Module - 05

Sensors in Analytical Techniques

Electrode System: Introduction, types of electrodes. Ion selective electrode – definition,
construction, working and applications of glass electrode. Determination of pH using glass
electrode. Reference electrode - Introduction, calomel electrode – construction, working and
applications of calomel electrode. Concentration cell – Definition, construction and
Numerical problems.

Sensors: Introduction, working principle and applications of Conductometric sensors,

Electrochemical sensors, Thermometric sensors, and Optical sensors.

Analytical Techniques: Introduction, principle and instrumentation of Colorimetric sensors;

its application in the estimation of copper, principle and instrumentation of Potentiometric
sensors; principle and instrumentation of its application in the estimation of iron,
Conductometric sensors; its application in the estimation of weak acid.

Self-learning: IR and UV- Visible spectroscopy.

Introduction:
Electrochemistry is a branch of physical chemistry which deals with the
interconversion of chemical energy into electrical energy or vice versa. A device in
which an electrochemical change takes place in the system is also known as
Electrochemical cell.

Electrochemical cells are broadly classified into two types:

Galvanic cell: A galvanic cell is an electrochemical cell which converts chemical

energy into electrical energy. It is also known as voltaic cell.

Electrolytic cell: An electrolytic cell is an electrochemical cell which converts

electrical energy into chemical energy.

Cell Potential (EMF) of cell

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

The standard cell potential (E0cell) is the difference of the two electrodes, which
forms the voltage of that cell. To find the difference of the two half cells, the
equation used is,

Eocell = Eocathode - Eoanode

Where, Eocell is the standard cell potential

Eocathode is the standard reduction potential for the reduction half reaction occurring at
the cathode.

Eoanode is the standard reduction potential for the oxidation half reaction occurring at
the anode.
 Electrode System
Introduction:
 An Electrode can be defined as the point where current either enters
or leaves the electrolyte or circuit. When the current leaves the
Electrode it is known as the cathode while when the current enters the
Electrode it is known as an anode. Electrodes are the main component of
electrochemical cells.
 Electrodes are good conductors of electricity. Electrodes are used to
make contact between non-metallic parts such as electrolytes,
semiconductors, air, etc. of the circuit.
 Electrodes are the main component of electrochemical cells. Although
inert Electrodes also exist which don’t take part in the reaction.
 An electrode can be of gold, platinum, carbon, graphite, metal, etc. The
electrode provides a surface for oxidation reduction reactions in the cells.
Types of Electrodes

Metal – metal ion electrode: In this electrode a metal is dipped in its metal ion
solution.
Ex. Zinc in zinc sulphate solution; Zn/ZnSO4 (Zn/Zn2+)
Copper in copper sulphate solution; Cu/CuSO4 (Cu/Cu2+), etc

Metal – metal insoluble salt-salt anion electrode: This is the electrode in which
metal is in contact with its sparingly soluble salt dipped in anion solution of the salt.
Ex. Calomel electrode, Hg(l)/Hg2Cl2(s)/Cl-(aq)
Silver –silver chloride electrode, Ag(s)/AgCl(s)/ Cl-(aq)
Lead- lead sulphate electrode, Pb(s)/PbSO4(s)/SO42-(aq), etc

Gas electrode: A gas electrode consists of gas, bubbled about inert metal wire
(platinized platinum electrode) immersed in a solution containing ions with which
gas is irreversible. Platinum is used as conductor and to adsorb the gas.
Ex. Standard hydrogen electrode, Pt| H2(g) (1 atm.)| H+(aq) (1 M)
Chlorine gas electrode, Pt| Cl2(g)(1 atm.)| Cl-(aq) (1 M), etc.
Metal - amalgam electrode: This is an electrode which consists of metal amalgam
immersed in a solution containing metal ions.
Ex. Lead amalgam electrode, Pb-Hg(s)/Pb2+ (aq)
Zinc amalgam electrode, Zn-Hg(s)/Zn2+ (aq)

Oxidation – reduction electrode: This consists of platinum wire dipped in a system

containing both oxidized and reduced form of a substance. The potential is
developed due to spontaneous conversion of the substance from one form to more
stable form. The platinum facilitate the redox reaction.
Ex. Pt, /Fe2+, Fe3+ Pt, /Sn2+, Sn4+ Pt, /Cr3+, Cr6+

Ion – selective (membrane) electrode: This consists of a membrane which

exchanges a specific ion between solutions in which it is dipped.
Ex. Glass electrode, Ag(s)/ AgCl(s)/ 0.1M HCl/ Glass
1. Ion selective electrode
“Ion selective electrode is very selective towards particular type of ions and
develop a potential proportional to the concentration of that ions. The sensitive
part of electrode is its membrane which allows the exchange of selective ions”.

Ion selective electrode (ISE) are comparatively simple membrane based

potentiometric devices which are capable of accurately measuring the
concentration of ions in solution.

Ex: Glass electrode, Crystalline electrodes, Ion-exchange electrodes,

Enzyme electrodes, Alkali metal ISE.

Working mechanism of ion selective electrodes

Solution to Internal Internal
External
analyzed standard referenc
referenc Membrane
(analyte) solution e
e
(Mn+) = C2 (Mn+) = C1 electrode
electrode
Working and applications of glass electrode

GLASS ELECTRODE
Construction Glass electrode:
1. Glass electrode is constructed by immersing Ag-AgCl internal reference
electrode in a glass bulb containing 0.1M HCl solution.

2. The glass bulb is made up of a long glass

tube with a thin highly conducting glass
membrane at the bottom.

3. The glass membrane is selective to H+ ions

in the solution, and is made up of silicate glass
having composition of 72% SiO2, 22% Na2O
and 6 % CaO.

The electrode can be represented as

Ag/AgCl/0.1M HCl/Glass membrane

Working of glass electrode

When a glass bulb containing 0.1M HCl is immersed in an acidic solution of

different concentration, a boundary potential (Eb) is developed across the gel
layers of the glass membrane.

This boundary potential (Eb) arises due to the difference is concentration of H+

ions inside and outside of the glass bulb.

𝐸𝑏=0.0591 𝑙𝑜𝑔𝐶2/𝐶1
C1 = Concentration of H+ inside the bulb, is a constant, C2 = concentration H+
outside the bulb.
𝐸𝑏=0.0591 𝑙𝑜𝑔[𝐶2]− 0.0591 𝑙𝑜𝑔[𝐶1]
Substitute − 0.0591 𝑙𝑜𝑔[𝐶1]=𝐾, a
constant Then the equation becomes
𝐸𝑏=𝐾+0.0591 𝑙𝑜𝑔[𝐶2]=𝐾+0.0591
𝑙𝑜𝑔[𝐻+]
 Substitute log (H+) = - pH
The final equation for Eb is obtained as 𝐸𝑏=𝐾−0.0591 𝑝𝐻
The potential of glass electrode (EG) includes contribution from 3 factors

 Boundary Potential (Eb)

 Potential of Ag-AgCl reference electrode dipped inside the bulb E Ag/AgCl
 Asymmetric potential due to slight in homogeneity of the inner and outer
surface of the glass membrane E Asy.

𝐸𝐺=𝐸𝑏+𝐸𝐴𝑔/𝐴𝑔𝐶𝑙+𝐸𝐴𝑠𝑦

𝐸𝐺=𝐾−0.0591 𝑝𝐻+𝐸𝐴𝑔/𝐴𝑔𝐶𝑙+𝐸𝐴𝑠𝑦
𝐸𝐺=𝐿−0.0591
𝑝𝐻
𝐿=𝐾+𝐸𝐴𝑔/𝐴𝑔𝐶l+𝐸𝐴𝑠𝑦
Where constant
Application of Ion-selective electrode

 Clinical chemistry: Analysis of electrolyte such as Na+, K+ in blood,

serum etc. 
 Environmental chemistry: For the analysis of CN, F, NH3, NO3,
in water and wastes samples.
 Agricultural chemistry: For the analysis of K+, NH4+, etc, in soil
and plant sample
 Industry: For the analysis CN in electroplating bath.
 Pharmaceutical: For the analysis of F- and pH of the
toothpaste.
 Research and education: For the measurement of pH and other
types of ions sample.
Determination of pH using glass electrode

To measure of pH of an unknown solution a glass electrode is

coupled with calomel electrode and connected to potentiometer (or
pH meter for reading pH directly)

Hg/Hg2Cl2

KCl
The cell formed is represented as

Hg/Hg2Cl2/KCl// solution of unknown pH/Glass electrode

The potential established at the glass electrode is higher than that of

the calomel electrode hence glass electrode is taken as cathode.

E Cell = E Cathode – E anode

E Cell = E G – E SCE

Substituting for EG
E Cell = (L- 0.0591pH) – E SCE
The above equation𝑝𝐻=𝐿−𝐸
is arranged to−𝐸
obtain the expression for pH
𝑆𝐶𝐸 𝑐𝑒𝑙𝑙
0.0591

Note: EMF (Electromotive force) of the Cell - The potential difference b/w two
electrodes in the galvanic cell is know as EMF of the cell.
E Cell = E Cathode  E Anode
Reference electrode

An electrode having fixed potential, which can be used as a reference to

measure the potential of another electrode.
Construction
The saturated calomel electrode (SCE) is a reference
electrode based on the reaction between elemental
mercury and mercury chloride.
The calomel electrode consists of two glass tube. At the
inside glass tube, there is a paste of mercury and
mercurous chloride (calomel) (Hg2Cl2) at the bottom of
a narrow glass tube having a porous plug at the bottom.
Pure mercury is filled above paste and connected with
platinum wire for electrical connections. This narrow
tube placed inside an outer glass tube filled with a
saturated KCl solution.
KCI solution of 0.1 M or of 1 M can also be used. The
porous plug at the bottom of outer tube acts as salt
bridge.
 Calomel electrodes can be represented as

Hg(l)  Hg2Cl2 (s)  KCl (aq)

Working
:
Since the calomel electrode is reversible, two types of reactions are
possible depending upon the nature of another electrode with which it is
coupled.

When it acts as anode, the electrode reaction is

2𝐻𝑔+2𝐶𝑙−→2𝐻𝑔2𝐶𝑙2+2𝑒−

Thus, oxidation takes place when it is coupled with another

electrode having lower oxidation potential.

When it acts as cathode, the electrode reaction is

Thus, reduction takes place when it is coupled

with another electrode
having greater oxidation potential.

The net reversible electrode reaction

 2𝐻𝑔2𝐶𝑙2 + 2𝑒− ↔
2𝐻𝑔+2𝐶𝑙−
Electrode potential

𝐸 =𝐸 − 0.0591 𝑙𝑜𝑔[𝐶𝑙−] at 298 K

The electrode potential is decided by the concentration if chloride ions and the
electrode is reversible with chloride ions. At 298 K, the electrode potentials
are as follows.

0.1 M KCl electrode (0.334 V)

1 M KCl electrode (0.281 V)
Saturated KCl electrode (0.2422
V)

Applications of calomel electrode:

1. It is used as secondary reference electrode in the
measurement of single
electrode potentials.
Concentration cell
Electrolyte Concentration Cells
These cells consist of identical electrodes immersed in the solutions of the
same electrolytes but with varying concentrations. Potential difference
arises due to difference in electrolyte concentration.

Components of the Concentration Cell

Electrode The two electrodes are called the cathode (right side) and the
anode (left side). The anode loses electrons through oxidation reaction.
The cathode gains electrons through reduction reaction.
 Salt Bridge: The salt bridge offers the perfect solution for the
separation
of the two half-cells while providing a pathway for ion transfer.
 Voltmeter: The voltmeter is used to measure the cell potential of the
cell.
Construction:
The concentration cell is a type of galvanic cell where the half-cells
consist of the same substance but at different concentrations. These cells
give a small potential difference while moving towards chemical equilibrium
which can be measured using a voltmeter.
Example: The anode consists of Cu/Cu2+(0.001M) whereas the
cathode consists of Cu2+(0.1M)/Cu. In this cell, the flow of electrons from
the anode to the cathode is due to the reduction of Cu2+ ions at the cathode
into metallic copper.
Cell representation

Cu  Cu+2 (C1 = 0.001M)   Cu+2 (C2 = 0.1 M)  Cu

Cell reaction
At anode
Cu Cu+2 (C1 = 0.001 M) + 2e

At cathode
Cu+2 (C2 = 0.1 M) + 2e ̶

Cu

Nernst equation for concentration cell

Nernst equation for anodic reaction:
𝐸𝑎𝑛𝑜𝑑𝑒 = 𝐸𝑜 𝑎𝑛𝑜𝑑𝑒 + (2.303𝑅𝑇 /𝑛𝐹)
𝑙𝑜𝑔 𝐶1

Nernst equation for cathodic reaction:

Cell potential:
When reduction potential of both electrodes is taken into account

𝐸𝑐𝑒𝑙𝑙 = (𝐸𝑜 𝑟𝑒𝑑 (𝑐𝑎𝑡ℎ𝑜𝑑𝑒) − 𝐸𝑜 𝑟𝑒𝑑 (𝑎𝑛𝑜𝑑𝑒)) + (2.303𝑅𝑇 /

𝑛𝐹) 𝑙𝑜𝑔 𝐶2 /𝐶1
In concentration cell, both electrodes are same, hence

𝐸𝑜 𝑟𝑒𝑑 (𝑐𝑎𝑡ℎ𝑜𝑑𝑒) − 𝐸𝑜 𝑟𝑒𝑑 (𝑎𝑛𝑜𝑑𝑒)=

0
Sensor
• Sensor is a device that detects and responds to some type of input from the
physical environment
• Input could be light, heat, motion, moisture, force, pressure, displacement, etc.
• It produces a proportional output signal (electrical, mechanical, magnetic, etc.)
• The sensor is device that interacts with a specific chemical or biological species
(analyte), detects it and measure its physical/ chemical information into
measurable electrical signal proportional to its quantity.
• Physical/Chemical phenomena such as Temperature, pressure, motion, light, or
sound / composition, concentration, chemical activity, partial pressure etc.

Sensors Play Key Role in:

 Environmental monitoring
 Industrial process monitoring
 Gas composition analysis
 Medicinal field for disease diagnosis and health monitoring
 Agricultural area for soil monitoring
COMPONENTS OF SENSOR

• Receptor is a chemical or biological recognition element and is able to interact with the
analyte molecules specifically and selectively.
• Receptor produces a signal corresponding to interaction.
• During the interaction certain physical or chemical properties of the sensing element
changes proportionately to the analyte concentration.
• Transducer is a energy conversion device, that converts a physical quantity or non-
electrical signal created by the receptor-analyte interaction into a readable or
measurable electrical signals like voltage, current or resistance.
• The actual concentration value is non-electric quantity is transformed into an electric
quantity like voltage, current or resistance.
Conductometric sensors

Conductometric sensors are chemical sensors which measure the electrical

conductivity of an analyte on the basis of the concentration of that analyte.
• The principle of conductometric detection based on the dissociation of analyte
into ionic species under the applied electric field.
• This leads to the migration of ions toward oppositely charged electrodes, results
in the change in electrical conductivity of the solution.
• The change in conductivity is measured by the conductometric sensor.

CONSTRUCTION

• It is made up of two platinum foils with

unit cross sectional area and unit distance
unit between them.
• Volume between two electrodes is 1cm3.
 WORKING
• When a potential difference is applied to the
electrodes, there is an electrical field within the
electrolyte.
• The positively charged ions move towards cathode
and negatively charged ions are move towards
anode.
• Thus, movement of ions toward the electrodes
results in neutralization of ions as neutral atoms or
molecules.
• This chemical change is recognized by transducers
which converts this chemical change into
conductance (electrical signal).

APPLICATIONS
• To estimate the acids, bases and their mixtures
• To check the amount of ionic impurities in water samples
• In measuring acidity or alkalinity of sea water or fresh water
• Used in enzyme catalyzed reaction to determine the analyte concentration and enzyme
activity
• Used to determine the analytes of biomedicine/biosamples
ELECTROCHEMICAL SENSORS
• Electrochemical sensors are devices that detect and measure the concentration of a
target analyte by converting the effect of electrochemical reaction between analyte and
electrode surface into an electrical signal.
• Electrochemical sensors consist of a set of electrodes acts as transducer element.
Hence, these sensors are also known as Electrochemical cells.
• Depending on the mode of signal transduction,

Electrochemical sensors can be classified in to following types:

 Potentiometric sensor (measure voltage)

 Amperometric sensor (measure current)
 Conductimetric sensor (measure resistance or conductivity)
 WORKING
• Electrochemical sensing always requires a closed circuit. Current must flow to make a
measurement. Since we need a closed loop there should be at least two electrodes which
act as a transducer.
• The surface of electrode is used as the site of the reaction.
• The electrode will interact with analyte by either oxidizing or reducing the analyte based
on the nature of electrode and induces the flow of electrons.
• The current that is produced from the reaction is monitored and used to calculate the
important data such as concentration of the sample.
APPLICATIONS
• Used to detect dissolved oxygen in boiler water
• Used in water analysis and environmental monitoring like measurements of
toxic metal concentration in water, pH of water and detection of oxides of
nitrogen, sulphur and carbon.
• Used in soil parameter analysis and in agriculture applications to detect
pesticides.
• Used in clinical field like in-situ monitoring of blood glucose, Ca*, Fe2+ and
uric acid.
• Used in security and defense applications like detection of toxic gases and
warfare agents.
Thermometric sensors
Temperature sensors are simple devices that detect the amount of cold or
heat present and convert it into a simple unit. But, do you ever think about
how the temperature of the soil, land boreholes, great concrete dams, or
houses is detected? Well, this is done by using some of the particular
temperature sensors.

A thermometric sensor is a type of sensor used to measure temperature by

detecting and quantifying the physical change in a material or substance that
occurs as a result of temperature variations. These sensors convert temperature
changes into an electrical signal, which can then be measured and interpreted.
 Working Principle of Thermometric sensors

Main component of a thermometric sensor is a small tubular catalytic reactor fitted with a
temperature transducer. Analyte (reactant) is fed in to the reactor. The wall of the reactor is
coated with a catalyst or enzyme capable of catalysing the reaction, liberating heat energy.
Heat liberated is quantified by means of a temperature transducer. The change in
temperature is converted to the output voltage by transducer which is amplified and fed to
the data storage and processing unit. In order to convert change in temperature into an
electric signal, two main kinds of transducers which exhibit thermoelectric effect are used:

1. Resistive transducer: Most commonly used resistive

transducer is the thermistor. It is a ceramic
semiconductor device made of oxides of transition
metals. Most thermistors have a negative temperature
coefficient. That is, their resistance decreases with
increasing temperature. The decrease in resistance is
converted to output voltage using a Wheatstone
bridge resistor.
2. Thermocouple: A thermocouple is a device that converts the temperature difference

directly into an electrical voltage. It consists of a loop formed by two different materials
(metals or semiconductors). The output voltage is proportional to the temperature difference
between the two junctions.
Applications
• Industrial Processes: Monitoring and controlling temperatures in
manufacturing, food processing, and chemical plants.
• Automotive Industry: For engine temperature monitoring and climate control
systems.
• Healthcare: Used in medical devices like thermometers to monitor body
temperature.
• Home Appliances: Used in devices like refrigerators, ovens, and air
conditioning systems to regulate and measure temperature.
• Energy Systems: In power plants, for monitoring boiler temperatures, turbines,
and other critical components.
• Environmental Monitoring: For weather stations and climate studies to track
temperature variations in the atmosphere or water bodies.
Optical sensors

Optical sensors are a broad class of device for detecting light intensity. This can
be just a simple component for notifying when ambient light levels rise above
or fall below a prescribed level, or a highly sensitive device for detecting single
photons. Most optical sensors produce an electrical output.

Working principle
 Optical sensors use visible or ultraviolet light to interrogate sensors for
analysis. Optical sensors can be represented in general terms as a
wavelength-selectable light source, the sensor material itself interacting with
analytes, and a light detector (Fig. 1).
 What the detector monitors varies by technique (e.g., refractive index,
scattering, diffraction, absorbance, reflectance, photoluminescence,
chemiluminescence, etc.), can cover different regions of the electromagnetic
spectrum, and can allow measurement of multiple properties.
 The focus of this article, however, is on optical sensor arrays that use
absorbance, reflectance, or fluorescence array detectors (i.e., digital cameras
or scanners).
 Colorimetry (i.e., quantitative measurement of absorbance or reflectance
spectra) is, of course, one of the oldest of analytical techniques, and
colorimetric sensors stretch back even before the beginnings of chemistry.
 Colorimetric detection is a fairly simple technique, and the advent of
universal digital imaging has given it new and exciting possibilities.
 We will use the general term colorimetry to include simple colour (i.e.,
RGB) imaging, hyperspectral imaging (i.e., more colour channels), and full
spectrophotometry (i.e., hundreds of colour channels with nanometre
resolution).
Applications of Optical Sensors
 Application of these optical sensors ranges from computers to motion
detectors. For optical sensors to work effectively, they must be the
correct type for the application, so that they maintain their sensitivity
to the property they measure.
 Optical sensors are integral parts of many common devices, including
computers, copy machines (xerox) and light fixtures that turn on
automatically in the dark.
 And some of the common applications include alarm systems, synchros
for photographic flashes and systems that can detect the presence of
objects.
Analytical techniques
Introduction
Analytical chemistry is the study of the separation, identification
and quantification of the chemical components of natural and artificial
materials.

Analytical methods can be divided into classical and instrumental methods.

Chemical
1. Classicalmethod
methodsuse separation
(Chemical such as precipitation, extraction, and
method)
distillation and analyses the samples qualitatively by colour, odour, or melting
classical quantitively analysis is achieved by measurement of weight
gravimetrically or volumetrically.

2. Instrumental methods (Physical method)

Physical method or advanced instrument to measure physical quantities of the
analyte by relating the concentration with light absorption, fluorescence,
conductivity or Potential.
The instrumental methods have greatest advantage that it can investigate the
structure of complex organic molecules, reaction kinetics and even the
biochemistry of living cells.
Colorimetry
1. Simple technique used to determine the concentration of compounds in a
solution.
2.This method is used for solution which are themselves colored (or) which
gives colour with a suitable reagent.
3.The colour intensity of the solution is directly proportional to the
concentration of the solution.

Theory
This method is based on Beer- Lambert law
According to this law when a monochromatic light is passed through a
solution, part of light is absorbed by the solution. The extent of absorption
depends on the concentration of the solution and the path length of the light
trough the solution.
A=Є Cl
Where, A →Absorbance
C →Concentration of solution.
l → path length
Є → Molar absorption coefficient which is dependent on the
material
Instrumentation
Photo electric calorimeter are made of the following components.
1. Tungsten lamp as light source
2. A filter which provides the desired wavelength range.
3. A sample cell
4. A photocell detector

 Monochromatic light of suitable wavelength can fall on the sample cell.

 First blank solution is taken in the sample cell and placed in the path of light beam.
 Its absorbance is adjusted to zero.
 Then the analyte solution is placed in the path of light and it’s absorbance is
measured.
 A plot of absorbance versus standard concentration of analyte is used to find
the unknown concentration of analyte in the samples.
Application colorimetry
1. Colorimetry is used various laboratories including clinical laboratories
for biochemical estimation.
2. Colorimetry is used in clinical laboratories for the analysis
of biomolecules such as glucose, urea, etc.
3. Colorimetry is used soil testing laboratories for analysis of pesticides, soil
nutrients and plant nutrients.
Colorimetry is used in the estimation of copper in sample solutions.
Cu2+ ions are treated with NH3 to form a deep blue colored cupra-ammonium
complex
ion.
4. From a burette add 2, 4, 6 and 8 Cm3 of given copper sulphate solution into four
separate 50 cm3 in volumetric flask.
5. From another burette add 5cm3 of ammonia to each one of them, to the unknown
solution and blank solution flask.
6. To the entire six flasks add water up to the mark. Mix well wait for 10 minutes.
7. In the colorimeter set the wavelength of light to be 620 nm.
8. Using blank solution, set absorbance of colorimeter as zero
9. Record Optical density values for all the solutions including Test.
10.Plot a graph of absorbance against volume of CuSO4. Determine the volume of
CuSO4 is
Potentiometer

Theory
The measurement of e.m.f. (electromotive force) to determine the concentration
of ionic species in solution is referred to as potentiometry.
The relation between electrode potential and metal ion concentration is given
by Nernst equation.

E = E + (0.591/N) log Fe+2 / Fe+3

Instrumentation
1. Potentiometer consists of a reference electrode, and indicator electrode
and a device for measuring the potential.
2. The indicator electrode respond rapidly to the changes in the potential due
to the concentration changes of the analyte.
3. A known volume of the analyte is taken in a beaker and its potential is
determined by connecting the assembly to a potentiometer.
4. The titrant is added in increments of 0.5ml and the potential is measured
each time.
5. The equivalent point there is a sharp increase in the potential against the
volume of titrant.
6. Redox titration is that of ferrous
ammonium sulphate (ΔE/ΔV)
against K2Cr2O7 or KMnO4. The
oxidizing agent is usually taken in
the burette
Application
1. It is used in oxidation reduction titrations to estimate the concentration of
analyte in the sample solution.
2. The potential of the electrode depends on the concentration of the
substance
being oxidized or reduced.

Advantages
3. Potentiometric titrations (estimation) does not depend on color change
or
redox indicator.
2.Several analyte present in the same solution can be estimated by as single
titrating solution.
Conductometer
Theory
Electrolyte solution conducts current by the migration of ions under the
influence of an electric field.
E=IR
Where; I → current, R→ Resistance
Ohm’s law states that the current (I) flow through conductor is directly
proportional to the applied potential (E) and inversely to the resistance (R) of
conductor.
The reciprocal of resistance is called the conductance. The resistance of
homogenous material of uniform cross-section with an area of “a” sq. cm and
length ‘l’ cm is given by
R=  (l/a)
 → Specific resistance, l→ length, a → area cross- section.
Specific conductance
Specific conductance of an electrolyte solution is the conductance of the
solution present between two parallel electrodes of 1cm3 area of cross-section
and 1cm apart.
K= (1/R) (l/a)
Where l/a is known as the cell constant
‘R’ is the resistance of solution ; K = Cell constant
Resistance
Instrumentation
1.It consists of a platinum electrode each of unit area of
cross-section placed unit distance a part.
2.The electrodes are dipped in the electrolyte solution
taken in a beaker.
3. It is connected to a conductance measuring device.
4.The titrant is added from a burette and solution is
stirred.
5. The conductance is measured after the addition
of the titrant at intervals of 0.5 ml.
Application of conductometry
1. Strong acid with strong base (HCl vs NaOH)
NaOH + HCl → NaCl + H2O
a. Consider the titration of strong acid HCl with a strong base NaOH.
b. You will notice that on addition of NaOH the conductance of acid solution
decreases gradually until the acid is completely neutralized.
c. A plot of conductance against the volume of NaOH is shown in the figure.
d. The point of intersection of the two lines is the neutralization point.
e.The conductance decreases, because the small and highly mobile H+ in the acid
is gradually replaced by heavier and less mobile Na+ ions. Addition of base
beyond neutralization points increase in the number of more mobile OH- ions and
conductance increases.
2. Weak acid with strong base
Consider the titration of acetic acid with a strong base NaOH. (CH3COOH
versus NaOH)
NaOH + CH3COOH → CH3COONa + H2O
Consider the titration of acetic acid with a strong base NaOH, the conductance
of weak acid solution increases until the acid is completely neutralized.
A Plot of conductance against the volume of NaOH is shown in the figure below.
The point of intersection of the two lines is the neutralization point.
3. Acid mixture with a strong base (HCl and CH3COOH versus NaOH)
Consider the titration of acid mixture (HCl and CH3COOH) with strong base
NaOH
1. You will notice that on addition of NaOH the conductance of the acid mixture
solution decreases steeply. The conductance decreases steeply because the
small and highly mobile H+ ions in the strong acid is gradually replaced by
heavier and less mobile Na+ ions.
HCl + NaOH → NaCl + H2O
2. Addition of base beyond the first neutralization point leads to moderate
increase in conductance. The conductance increases moderately, because the
poorly conducting weak acid (acetic acid) is gradually converted to highly
conducting salt (Sodium acetate) until the second neutralization point.
CH3COOH + NaOH → CH3COONa + H2O
Further addition of NaOH increases number of highly mobile OH- ions. Hence
conductance increases steeply.
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