒂𝒒)]

𝑹𝑻 [𝑪𝒖+𝟐 (𝒂𝒒)]
E Cell = Eo cell + ln ( Eo cell = Eo Cu +2/ Cu - Eo Zn+2/ Zn )
𝒏𝑭 [𝒁𝒏+𝟐(𝒂𝒒)]

Eo cell is cell potential in standard state. By converting natural logarithm to the

base 10, and substituting the values R, T (298K) and F, we get
𝟎.𝟎𝟓𝟗𝟐 [𝑪𝒖+𝟐 (𝒂𝒒)]
E Cell = Eo cell + 𝟐
log [𝒁𝒏+𝟐(𝒂𝒒)]

This equation is also written as,

𝟎.𝟎𝟓𝟗𝟐 [𝒁𝒏+𝟐 (𝒂𝒒)]
E Cell = Eo cell - 𝟐
log [𝑪𝒖+𝟐(𝒂𝒒)]

For a reaction which involves mono-valent and bivalent ions,

Let us consider the cell,
Ni (s) / Ni+2 (aq) // Ag + (aq) /
Ag(s) The EMF of the cell is written as
𝑹𝑻 [𝑨𝒈+ (𝒂𝒒)]
E Cell = Eo cell + 𝟐𝑭 ln [𝑵𝒊+𝟐(𝒂𝒒)]

For a general electro chemical change of the

type aA+ bB cC + dD
the Nernst equation can be written as
𝟐.𝟑𝟎𝟑𝑹𝑻 [𝑪] [𝑫]𝒅
E Cell = Eo cell – 𝒏𝑭
log [𝑨]𝒂 [𝑩]𝒃
 3.3 REFERENCE ELECTRODES:

The electrode of standard potential, with which the potentials of another electrode
of interest is compared, is called a ‘Reference Electrode’.
- The standard Hydrogen electrode is taken as reference electrode for determining
the standard electrode potentials. Its potential is taken as Zero.
- There are some problems using the hydrogen electrode. They are
o Maintenance of activity of Hydrogen ions at unity.
o Keeping the pressure of the gas uniformly at 1 atm.
o Hydrogen gets poisoned even if impurities are present in traces.
- To overcome this, other electrodes are also used as standard electrodes. They are
o Calomel electrode
o Silver- Silver chloride electrode
o Glass membrane electrode

1. Calomel electrode:
- It is a secondary electrode consisting of a glass tube having a side tube on each
side.
- Mercury of high purity is placed at the bottom of this tube and is connected to the
other circuit by means of platinum wire sealed in a glass tube.
- The surface of mercury is covered with a paste of mercurous chloride (calomel)
and mercury in potassium chloride solution.
- KCl is taken as electrolyte solution.
- The electrode is connected with the help of side tube on left through a salt bridge
with the other electrode, whose potential is to be determined.
- The potential of the calomel electrode depends on the concentration of the
potassium chloride solution.
- The potential can be accurately determined by connecting it to a standard
hydrogen electrode and the results are analyzed.
- The results obtained are reduction potentials of this electrode (Hg/HgCl2) for
different concentrations of KCl at 24oC.
 Ex: For 0.1N KCl solution E=+0.3338V
For 1.0N KCl solution E=+0.2800V
For saturated KCl solution E=+0.2415V
- The positive value indicates that when combined with standard hydrogen
electrode, reduction takes place at this electrode.

2. Silver-Silver chloride electrode:

- It is recently used as reference electrode in connection with the accurate
determination of standard potentials due to its reversible and stable nature.
- This can be combined with cells containing chlorides without inserting liquid
junctions.
- For effective functioning of this electrode, the solution that is in contact with the
silver surface is saturated by providing a coating of AgCl on the surface.
- This is done by using the silver electrode as an anode in a chloride solution (KCl
or HCl) at a very low current density for about half an hour.
- The electrode is represented as
Ag/ AgCl (s), H+ Cl-/H2 (1atm)
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3. Glass membrane electrodes:

Construction: A glass membrane electrode is constructed in a similar way to that

of pH electrode. Consists of thin-walled glass bulb (the glass is a special type

having low melting point and high electrical conductivity) containing a Pt wire
in 0.1M HCl.

The glass electrode is represented as

Pt, 0.1 M HCl / Glass

Glass electrode is used as the “internal reference electrode”. The

pH of the solutions, especially coloured solutions containing
oxidizing or reducing agents can be determined. The thin walled
glass bulb called glass membrane functions as an ion-exchange
resin, and an equilibrium is set up between the Na + ions of glass
and H+ ions in solution. The potential difference varies with the H+
ion concentration, and is given by the expression.

EG = E°G + 0.0592 V pH

Determination of pH of a solution by glass electrode:

The glass electrode is placed in the solution under test and is

coupled with saturated calomel electrode as shown in the figure...

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The emf of the cell is measured. From the emf, the pH of the solution is
calculated as follows
Ecell = Eright - Eleft
Ecell = E
cal -
E
glass
Ecell =0.2422 V - [ E°G + 0.0592 V pH ]

Ecell = 0.2422 V - E°G - 0.0592 V pH

pH =0.2422V –E cell/0.0592V

Advantages of Glass Electrode

1. It can be easily constructed and readily used.

2. The results are accurate.

3. It is not easily poisoned.

4. Equilibrium is rapidly achieved.

Limitations

1.Since the resistance is quite high, special electronic

potentiometers are employed for measurement.
2. The glass electrode can be used in solutions only with pH range
of 0 to 10. However above the pH 12 (high alkalinity), cations of
the solution affect the glass and make the electrode useless.

3.4 ELECTROCHEMICAL CELLS:-

An electrochemical cell is a device which is used for converting chemical
energy into electrical energy with the help of redox reactions. Redox chemical
reactions are those in which oxidation and reduction takes place at the same time.
Redox reactions occur in many places.
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Eg: Respiratory system, Photosynthetic system, Rusting of Iron, Combustion o
petroleum etc..
There are 2 types of cells to carry out of electrochemical processes.
1. Electrochemical cell - uses the electrical energy to electrolysis.
2. Galvanic/voltaic cell - uses the energy released from a spontaneous chemical
reaction to generate electricity.

- The substance which loses electrons is called oxidized and the process is
called Oxidation and the substance which gains electrons is called Reduced
and the process is Reduction.
- In redox chemical reactions, oxidation and reduction takes place at the same
time.
Eg: Zn-CuSO4 reaction in a beaker.
If a Zn rod is placed in a solution of CuSO 4, oxidation of Zn metal occurs by Cu +2
ions.
The Zn strip starts dissolving forming Zn+2 ions in solution.
Zn+2 (aq) + 2e- Zn(s ) Oxidation half reaction

At the same time Cu starts precipitating out from the

solution Cu+2 (aq) + 2e- Cu (s)
Reduction half reaction
The overall reaction is a redox reaction obtained by adding two half reactions.
Zn(s) + Cu+2 (aq) Zn+2 (aq) + Cu (s) -- Redox reaction

- Zn metal can be oxidized by Cu +2 ions but Cu metal cannot be oxidized by

Zn+2 ions.

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- Electrochemical cell can be defined as ‘a device in which a redox
reaction tales place indirectly and the decrease in potential energy of
the reaction appear largely in the form of electrical energy’.
GALVANIC CELL:-
- The energy from a battery comes from a spontaneous redox reaction in
which the electrons are forced to move through a wire.
- The apparatus that provides electricity through redox reaction is called
galvanic cell, invented by Luigi Galvani (1737-1798) and also called as voltaic
call (Alessandro Volta (1745-1827).
- Galvanic cell is made up of two half cells (an individual oxidation and
reduction takes place at two electrodes).

- On the left Zinc electrode dips into a solution of ZnSO4 (oxidation) and on
the right a Copper electrode dips into a solution of CuSO4 (Reduction).
- The two electrodes are connected by an external electrical circuit and
two solutions are separated by salt bridge. The electrode reactions are:
At anode: Zn (s) Zn2+ (aq)+2e- (oxidation)
At cathode: Cu2+(aq)+2e- Cu (s) (Reduction)

Zn (s )+Cu2+(aq) Zn2+ (aq)+Cu(s)

- The Zn dissolves in aqueous solution releases electrons to get positive charge
(Zn2+) called oxidation. On the other hand Cu 2+ accepts electrons to form
copper called reduction.
- When these reactions takes place, electrons left behind by oxidation of the
Zinc travel through external circuit to the other electrode where they are
transferred to the Cu ions and are reduced to Cu metal.
- The overall reaction that takes place in a galvanic cell is called cell reaction.
- Electric current flows from positive electrode to negative electrode. So the Zn
electrode is called negative electrode, while the Cu electrode is called
positive electrode. However the electrons flow from the negative electrode to
positive electrode through external electrical circuit.

- The flow of electrons from one electrode to other electrode in Galvanic cell
indicates that the electrodes have different potentials.
- The difference of potentials which causes electrons to flow or current from
one electrode which is at higher potential to another electrode which is at
lower potential is called Electro motive force (EMF) of the cell.

EMF MEASUREMENT (ELECTRO MOTIVE FORCE):-

The flow of current from one electrode to another electrode in a galvanic
cell indicates that the two electrodes have different potentials.
- The difference of potential which causes the flow of current from one
electrode which is at higher potential to another electrode which is at lower
potential is called “EMF of the cell”
- An EMF of a cell can be measured by connecting two electrodes to the
two terminals of a voltmeter.
This method is inaccurate because of the following problems.
(a) Changing in the equilibrium of the cell by voltmeter—because voltmeter uses
some of current from the cell.
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(b) With flow of current, a part EMF is used in overcoming the internal resistance
of cell.
- EMF of the cell can be measured without disturbing the chemical equilibrium
by using Poggendorff’s compensation principle.
- In this technique the EMF is measured using potentiometer. Where principle is
EMF to be measured is balanced by equal and opposite EMF from another
cell or battery and there is no net flow of current in the circuit. The electrical
assembly used is called Potentio meter.
- Potentiometer consists of a uniform wire AB of high resistance, connected to
a storage battery of constant EMF which should be longer than the EMF of
cell to be measured.
- The Cell ‘X’ whose EMF is to be determined is connected to the positive
pole ‘A’ and then through a galvanometer ‘G’ to a sliding contact D.

S= Standard cell EMF.

- The sliding contact ‘D’ is moved along the wire AB till there is no current flow
in the galvanometer. The position ‘D’ is then noted.
- The EMF of cell (Ex) is proportional to the distance AD
Ex  AD
- The cell ‘X’ is now replaced by standard cell ‘S’, whose EMF Es is known.
- The position of sliding contact is readjusted by moving it over the wire AB till
the point of no current in the Galvanometer i.e. the ‘null point’, indicated as
‘D1’
Es AD1
Ex
  AD AD
 E   ES
Es x
AD1
AD1
Knowing the Es, Ex can be calculated easily.
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- The standard cell must be capable of giving constant and reproducible emf
and its variation with temperature should be negligibly small.
- 3.5 POTENTIOMETRIC TITRATIONS:
- Principle: Emf of a cell depends on the concentration of the electrolytes
with which the electrodes are in contact. Therefore, the electrode reaction
is,
- M n + + ne- M
- As the concentration of M n+ changes, the emf of the cell also
changes correspondingly.
- Thus, the potentiometric titrations involve the measurement of
emf between reference electrode and an indicator electrode,
with the addition of the titrant.
-

- Redox titration (FeSO4 Vs K2Cr2O7)

Known amount of FeSO4 solution is taken in a beaker and the indicator
electrode (platinum electrode) is inserted in it. It is then connected to a
reference electrode (calomel electrode), to form a galvanic cell. The cell is
then connected to the potentiometer and its Ecell is determined. When it is
titrated against the standard K2Cr2O7 solution, taken in the burette, the emf is
going on increasing as the concentration of Fe3+ increases due to the
following reaction.

K Cr O
2 2 7

Fe+2  Fe+3 + e-
- At the end point the emf suddenly increases. After the end
point there is no change in the potential. When the emf is
plotted against the volume of K2Cr2O7 added, a curve of the
type shown in figure is obtained. The end point is the point,
where the slope of the curve is maximum.
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Ecell Vs Vol. of K2Cr2O7

A more sensitive and satisfactory method of detecting the end point will be
the graph of ∆𝐸/∆V against volume of K2Cr2O7. The resulting curve rises to a
maximum at the equivalent point, which is the end point.

Advantages of potentiometric titrations:

- 1. The necessary apparatus required is cheap and
easily available.
- 2. This method can be used for coloured solution.
- 3. Fixing up end point is easier when compared to the
titrations in which indicators are used to fix up end points.
- 4. Very dilute solutions can be titrated with accuracy.
- 5. Several components may be titrated in the same solution.

3.6 Conductivity: Electrons play an important role when an

electric current passes through a solid material. Similarly ions
(cation and anion) also play an important role when a current
passes through a liquid such as an aqueous solution. Since
conductivity is an indicator of how easily current passes
through a solution. The conductivity mainly depends on
quantity of ions and their mobility in that solution. Ohm’s law
provides the fundamental rules for all types of conductivity.
Ohm’s law: The resistance of a conductor is directly proportional to its
length and inversely proportional to its cross sectional area

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R  l/a
Conductometric Titrations: Electrolyte solutions conduct
electrical current through them by the movement of ions to
the opposite electrodes. Thus, conductivity (or) conductance
of an electrolyte solution is a measure of its ability to conduct
electricity. Like metallic conductors electrolytes also obey
ohm’s law.

Conductivity cell:
The solution whose conductivity is to be determined is placed
in a special type of cell “known as the conductivity cell”. Thus,
conductivity cell is a cell used to measure the conductivity of
the solution.
Construction: A conductivity cell consists two electrodes, fitted
in the cell, made of platinum plates coated with platinum
black. These are welded to platinum wires fused in two thin
glass tubes and are connected to copper wires. An AC
voltage is applied between the electrodes of cell and the
resulting current is measured. Conductive ions, produced from
the salts, produce a path for current to flow. Therefore high
conductivity indicates high ionic concentration.
Conduct ometric Titration
Principle: Conductometric titration is a volumetric method based on
the measurement of conductance of the solution during the titration.
The conductance of a solution depends on
1. The number and charge on the free ions, and
2. The mobility of the ions

Acid Base Titrations:

1. Strong acid Vs Strong base (HCl Vs NaOH)

Known amount of acid (HCl) is taken in the conductivity cell and the
alkali (NaOH) in the burette. Initially the conductivity of the HCl
is high , this is due to the presence of fast moving H ions (Point A in
the graph). As the NaOH is added gradually, conductance will be
going on decreasing until the acid has been completely neutralized
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(indicated by the line AB . This is due to the replacement of fast
moving H ions by slow moving Na ions. The point ‘B’ indicates
complete neutralization of all H ions.

HCl + NaOH  Na+Cl- +H2O

Further addition of NaOH will introduce the fast moving OH- ions.

Therefore the conductance, after reaching a certain minimum

value, will begin to increase (indicated by the line BC. On plotting
the conductance against the volume of alkali added, the two lines
intersect at a point ‘B’ gives the end point. This corresponds to the
volume of NaOH required for neutralization.

2. Weak acid Vs Strong base CH3COOH Vs NaOH

Known amount of weak acid CH 3COOH is taken in the conductivity cell and the
alkali (NaOH) in the burette. Initially the conductivity of CH 3COOH is low; this
is due to the poor dissociation of CH 3COOH. (Point A in the graph). As NaOH is
added gradually, conductance will be going on slowly increasing (indicated by
the line AB). This is due to the formation of highly ionized CH3COONa.

CH3COOH +NaOH------- CH3COONa +H2O

Poor ionized highly ionized

 The point B indicates the complete neutralization of CH3COOH.
Further addition of NaOH introduces excess of fast moving OH -ions.
Therefore the conductance of the solution begins to increase even
more sharply than before (line BC).On plotting the conductance
against the volume of alkali added, the two lines intersect at point
‘B’ gives the end point

3. Strong acid Vs weak base (HCl Vs NH4OH)

Known amount of HCl is taken in the conductivity cell and NH4OH is added
gradually from the burette. Initially the conductivity of HCl is high (Point A in
the graph). As the NH4OH is added gradually the conductance will be going on
decreasing until all the acids been completely neutralized (line AB). This is due to
the replacement of H+ ions by slow moving NH+4 ions.

HCl+NH4OH --- NH4Cl +H2O

Further addition of poorly ionized NH4OH does not

Cause any appreciable change in the conductance
(slow increase) (line BC).
The point of intersection ‘B’ is the end point.

4. Weak acid Vs weak base (CH3COOH Vs NH4OH)

When CH3COOH is titrated against NH 4OH, conductivity is going

on increasing (indicated by the line AB). This is due to the
formation of highly ionized salt CH3COO-NH4+. After the
neutralization of CH3COOH, further addition of poorly ionized
NH4OH does not cause any appreciable change in the
conductance (slow increase) (line BC). The point of intersection
‘B’ is the end point.

CH3COOH + NH4OH → CH3COONH4 +H2O

SVCE TIRUPATI

3.7 Electrochemical sensors: Sensors are sophisticated devices that are frequently
used to detect and respond to electrical or optical signals. A Sensor converts the
physical parameter (for example: temperature, blood pressure, humidity, speed, etc.)
into a signal which can be measured electrically.

An electrochemical sensor is made of a reference electrode and a sensing electrode

(working electrode) separated by electrolyte. The mode of operation for
electrochemical sensors involves the production of an electrical signal by reaction
with the analyte of interest.

Working of sensors:

Types of sensors: There are two types of sensors.

1. Potentiometric sensors

2. Amperometric sensors

Potentiometric sensor: A potentiometric sensor is a type of chemical sensor that

may be used to determine the analytical concentration of some components of

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BTECH_S&H-SEM1
the analyte gas or solution. These sensors measure the electrical potential of an
electrode when no current is present.

Principle: The signal is measured as the potential difference (voltage) between

the working electrode and the reference electrode. The working electrode's
potential must depend on the concentration of the analyte in the gas or solution
phase. The reference electrode is needed to provide a defined reference potential.

Biocatalytic membrane electrodes (biosensors): These devices

feature an immobilized enzyme that catalyzes a specific reaction,
often, one that changes the pH. In that case the actual sensing
device is a pH electrode. The substrate complexes with the enzyme;
the enzyme product diffuses to the ion selective membrane. The
glass membrane electrode was the I ISE to be discovered and
characterized and used for pH measurements.

Types of membranes:

Glucose: Glucose oxidase catalyzes formation of gluconic acid 6 pH changes

Urea: Urease hydrolyzes urea 6 NH4 + ; pH change

Characteristics of ISE: An ISE can be considered a suitable sensor for quantitative

ion analysis. Of these slope, selectivity, limit of detection and electrode working life
are the most important.

Applications of ISEs

1. The ISEs are used for the detection of commonly occurring

inorganic cat ions and anions with membrane based potentiometric
sensors.
2. It is also used to detect the species like organic ions, proteins
and enzymes, vitamins, medicines and other species of complex
molecular composition that can also be detected.

3. ISE is commonly used as detectors in auto titrations, where the

electrode is used to detect the end point of titrations.

Example: A Urea Potentiometric Biosensor Based on a Thiophene

Copolymer.
A potentiometric enzyme biosensor is a convenient detector for
quantification of urea concentrations in industrial processes, or for
monitoring patients with diabetes, kidney damage or liver
malfunction. Urease was covalently attached to the smooth
surface of the copolymer via carbodimide (RN=C=NR) coupling.
The electrochemical behaviour and stability of the modified Urease
in glass electrode were investigated by cyclic voltammeter. By
this
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SVCE TIRUPATI
cyclic voltammeter the peaks for Ascorbic acid and Uric acid will
be separated.
There are two methods for the measurement of UA (uric acid),
enzymatic and non enzymatic.
The enzymatic procedures using urease have been developed
based on amperometric detection of H2O2produced in the
reaction.

Uric acid+O2 +H2O  Allantonin+H2O2+CO2

Uric acid +M (ox)+2H2O----> Allantonin +M(red)+CO2+2H+

M (red ) M(ox)+2e-

Amperometric sensors: Amperometric sensors measure current response to detect

the concentration of an analyte at a fixed potential. A simple form
of amperometric measurement is single-potential amperometry or
DC amperometry. A voltage is applied between two electrodes during
measurement.

Principle: The amperometric and polarographic methods rely on the

same principle that the diffused current (i d) is proportional to the concentration.
Thus, when an electro active material (metal ion) is removed from a solution using
some reagent (ligand), a decrease in the diffused current is observed.

Example: Glucose Sensor

The glucose sensor is widely used in clinical laboratories for the

determination of glucose in blood. This device is similar in
construction to oxygen sensor shown in the above figure. The
membrane in this case is more complex and consists of three layers.
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SVCE TIRUPATI
The outer layer is a polycarbonate film that is permeable to glucose
but impermeable to proteins and other constituents of blood. The
middle layer is an immobilized enzyme, glucose oxidase in this
instance. The inner layer is a cellulose acetate membrane, which is
permeable to small molecules, such as hydrogen peroxide. When
this device is immersed in a glucose-containing solution, glucose
diffuses through the outer membrane into the immobilized enzyme,
where the following catalytic reaction occurs.

Glucose +O2 --- H2O2 + gluconic acid

The hydrogen peroxide then diffuses through the inner layer of

membrane and to the electrode surface, where it is oxidized to
give oxygen.

H2O2 + 2OH-  O2 + 2H2O +2e-

The resulting current is directly proportional to the glucose concentration of the

electrolytic solution.

3.8 BATTERIES:-
- 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.

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SVCE TIRUPATI
- A device which converts chemical energy to electrical energy is called Battery,
which are commercial electrochemical cells.
- They are of 3 types.
1. Primary cells
2. Secondary Cells
3. Fuel cell

1. Primary cells: -
- In these cells the cell reaction is not reversible.
- When the reactants almost converted to products, further no more electricity
is produced and the battery becomes dead. Hence they cannot be recharged.
Eg: - Zinc-air battery

Nickel - cadmium battery

2. Secondary cells; -
- In these cells, the cell reaction can be reversed by passing direct electric current
in opposite direction. They can be used again and again by recharging the cell.
Eg: - Lead acid battery
Lithium ion battery
1. Primary Battery
Ni—Cd storage cell / Ni-Cad battery: - This is recently developed, portable,
rechargeable cell and its voltage is fairly constant (about 1.4V).
It consists of ‘Cd’ anode, a cathode composed of a paste of ‘NiO (OH) 2 ’(s).
Electrolyte : KOH solution
Anode: Cd (s) +2OH-(aq)  Cd (OH)2 (s)+ 2e– (oxidation)
Cathode: 2 NiO(OH)2 (s)+ H2O(l)+2e-  2 Ni(OH)2 (s) + 2OH- (aq)
(Reduction) Net cell reaction: 2 NiO(OH)2 (s)+ Cd(s)+2H2O  Cd(OH)2(s) + 2
Ni(OH)2(s)

- This reaction can be readily reversed, because the reaction

products, Cd(OH)2 and Ni(OH)2 adhere to electrode surfaces.
Applications:
- They are mainly used in electronic calculators, CD
players, electronic cars, cordless electronic shavers and
transistors.
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SVCE TIRUPATI
- They have long durability without any maintenance.

BTECH_S&H-SEM1
Zinc-Air battery:

Zinc-air batteries work by the oxidation of Zn with oxygen from the air. These
batteries have high energy densities and are relatively inexpensive to produce. Sizes
range from very small button cells for hearing aids, larger batteries used in
film cameras that previously used mercury batteries, to very large batteries used
for electric vehicle propulsion and grid-scale energy storage.

Construction: A mass of loose granulated zinc particles mixed with an electrolyte

such as KOH to form a porous anode. The gas diffusion electrode , in the other
side, acts as cathode.

Working: During discharge, a mass of zinc particles forms a porous anode, which
is saturated with an electrolyte. Oxygen from the air reacts at the cathode and
forms hydroxyl ions which migrate into the zinc paste and form zincates (Zn(OH)42−),
releasing electrons to travel to the cathode. The zincates decays into zinc
oxide and water returns to the electrolyte. The water and hydroxyl from
the anode are recycled at the cathode, so the water is not consumed. The
reactions produce a theoretical 1.65 volts, but this is reduced to 1.35–1.4 V in
available cells.

Chemical reactions:

The various chemical reactions occurring in the cell are

Anode:

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SVCE TIRUPATI
Zn  Zn2+ + 2e-

Zn2+ + 4OH− → Zn (OH) 4

2− + 2e− (oxidation)

Electrolyte : Zn (OH) 4
2− → Zn O + H2O + 2OH−

Cathode: 1/2 O2 + H2O + 2e− → 2OH− (Reduction)

Overall cell Reaction : 2 Zn + O2 → 2 Zn O (E0 = 1.59 V)

Factors affecting rate of reaction

1. The rate of reaction can be controlled by varying the oxygen

flow.

2. The rate of reaction can be increased by replacing oxidized

Zinc/electrolyte paste by fresh paste.

2. SECONDARY BATTERY:

Lithium Ion cells or Rechargeable cells:

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BTECH_S&H-SEM1
- These cells do not contain metallic ‘Li’ instead it contains lithium ions (Li +).
Anode: Graphite
Cathode: Lithium Cobalt oxide
- In these cells the true oxidation/ reduction does not takes place, instead of that
transport of Li+ ions through the electrolyte from one electrode to the other takes
place.
- When the cell is constructed, it is in its uncharged state with no Li + ions between
the layers of ‘C’ atoms in the graphite.
- When the cell is charging, Li + ions leave LiCoO2 and travel through the electrolyte
to the graphite C6.
LiCoO2 + Graphite (C6)  Li(1-x) CoO2+ Lix C6.
- When the cell spontaneously discharges to provide electrical power, Li + ions move
back through the electrolyte to the cobalt oxide while electrons move through the
external circuit from the graphite electrode to the cobalt oxide electrode.
Li1-x CoO2 + LixC6  Li1-x+y CoO2+Lix-yC6
Y=amount of Li+ transferring from LixC6. LiCoO2 1-x
X= transferring amount of Li+ from LiCoO2 to graphite.
- Thus the charging and discharging cycle simply sweep Li+ ions back and forth
between two electrodes with electrons flowing through external circuit to keep
the charge balance.
SVCE TIRUPATI

3. FUEL CELL/FLOW BATTERY: -

- The reactants are continuously supplied from an external source to the cell and
the reaction products continuously removed, such cells are called as fuel cells.
- In a fuel cell electrical energy is obtained without combustion from O 2 and gas
can be oxidized. Hence fuel cell converts chemical energy of the fuel directly to
electricity.
The important steps in the fuel cell
Fuel + O2  oxidation product + electricity
- In which fuel is gas/liquid and oxygen being oxidized. In fuel cell the chemical
energy is provided by fuel and easily converts to electrical energy.
- Fuel cells are characterized by,
(1) High efficiency
(2) Low noise levels
(3) Free from vibration, heat transfer.
- The most important fuel cells are
(1) H2-O2 fuel cell
(2) Methanol fuel cell
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SVCE TIRUPATI
(1) H2-O2 fuel cell: - It is successful and simplest cell.
- Electrodes: - Porous Platinum electrode, electrolyte –
35-40% KOH.
- It consists of hot concentration KOH electrolyte solution
and Two porous Pt electrodes are dipped in KOH solution.
- At anode H2 gas and at cathode O2 gas is supplied, which are come in contact
with electrodes and shows following reactions.
Cathode: O2 + 2H2O+4e- 4OH- (aq)

Anode : H2+4OH- 
4H2O+4e-
H2+O2  2H2O

Applications:-
(1) They are used as energy source in space vehicles, submarines or military
vehicles.
(2) The reaction product is water, which is harmless and used as source of fresh
water to the astronauts.
(3) The weight of fuel battery for 15 days is about 250 Kg.
Disadvantages:-
(1) Energy cost of generating H2 fuel.
(2) Difficult in storage and highly flammable.
(3) Availability of alternative fuels.
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BTECH_S&H-SEM1
 (2)Methanol fuel cell/proton exchange fuel cells:-
-Electrodes:- Porous Pt electrodes, separated by proton transport membrane.
-Anode: Oxidation of CH3OH and H2O absorbed on catalyst to from -CO 2 with lose
of H+ (Protons) and electrons.
- Cathode: - H2O is liberated by reduction of O 2, which accepts electrons and
protons. Protons are transported from anode to cathode through proton transport
membrane, while electrons transport through electric circuit.
- The liberated H2O (at cathode) is consumed at anode.
Oxidation: CH3OH+H2O  CO2+6H++6e-
Cathode : 3/2 O2 + 6H++6e-  3H2O
Reaction: CH3OH+3/2 o2  Co2+2H2o

Advantages:-
(1) Storage of methanol is much easier than H2 (does not high pressure or low
temperature) since methanol is liquid form -97.00 C to 64.70 C (-142.60 F to 148.50F)
(2) The energy density of methanol is greater than H2.
 Disadvantages:-
(1) During methanol oxidation, CO formed which is strongly adhere on to pt
catalyst, reducing, the surface area and lowering the performance.
(2) CH3OH is toxic and flammable and so utmost care is necessary.
(3) Limited power is produced by them.
9. Practice Quiz
1. Pure water does not conduct electricity because it is [ a]
a) Almost not ionized b) decomposed easily c) Low boiling d) neutral
2. Conductivity of a solution is directly proportional to [ a ]
a) Number of ions b) dilution c) Volume of the solution d) current density
3. Kohlrausch law is related to [ c]
a) Equivalent conductance b) Molar Conductance
c) Molar Conductance at infinite dilution d) specific conductance
4. What is the voltage produced by H 2 – O 2 fuel cell, operating under
standard conditions. [b
]
a) 1 V b) 1.23 V C) 2 V d) 0.5 V
5. In conductometric titrations ---- energy source is used [ a]
a) A.C b)D.C C) Both d) None
6. In Methanol Oxygen fuel cell transfer takes place [ a]
a) six electrons b) Six protons c) water d) Oxygen
7. The potential of two metals used in a cell are 0.35v and 0.25v. The
EMF of the cell formed by connecting them is [a ]
(a) 0.5 V (b) 1.20 V (c)-0.5 V (d) None of these
8. A galvanic cell converts
[a ]
a) chemical energy into electrical energy
b) electrical energy into chemical energy
c) chemical energy into heat energy
d) electrical energy into heat energy
9. The name of the reaction at anode is
[b ]
a) reduction b) oxidation
c) both oxidation and reduction d) no reaction takes
place
10. Specific conductance is the reciprocal of [ c]
(a)resistance (b) cell constant (c)specific resistance (d)none
10. Assignment Questions:

Question BL CO
S.No
1 Calculate the emf of the Zinc –Silver cell at 250C when
3 3
[ZN2+]= 0.10M and [Ag+]=10.0M(E0 cell at 250C=1.56V).
2 3
Explain the construction and working of Lithium ion battery. 2
3 3
Explain the types of conductometric acid base titrations. 2
Explain the construction, working and applications of H2-O2 fuel 3
4 2
cell.
5 3
Describe the working of amperometric sensor. 2

11. Part A- Question & Answers

S.No Question& Answers BL CO

1 What is electrode potential

Ans: The tendency of an electrode to lose or gain electrons when it is

2
in contact with a solution of its own salt is called “Electrode
3
potential”.

2 What is secondary battery and give two examples.

Ans: The battery in which the electrode reactions can be reversed by

passing an external electrical energy is called as secondary battery 2 3

or secondary cell or rechargeable. Ex: Ni-Cd battery, Lead acid

battery.

3 Define fuel cell and give any two examples.

Ans: Fuel cell is a voltaic cell, which converts the chemical energy of 2 3

the fuel directly into electricity without combustion.

 Fuel+O 2  Oxidation product +Electricity

4 What are the advantages of glass electrode?

(i) It can be easily constructed and readily used.

(ii) The results are accurate. 2 3

(iii) It is not easily poisoned.

(iv) Equilibrium is rapidly achieved.

5 What are sensors mention their types?

Sensors are devices which convert one form of energy into another.
There are so many sensors of which the followings are some
important sensors.

1. Potentiometric sensors 2 3

2. Amperometric sensors

3. Electrochemical sensors

6 Define conductivity
2 3
Conductivity (or) conductance of an electrolyte solution is a
measure of its ability to conduct electricity.

7 What are electrodes?

An electrode is a solid electric conductor that carries electric current

into non-metallic solids (or) liquids (or) gases. They are typically good
electric conductors. Types of electrodes 2 3

1. Anode: Anode is an electrode at which oxidation occurs

2. Cathode: Cathode is an electrode at which reduction occurs.

 8 What are the factors affecting electrode potential?

The rate of the above reactions depend on (i) The nature of the 3
2
metal. (ii) The temperature. (iii) The concentration of metal ions in
solution.

9 What is standard electrode potential?

It is the measure of tendency of a metallic electrode to lose or gain

electrons, when it is in contact with a solution of its own salt of 1 3
2
molar concentration at 250C .

10 Define emf. 2 3

Electromotive force is defined as, "the difference of potential which

causes flow of electrons from one electrode of higher potential to
the other electrode of lower potential.

12.Part-B Questions

S.No Question BL CO

1 Calculate the emf of the Zinc –Silver cell at 250C when

3 3
[ZN2+]=0.10M and [Ag+]=10.0M(E0 cell at 250C=1.56V).
2 3
Explain the construction and working of Lithium ion battery. 2
3 3
Explain the types of conductometric acid base titrations. 2
4 Explain the construction, working and applications of H2-O2 fuel 3
2
cell.
5 3
Describe the working of amperometric sensor. 2
6 Explain about the Zinc-Air battery. 2 3
7 Describe the potentiometric titration. 2 3
8 Derive the Nernst equation. 2 3
12. Supportive Online Certification Courses
1. Engineering chemistry-1 by Prof. Mangala Sunder conducted by IIT Guwahati-
12 weeks
2. Electrochemistry by Vinay Arya conducted by Udemy -2 weeks.

13. Real Time Applications

S.No Application CO
1 Analysis of conductance of solutions. 1

2 Determination of pH of solutions. 1

14. Contents Beyond the Syllabus

 EMF of a cell
 Types of conductance

15. Prescribed Text Books & Reference

Books Text Book
1. Jain and Jain, Engineering Chemistry, 16/e, DhanpatRai, 2013.
2. Engineering chemistry by SS.Dara, SS.Umare by S Chand publications.
3. Chemistry for Engineers by Dr.B.K.Ambasta.

16. Reference Books:

1. G.V.Subba Reddy, K.N.Jayaveera and C. Ramachandraiah, Engineering

Chemistry, Mc Graw Hill, 2020.
2. Engineering chemistry by Dr.A.Ravi krishnan,Dr.M.Bakkiya Lakshmi -2020