Dr.

Gangadhar B Bagihalli

MODULE 5: Sensors in Analytical Techniques

Syllabus:

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, Potentiometric sensors; its application in the estimation of iron,
Conductometric sensors; its application in the estimation of weak acid.

Introduction:

Electrochemistry is the branch of science, which studies the conversion of chemical

energy into electrical energy and vice versa. In the middle of eighteenth century M. Lemonsov
demonstrated that chemical and electrical energy are mutually related to each other. Furthermore,
L. Galvani reported that when dissected muscles of a frog were connected to copper and iron
wires which lead to contraction of muscles. A. Volta discovered the first sources of electricity, a
voltaic file. Later in 1872, F.D. Eagles suggested that chemical reactions taking place in galvanic
cells were the sources of electrical energy. The basic theory of electrolysis was first laid down by
T. Grotgus, in 1805. The importance of galvanic cell energy was demonstrated by D. Gibbs & H.
Helmoltz in 1882 and in 1889. V. Nernst derived an equation related to electrode potential and
electrolyte concentration. Number of scientists worked in the field of electrochemistry and
developed valuable theoretical concepts, namely I. Hittorf, F. Kohlrausch, A. Arrhenius, P.
Debye and L. Hickel. Over the years these theoretical concepts were accompanied with practical
applications in electrochemistry which includes electroplating, electro-refining of metals,
electro-extraction of metals, etc. Various galvanic cells are the effective sources of portable
energy.

In present scenario the study on electrochemistry is of great importance for many

scientists and technologists. In order to go depth in electrochemistry fundamental concepts must
be clear.

Note:1

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 Dr. Gangadhar B Bagihalli

Electrochemistry: It is a branch of chemistry which deals with the study of transformation of

chemical energy into electrical energy and vice versa”

Note:2

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

Note:3

Types of electrochemical cells:

1. Galvanic cells-are devices which convert chemical energy into electrical energy. Example-
Dry cell, Lead-acid cell, Ni-Cd cell etc.

2. Electrolytic cells-are devices which convert electrical energy into chemical energy.

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 CuSO4 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 red ox reaction.
-
e

Salt bridge

+
- Copper
Zinc
_
Anode Cathode

ZnSO4 CuSO4

Solution Solutio
n

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

At the zinc electrode zinc goes into the solution as Zn2+ ions liberating electrons 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, ic at copper electrode reduction takes place

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 Dr. Gangadhar B Bagihalli

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

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”

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

EMF of a cell:

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”

The EMF of a cell represents the driving forces for cell reactions. It can be represented by
thermodynamic relation.

∆G= -nFE

Where, ∆G- Free energy change accompanying during cell reaction, n- number of electrons
transferred during cell reaction and F- Faraday constant. The cell reactions are spontaneous when
∆G is –ve.

Nernst equation for emf of cells:

0.0591  Species.at.Cathode
Ecell  E 0 cell  . log 
n  Species.at. Anode 

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Types of electrodes:

Depending on the electrochemical applications the electrodes have been classified into six types:

1. Metal-metal ion electrode: It consists of a metal (M) dipping into a solution containing
its own ions (Mn+). The electrode potential depends on the nature of the electrode and
activity of metal ions.
e.g., Zn / Zn2+

2. Metal-metal salt ion electrode: An electrode of this type consists of a metal in contact
with a sparingly soluble salt of the same metal, immersed in a solution containing anion
of the same metal salt. The electrode potential depends upon the activity of the reversible
ions.
e.g., Hg / Hg2Cl2/ Cl-, Ag /AgCl /Cl-

3. Gas electrode: It consists of a gas bubbling about inert metal electrode in a solution
containing ions to which the gas is reversible. The electrode potential depends upon the
pressure of the gas and the activity of the reversible ions.
e.g., Pt / H2 (g) / H+, Pt /Cl2 / Cl-

4. Amalgam electrode: This electrode is same as that of metal-metal ion electrode except
the fact that here metal-amalgam is in contact with its own metal ions. e.g., Pb-Hg/Pb2+

5. Redox selective electrode: An electrode of this type consists of an inert metal (e.g., Pt)
in contact with a solution containing ions of a substance in two different oxidation states.
The electrode potential depends upon the ratio of the activities of the two ions. The role
of inert metal electrode is to pick up electrons and to provide electrical contact.
e.g., Pt / Fe3+, Fe2+

6. Ion selective electrode: Ion-selective electrode (or membrane electrode) is used for
determining the activities of various ions in aqueous solutions. The potential developed
by this electrode depends only on the activity of ionic species of interest.
e.g., Glass electrode, which is specific to H+ ions.

Reference electrodes:

“Reference electrode are the electrode with reference to those, the electrode potential of
any electrode can be measured”

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Calomel electrode:
Calomel electrode is extensively used as secondary reference electrode. This is a metal-
metal salt type electrode. Hg2Cl2 is called calomel. Calomel electrode consists of Hg, Hg2Cl2 and
solution of KCl. Calomel electrode is shown in Fig. Calomel electrode is made up of glass tube.
Hg is placed at the bottom of the glass tube which has side tubes at both sides. Platinum wire is
sealed through the glass tube and dipped into the Hg, which provides the external electrical
contact. Hg is covered with paste of Hg+ Hg2Cl2 and KCl solution. Depending on the
concentration of KCl the calomel electrode is called decinormal, normal and saturated.

The calomel electrode can be represented as Hg / Hg2Cl2 /Cl-

Figure

Calomel electrode may act as anode or cathode with respect to other electrode.

When it acts as anode, the electrode reaction is:

2Hg  Hg22+ + 2e–

Hg22+ + 2Cl-  Hg2Cl2

2Hg + 2Cl-  Hg2Cl2 + 2e–

When it acts as cathode, the electrode reaction is:

2Hg2+ + 2e–  2Hg

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 Dr. Gangadhar B Bagihalli

Hg2Cl2  Hg22+ + 2Cl-

Hg2Cl2 + 2e–  2Hg + 2Cl-

Thus, The net reversible calomel electrode reaction is given by

Hg2Cl2 + 2e– 2Hg + 2Cl-

Apply the nernst equation for revisable electrode reactions:

E = E0 - 0.0591 log [Cl-]2

2

E = E0 - 0.0591 log [Cl-]

Calomel electrode Ecalomel (at 25C)

Hg (l) | Hg2Cl2 (s) | satd. KCl 0.242 V
Hg (l) | Hg2Cl2 (s) | 1M KCl 0.280 V
Hg (l) | Hg2Cl2 (s) | 0.1M KCl 0.334 V

Advantages of Calomel Electrode:

 It is simple to construct.
 The electrode potential is reproducible and stable.
 It is used as a reference electrode.

Applications: It is used in pH measurement, general aqueous electrochemistry and cyclic

voltammetry.

Limitations: The calomel electrode contains mercury, which poses health hazards. It potential
alters at higher temperatures (60C).

Measurement of standard electrode potential using calomel electrode:

The absolute electrode potential of single electrode can’t be determined. This because a
single electrode of a cell works only when it is coupled with another single electrode and doesn’t
work independency.

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 Dr. Gangadhar B Bagihalli

Therefore, the electrode potential of single electrode can be measured by using some
reference electrode whose valve is known.
In order to measure the electrode potential of given electrode, it is coupled with calomel
electrode through salt bridge. Then the valve of emf of cell, Ecell is measured using electronic
voltmeter.
For example, to measure the potential of the zinc electrode is coupled with calomel
electrode through a salt bridge and voltmeter, as in diagram.

The cell can be represented as

Zn/Zn2+|| Cl-|Hg2Cl2/Hg
From the deflection in the voltmeter, the anode and cathode of the above cell can be
identified. In the above cell, it was found that the given Zn electrode acts ad anode and calomel
electrode acts as cathode.
The emf of the so formed cell is determined by using one of the cell conventions
We know that,
Ecell=E cathode-E anode
Ecell=Ecal. - Ezn/zn2+
Ecell= 0.242 - Ezn/zn2+
0.242 - Ezn/zn2+ = Ecell

Ezn/zn2+ = 0.242 – Ecell

Similarly to measure the electrode potential of copper. The copper is coupled with
calomel electrode.

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 Dr. Gangadhar B Bagihalli

The cell representation is,

Hg/Hg2Cl2/Cl-|| Cu2+/Cu
From the deflection in the voltmeter, the anode is calomel electrode and cathode is copper
electrode.
The emf of the so formed cell is determined by using one of the cell conventions
Therefore E cell=E cathode-E anode
E cell=ECu2+/Cu-ESHE
0.34 =ECu2+/Cu-0
ECu2+/Cu= 0.34V
Hence the potential of copper electrode is +ve.
Ecell=E cathode-E anode
Ecell= ECu2+/Cu – Ecal.
Ecell= ECu2+/Cu – 0.242.
ECu2+/Cu – 0.242 = Ecell
ECu2+/Cu = Ecell + 0.242

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 Dr. Gangadhar B Bagihalli

Ion selective electrodes:

Ion-selective electrodes (ISE) or membrane electrodes are used in a wide variety of

applications for determining the activities of various ions in aqueous solutions. An Ion-selective
electrode is a sensor which converts the activity of a specific ion dissolved in a solution into an
electrical potential which can be measured by a suitable device. The voltage is theoretically
dependent on the logarithm of the ionic activity, according to the Nernst equation. The sensing
part of the electrode is usually made as an ion-specific membrane, along with a reference
electrode.
They are widely used in Pollution monitoring, Food processing, Explosives, Biomedical
Laboratories and Electroplating.

Ion selective electrode consists of ion selective membrane in contact with an analyte
solution on one side and an internal reference solution on the other side. An internal reference
electrode is constituted with reference solution. The electrode can be represented as

The observed potential of an ion selective electrode is a kind of junction potential that develops
across a membrane that separates the analyte solution from internal std. solution.

Ej = 0.0591/n log C1/C2

Where, C1 & C2 are the concentration of the analyte and reference solution respectively. If the
concentration of the inner std. solution is kept constant, then

Ej = k + 0.0591/n log C1 (k = -0.0591/n log C2 = Constant)

The overall potential of the electrode also includes that of the reference electrode and thus,

EM = Ej + Eref

EM = k + 0.0591/n log C1 + Eref

EM = E0M + 0.0591/n log C1 (E0M= k + Eref)

The electrode is combined with an external reference electrode and EMF of the so formed cell is
determined by potentiometric method. Knowing the electrode potential of the reference
electrode, the electrode potential of the ion selective electrode is calculated which in turn gives
the ion concentrations.

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 Dr. Gangadhar B Bagihalli

Advantages:

 ISEs are one of the few techniques which can measure both positive and negative ions
(H+, Na+, Ca2+, NH+, Cl-, F-, NO3-, S2-, etc).
 Glass electrode can be used in aqueous solutions over a wide temperature range and is
unaffected by sample colour or turbidity.
 It is not affected by oxidizing or reducing species present in the analyte.
 It is particularly useful in biological/medical applications because it measures the activity
of the ion directly, rather than the concentration.
It is simple to operate, requires little sample and gives reproducible pH value.

Glass electrode:

It is pH sensitive electrode most widely used for pH determinations. Glass electrode is

displayed in Fig. The glass electrode consists of a glass bulb made up of a special type of glass
with high electrical conductance. The glass bulb is filled with a solution of a constant pH (0.1M
HCl) and inserted with Ag-AgCl electrode; which is the internal reference electrode. The
electrode is dipped in an H+ ion solution.

Figure

The glass electrode is represented as Ag/AgCl/(0.1M HCl)/glass. When it is dipped in a solution

it is represented as

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The glass membrane exchange ions with the solution,

H+ + MG1 M+ + HG1

(Solution) (Membrane) (Solution) (Membrane)

The exchange of ions by the inner and outer membrane gives rise to a boundary potential.
This boundary potential consists of two potentials E1 & E2, which are associated with the outer
and inner membranes respectively.

Eb = E1- E2

From thermodynamic consideration it has been shown that E1 & E2 are related to the
hydrogen ion activities at each face. This is represented by Nernst equation type relation

E1 = j1 – 0.0591/n log a11/a1

E2 = j2 – 0.0591/n log a12/a2

Where j1 and j2 are constants, a1 and a2 are activities of H+ ions in the outer and inner
solution, respectively. a11 & a12 are the activities of H+ ions at the external and internal surface of
the glass membrane.

Since the glass at the inner & outer membranes are identical J1 = J2 and a11 = a12

Then,

Eb = E1- E2

Eb = 0.0591 log a1/a2 (n=1 for H+ ion)

Eb = L’ +0.0591 log a1 (L’ = -0.0591 log a2 = -0.0591 logC2)

Eb = L’ +0.0591 log C1

Eb = L’ - 0.0591 pH (C1 = -log H+ = pH)

The potential of the glass electrode EG has three components.

1. The boundary potential

2. The potential of the internal reference electrode, i.e., Ag/AgCl
3. A small asymmetry potential.

EG = Eb + Eref + Easy

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 Dr. Gangadhar B Bagihalli

= L’ + 0.0591 log C1 + Eref + E asy

= E0G + 0.0591 log C1

= E0G - 0.0591 pH (E0G= L’+ Eref + E asy)

Note: 1. In Glass electrode the glass used is made up of Na2O (22%), CaO (6%) and
SiO2 (72%). It can sense hydrogen ions up to a pH of about 9.
2. Asymmetric potential: In EG = Eb + Eref
Eb = 0, when C1 = C2. However, it has been observed that, when C1 = C2 a small
potential is developed, that potential is called as asymmetric potential (Easy).
Therefore, EG = Eb + Eref + Easy

Determination of pH of a solution using glass electrode:

To determine the pH of a given solution, the glass electrode dipped in a solution whose
pH needs to be determined. Figure shows the arrangement of electrodes in determining the pH.
It is combined with saturated calomel electrode.

pH Meter

Glass
Calomel
electrode
electrode

Solution of

unknown pH
Figure
Cell representation
Saturated calomel elctrode\\soln of unknown pH\glass\HCl (0.1M)\AgCl\Ag

The EMF of the so formed cell is determined potentiometrically.

Ecell = EG - ECal
Ecell = E0G - 0.0591 pH - Ecal
pH = E0G – Ecal-Ecell/0.0591
pH = K - Ecell/0.0591, where K- Glass electrode assembly constant.
E0G is calculated by dipping the glass electrode in solution of known pH.

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pH Meter:

For a direct reading pH meter may be used instead of potentiometer.

The advantage of pH meter is that there is no need to evaluate K which get cancelled by
external potential.

A reference electrode and a SCE are connected to pH meter. The electrode assembly is
dipped in a standard buffer solution and meter is calibrated to pH of the buffer.
The pH of buffer pHb is related to Ecell(b) by equation

pHb = K – Ecell(b)
__________ ---------------------- (1)
0.0591

Next electrode assembly is dipped in test solution and pH of test solution is given by

pH = K – Ecell
__________ ---------------------- (2)
0.0591
Substracting 1 from 2 we get

pH - pHb = K – Ecell K – Ecell(b)

__________ - ____________________
0.0591 0.0591

pH = pHb - ( Ecell – Ecell(b))

______________
0.0591

Concentration Cells:

A concentration cell is a Galvanic cell that has two identical half-cells of the same
material differing only in concentrations. Here, potential arises due to a decrease in free energy
due to difference of concentration (activity) between the two electrodes. Cell potential can be
calculated using the Nernst Equation. A concentration cell produces a voltage as it attempts to
reach equilibrium, which will occur when the concentration in both cells are equal.

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Concentration cells consist of two electrodes of the same substance in contact with solutions
of different concentrations and potential difference arises as long as concentration difference
exists. These cells are with or without transference of material from one electrode to the other.

Ag  AgNO3 (c1)   AgNO3 (c2)  Ag c2  c1

The above example is for electrolyte concentration cell without transference. Its
electrodes and cell reactions are:

Anodic reaction: Ag  Ag+ (c1) + e

Cathodic reaction: Ag+ (c2) + e  Ag

Cell reaction: Ag+ (c2)  Ag+ (c1)

The cell potential is given by

Ecell = Ecathode – Eanode

= E + 2.303 (RT/nF) log c2 - E + 2.303 (RT/nF) log c1

Ecell = 2.303 (RT/nF) log (c2 /c1)

For spontaneous cell reaction, c2  c1, the more concentrated solution should be in the
right half-cell and less concentrated solution should be in the left half-cell.

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REVIEW QUESTIONS

1. Mention the types of electrode with example. 6 marks

2. What are Reference Electrodes? Explain Construction and working of Calomel electrode.
7 marks
3. What are Reference Electrodes? Explain the measurement of electrode potential using
calomel electrode. 7 marks
4. What are ion-selective electrode and explain the construction and working of glass
electrode. 7 marks
5. What are ion-selective electrode and explain the determination of pH using glass
electrode. 7 marks
6. Define concentration cells and explain the construction and working of concentration
cell. 6 marks

Sensors:

Introduction

Development in Science and Technology during last century has resulted accelerated
growth in emission of anthropogenic pollution in to environment contributing to increasing
incidences of chronic diseases. Toxic gases, metals, pesticides and other dangerous chemicals
have spread throughout our environment. Therefore, monitoring of composition of air, water and
soil has become an area of intense interest. In health sector, for diagnosis and health monitoring,
it is required to determine clinically important chemicals present in body fluids. For various
industrial and agricultural applications qualitative detection and quantitative analysis of chemical
species is the major requirement. These demands have led to the development of many important
analytical approaches. These techniques are not suitable for routine and online analysis.
Therefore there is a growing demand to develop new instruments, techniques and procedure so
as to make analysis convenient, fast, reliable and selective. To meet these demands, Chemical
sensors of various types have been intensively developed. These sensors have number of
advantages over other classical methods of analysis like low cost, less time of analysis,
portability of the device, sample non-destruction and accuracy of result. Chemical sensors find
numerous applications like in home safety, food freshness, medical diagnosis and environmental
protection and are therefore likely to have a positive impact on our lives in the nea future.

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 Dr. Gangadhar B Bagihalli

Construction and Working of a Sensor

A chemical sensor is a device that is capable of giving real time analytical information
about a test sample. It interacts with a specific chemical or biological analyte, detects it and
produces the signal proportional to its quantity. Analyte is the target species which is being
detected and measured using a sensor.

Main basic components of a sensor are:

a) Receptor:
Receptor is a chemical or biological recognition element which is capable of interacting with
analyte specifically and selectively. It produces a signal corresponding to interaction in the form
of changes in potential, conductivity, current, mass, heat, pH, colour etc. If the receptor is of
biological origin (e. g., DNA, antibodies and enzymes), the device is referred to as a biosensor. If
the receptor is of chemical origin, the device is referred to as a chemical sensor.

b) Transducer:
During the interaction of sensing element with analyte, certain physical or chemical properties of
the sensing element changes proportionately to the analyte concentration. Transducer is used to
convert the signal created by the receptor-analyte interaction into a readable value or measurable
from physical quantity. In most chemical sensors, the sensing element and the transducer are
packaged together, in direct spatial contact, in the same unit.

c) Electrical signal and display:

The electronic system analyzes the signal given by the transducer, help in signal amplification
and coverts the signal from analog to digital form. These amplified signals are then displayed.
Signal can be displayed in various forms such as numeric value, graph, image etc.,

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Interaction between the receptor and anlyte can be monitored by several methods.Different
parameters are measured in each method like change in potential, conductivity, current, mass,
heat, pH, colour etc. For measurement of each parameter, different types of transducer are used.
There are several types of sensors available depending on type of transducer is used like
Electrochemical sensors, Conductometric sensors, Thermometric sensors and Optical sensors etc.

Electrochemical Sensors:

Electrochemical sensors use electrodes as the transducer component. Transducer of an

electro chemical sensor consists of working or sensing electrode, electrolyte counter electrode
and reference electrode. The sensing electrode has a chemically modified surface. This
modification ensures the selectivity, facilitating the reduction or oxidation of the analyte. The
electrolyte is part of the electric circuit of an electrochemical sensor system. The role of the
electrolyte is to transport charge within the sensor, contact all electrodes effectively, solubilize
the reactants and products for efficient transport and be stable chemically and physically under
all conditions of sensor operation. The following steps are involved in the working of an
electrochemical sensor.

1. Diffusion of the analyte to the electrode/electrolyte interface I(in the liquid phase)
2. Adsorption onto the electrode surface
3. Electrochemical reaction with electron transfer
4. Desorption of the products
5. Diffusion of the products away from the reaction zone to the bulk of electrolyte or gas
phase

Applications of Electrochemical sensors:

Varieties of electrochemical sensors in unique geometries or structures for large number

of chemicals are available. They are used in diverse areas as industrial safety, biochemistry,
clinical chemistry, health and medicine, agriculture, food safety, environmental protection,
automotive technology, space exploration, military threat detection and process control. Few
applications are given below.

1. The oxygen sensor is used for detection of dissolved oxygen in water boiler and to
monitor dissolved oxygen concentration in metal, glasses and in hydrogen fuel.
2. They are used in security and defense applications like detection of toxic gass,
warfare agents etc.

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3. They are used in water analysis and environmental monitoring, like measurement of
toxic metal concentration in water, detection of oxides of nitrogen and sulphur, CO,
pH of water etc.
4. They are used in diagnostic and health-care applications, like in situ monitoring of
glucose serum uric acid, blood Ca2+, Fe+2, Acetylcholine etc.
5. They are used in soil parameter analysis, evaluation and in agriculture applications.

Types of Electrochemical Sensors:

There are mainly three types of electrochemical sensors.

1. Potentiometric Sensor:
In this sensor, change in potential during the chemical interaction between receptor and
analyte is measured using combination of an indicator electrode and reference electrode.
Commonly, Platinum is used an inert electrode whereas saturated calomel electrode is used as a
reference electrode. Indicator electrode is used to measure change in potential due to redox
reaction occurring on the surface of the electrode. Using an ion-selective electrode as an
indicator electrode, concentration of particular ion can be measured with good selectivity. pH
glass electrode is an example for this class of electrode. In potentiometric sensor, measurement is
taken at zero current.

Potentiometric Sensor

2. Amperometric Sensor
An amperometric sensor is similar to a potentiometric sensor consisting of an electrolyte solution
in which the electrode are immersed. But, it is operated under an externally applied fixed
voltage. This potential causes the analyte to react and a current to pass. At fixed applied
potential, the magnitude of the current generated is directly proportional to the concentration of
analyte. Here, current passing through the cell is measured.

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Amperometric Sensor with two electrodes

In a sample amperometric sensor, two electrode namely counter electrode and working
electrode are used. Theoretically, in amperometric, potential between two electrodes must be
maintained constant. But, in reality, redox reactions at each electrode surface results in potential
change. Therefore to keep potential constant, a three-electrode system is commonly used. In the
three-electrode system, the current at the sensing electrode can be measured at constant potential.
This helps in maintaining a constant potential and measure the current at constant potential using
counter and working electrode.

In potentiometric and amperometry, the surface of sensing electrode is usually modified.

A layer of catalysts, enzymes which can facilitate redox reaction are coated. This modification
makes sensor more selective. Recently, miniaturized microelectrodes are used which show fast
response time and can measure small current. Materials commonly used for these electrodes are
noble metals; fluorine-doped tin oxide (FTO) coated glass, indium-tin-oxide conductive glass
(ITO), and different forms of carbon. Out of these electrodes, manufacturing process of FTO and
ITO-based electrodes is costly and more complex. Therefore, nanomaterial’s based on carbon
such as grapheme, carbon nanotubes and nanofibers and graphitic carbon nitride are gaining
more attention due to their low cost, applealing electrochemical properties, ease of
functionalization and wide potential window.

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Amperometric Sensor with three electrodes

3. Conductometric Sensor

Conductometric sensor is considered as a type of electrochemical sensor, even though it

is not used to measure electrochemical change. An electrochemical sensor measures the
electrochemical processes (redox reactions) at the surface of electrodes. But, a conductometric
sensor is based on measurements of physical properties of a homogeneous bulk solution like
electrolytic conductance by aqueous electrolyte solutions. In conductometric sensor,
determination of the concentration of analyte is based on measurement of changes that occur in
electrolyte solution. Hence the electrodes are just used to measure change in electrolytic
conduction of an electrolyte and they do not provide surface for any reaction. Therefore their
surface is generally not modified.

Conductance of a solution is based on:

a) The concentration (number) of ions contributing to conductivity of solution.

b) Mobility of each type of ion. Mobility of an ion depends on its size. Smaller the size
higher is mobility and higher is electrolytic conductance.
Electrode used in conductometric sensor is called as conductivity cell. It is used to measure the
change in electrolytic conductance of the solution during replacement of ions of a particular
conductivity by ions of different conductivity. It is made of two Pt foils with unit cross sectional
area and unit distance between them. Volume between two electrodes is 1 cm3. Conductance of
unit volume of the solution is called as specific conductance. There will be change in specific
conductance of solution when there is change in number of ions or type of ion. This change is
measured using conductivity cell.

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Specific conductance (k) is given by, k = 1/R X 1/a where 1/a is known as cell constant and R is
the resistance of the solution.

The conductitivity cell is dipped in the electrolytic solution taken in a beaker and it is connected
to a conductance measuring device called as conductivity meter.

Application of Conductometric sensors

1. Conductometric sensor can be used to monitor any chemical which can change the
electrolytic conductionce of solution on chemical reaction.
2. It is used to estimate acids, bases and their mixtures in a sample.
3. It is used to check the amount of ionic impurities in water samples.
4. It is used in measuring acidity or alkalinity of sea water and fresh water.
5. Conductometric biosensors are used in biomedicine, environment monitoring,
biotechnology and agriculture related applications.

Conductmetric Sensors

Optical Sensors:

Interaction of electromagnetic radiation with matter forms the basis of broad range
analytical methods commonly known as spectrochemical methods of analysis. Commonly,
electromagnetic radiation in the ultraviolet-visible-infrared domains is used for analytical
purposes. A broad range of chemical sensors have been developed on the ground of interaction
of the sensing element with electromagnetic radiation. Sensors based on the transduction of
interaction of electromagnetic radiation with the chemical species are called as optical sensors.

Optical transduction can be based on emission, absorption, reflectance and scattering of

light by the analyte. The optical signal arises from the interaction of the analyte with an incident
radiation. The interaction could result in absorption, emission, scattering or reflection of light.
The type of interaction depends on the wavelength of the probing radiation and on the structure
of the molecules in the analyte. The intensity of the radiation emanating from the analyte carries
information on the concentration of the analyte. It is measured by the optoelectronic instruments.

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In a simple optical sensor used to measure absorption of light, main components used are
a light source, a wavelength selector, a photodetector and a display of the output.

Schematic representation of simple optical sensors

In modern optical sensors, optical components such as a lens, optical couplers and
connectors are used for coupling light into optical fibers and solid-state optoelectronic
components. This has enabled the development of commercial portable optical sensor system.

Simple optical sensors are used to determine the concentration of colored chemical
species in solution. They are based on measurement of absorbance of transmittance of light of
particular wavelength by colored chemical species in the solution. They are governed by Beer-
Lamberts law.

Applications of Optical sensors:

1. Optical Sensors can be used in the determination of any chemical species which can
interact with electromagnetic radiation.
2. Optical Sensors have been developed for number of different types of chemical and
biochemical molecules and ions. For example, ion in solution (e.g., pH, metal ions
and anions), gases (e.g., CO2, O2, NH3, SO2, NO2, NO, etc.,), Vapors (e.g.,
moisture, volatile organic compounds, etc.,) and molecules (e.g., glucose, pesticides,
DNA, bacteria, etc.,) can be determined using optical sensors.
3. Optical sensors find important and varied uses in environmental, biotechnological,
food, pharmaceutical, medical and related applications.
4. Optical fiber based (bio)sensors are used in screening of drugs, detection of food-
borne pathogens, detection of explosives and environmental monitoring.

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Thermometric Sensors:

Thermometric sensor is based on the measurement of thermal change during the

interaction between analyte and receptor. Thermal changes are converted to measurable change
in the temperature or potential.

Thermometric transduction is feasible only in those processes which generate sufficient

heat to produce a measurable change of temperature. Chemical or biological species which
undergo catalytic chemical reactions and enzyme-catalyzed reactions liberating heat (exothermic
reactions) can be determined by thermometric sensors.

Working Principle of Thermometric sensors:

Main component of a thermometric sensor is a small tubular catalytic reactor fitted with a
tempetature transducer. Analyte (reactant) is fed in to the reactor. The wall of the reactor is
coated with catalyst or enzyme capable of catalyzing 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 transducers which are amplified and fed to the data storage
and processing unit.

In order to convert chage 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 if transition metals. Most thermistors
have a negative temperature coefficient. That is, their resistance deceases with
increasing temperature. The decrease in resistance is converted to output voltage
using a Wheatstone bridge resistor.
2. Thermocouple: A thermocouple 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 of thermometric sensors:

1. Thermal bio sensors are based on the temperature change induced by a simple
enzymatic reaction. They are used in the determination of metaboloties, bioprocess
monitoring, and environmental control. An example is the determination of glucose
using the glucose oxide-catalyzed reaction.
2. Thermometric chemical sensors are used for determination of combustible gases that
react with oxygen at the surface of a suitable catalyst.

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Review Questions:

1. What is electrochemical sensor? Explain working principle and applications of

electrochemical sensor? 7 marks
2. What is conductormetric sensor? Explain working principle and applications of
conductometry sensor? 7 marks
3. What is thermometric sensor? Explain working principle and applications of
thermometric sensor? 6 marks
4. What is optical sensor? E working principle and applications of optical sensor by
taking colorimeter as an example? 7 marks

Analytical Techniques:

INTRODUCTION:

Analytical Chemistry is branch of chemistry that deals with chemical analysis. Chemical
analysis involves identifying and determining the percentage composition in a sample of a
substance. The identification is carried out by qualitative analysis. Quantitative analysis gives the
percentage composition of the constituents. The sample under analysis is an analyte. Some
important techniques of quantitative analysis are titrimetry or volumetry, gravimetry and
instrumental methods.

In titrimetry, a known amount of the analyte present in the solution is allowed to react
with a standard solution of an appropriate reagent. The volume of the standard reagent required
to react with known amount of the analyte is determined by titration.

In gravimetry, a known amount of the analyte is precipitated by the addition of a reagent.

The precipitate is collected and weighed.

The term instrumental methods of analysis is usually applied to

(i) Methods based on emission or absorption of radiation

(ii) Electrochemical methods such as potentimetry, conductometry and polarography.

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(iii) Mass spectrometry.

(iv) Methods based on measurements of radioactivity.

In instrumental methods of analysis, the analytical instrument converts an analytical

signal from the analyte into an electrical signal that can be measured by a suitable device. The
electrical signal that can be read on a meter is a measure of the quantity of the sample. For
example, a photometer measures the amount of light absorbed by a colored solution (analytical
signal) by converting the light radiation into an electrical signal. The latter is measured using a
galvanometer. Similarly, a pH meter measures the electrical potential developed at an electrode
interface due to hydrogen ion concentration (analytical signal)

The detector identifies the analytical signal from the analyte and converts it into an a
transduced signal (electrical signal). The latter is then processed by the signal processor which
transforms the signal in such a form that it can be recorded on a meter, x-y recorder or
digitalizer. The signal processor can amplify, attenuate, differentiate, integrate or compare the
analytical signal. Modern analytical instruments make use of microprocessor based signal
processors.

The advantages of instrumental methods of analysis are

(i) They require small quantities (less than a milligram) of the analyte.

(ii) Methods adopted are easy when a large number of analytes have to be analyzed

(iii) The analysis can be conducted in a very short time

(iv) They give accurate results.

CONDUCTOMETRY:

Theory and Instrumentation:

Measurement of conductance can be employed to determine the end point in acid-base

titrations. In conduct metric titrations there is a sudden increase in conductance of the solution at
equivalence point. The principle underlying conductometric titrations is the substitutions of ions

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by other ions of different mobility. Therefore, the conductance of a solution depends on the
number and mobility of ions. The equivalence point is determined graphically by plotting
conductance (ordinate) against titer values (abscissa). From the equivalence point the
concentration of analyte can be determined. Conductometer consists of a conductivity cell& a
conductance measuring device.

Conductance is reciprocal of resistance therefore it obeys ohm’s law it is given by the

symbol C and in SI units it is called as Siemens (S or Ω-1)

C = 1/R were R = ρ. L/A

L is a distance between two electrode, A is surface area of the electrode and ρ is

proportionality constant is called as specific resistance.

Therefore Specific conductance (k) is reciprocal of specific resistance at a given temp. It

can be defined as specific conductance of an electrolyte solution is the conductance of the
solution present between two parallel electrodes of 1 cm2 area of cross section and 1 cm apart
and is given by.

K = 1/ ρ

K = 1/ ρ = [L/A]. [1/ ρ] = [L/A] . conductance

L/A = x is constant and called as cell constant. It is measured by the with the solution of
known specific conductance, Ex. KCl.

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Instrument:

The cell has 2 platinum electrodes placed at unit distance apart. The assembly responds
rapidly to the changes in the concentration of the analyte. The simple arrangement of
conductometric titration is represented as follows. Advantages of conductometric titrations

1) Mixture of acids can be titrated more accurately.

2) Colored solutions can be titrated.

3) Very weak acids such as H3 PO3, phenol, which cannot be titrated

potentiometrically in aqua solutions can be titrated conduct metric.

Applications:

a) Titration of strong acid v/s strong base

NaOH + HCl NaCl + H2O
Consider the titration of HCl against NaOH. The conductance initially falls till the
equivalence point. This is due to the replacement of highly mobile H+ ion (mobility 350 ohm-1 m-
1
) by the Na+ ion (mobility 40-80 ohm-1 m-1). After the equivalence point, the conductance
rapidly rises with further additions of strong base. This is due to increase in the concentration of
the OH- ions (mobility 198 ohm-1 m-1). A plot of conductance (ohm-1 m-1) against the volume of
NaOH (cm3) gives a graph as shown in the Fig. 1a. The point of intersection of the curves gives
the end point.

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b) Strong Acid v/s Weak Base

HCl + NH4OH NH4Cl + H2O

Consider the titration of HCI against NH4 OH. The conductance first falls, due to the
replacement of highly mobile H+ ion by the ions during neutralization. After the equivalence
point, the conductance does not change appreciably since NH4OH is a weak base. A plot of
conduct against the volume of NH4OH added is shown in Fig. 1b The point of intersection of the
two curves gives the neutralization point.

C) Weak Acid with a Strong Base:

NaOH + CH3COOH CH3COONa + H2O

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Consider the titration of acetic acid against NaOH. The conductance of the acid will be
initially low since acetic acid is a weak electrolyte. When NaOH is added to the acid, the salt
formed is highly ionized and the conductance increases. On complete neutralization of the acid,
further addition of base leads to an increase in the number of mobile OH ions. Hence the
conductance increases sharply. Thus a plot of conductance against volume of base added gives
two straight lines as shown in the Fig. 1c. The point of intersection of the two lines gives the
neutralization point.

d) Acid mixture with strong bse (HCl & CH3COOH v/s NaOH)
Consider the titration of acid mixture (HCl & CH3COOH) with strong base NaOH On the
addition of NaOH, the conductance of the acid mixture solution decreases steeply, because the
highly mobile H+ ions in the strong acid is gradually replaced by less mobile Na+ ions.

NaOH + HCl NaCl + H2O

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.

NaOH + CH3COOH CH3COONa + H2O

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Further addition of NaOH, increases number of highly mobile OH ions. Hence conductance
increases steeply.

Colorimetric Determination of Copper

Principle: When a monochromatic light of intensity Io is incident on a transparent medium, a part, Ia

of it is absorbed, a part, Ir is reflected and the remaining part, It is transmitted.
Io=la + Ir + It
For a glass-air interface Ir is negligible and therefore,
Io = Ia + It
It / Io = T called the transmittance, log 1/T = log I0 / It is called the absorbance or optical density. The
relation between absorbance, A, concentration, c (expressed in mol/dm3) and path length, t
(expressed in cm) is given by Beer-Lambert's law,
A = log I0 / It = Ect

Where, € is the molar extinction coefficient, t is the path length and is a constant for a given
substance at a given wavelength. If t, the path length is kept constant, then, A Vs C. Hence, a plot of
absorbance against concentration gives a straight line.

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Instrumentation:

The instrument used to measure the absorbance of a solution is called photoelectric

colorimeter. The photoelectric colorimeter used for measuring the absorbance of a colored
solution is shown in the Fig.

The photoelectric colorimeter consists of

(i) Tungsten lamp as the light source.

(ii) A filter which provides the desired wavelength range wherein the solution gives the
maximum absorbance.

(iii) A sample cell

(iv) A photocell detector.

Fig. photoelectric colorimeter

Light from a tungsten lamp is allowed to fall on the solution taken in the sample cell after
passing through the filter. First, a blank solution is taken in the sample cell and placed in the path
of the light beam. Its absorbance is adjusted to zero (or transmittance to 100) on the mater. Next
the analyte solution is placed in the path of the light beam and the quantity of light absorbed is
measured as its absorbance (or transmittance)

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APPICATIONS OF COLORIMETRY:

Colorimetry is a versatile method of determining the concentration of metals and

nonmetals present in small quantities in ores, soil samples and alloys. The sample is dissolved in
a suitable acid and known amount of the solution is treated with a reagent that produces a
characteristic colour with the desired constituent. The absorbance of the colour is measured at an
optimum wavelength (λ max) using a photoelectric colorimeter. This is illustrated for the
analysis of copper in a steel sample dissolved in hydrochloric acid.

Colorimetric Estimation of Copper

Principle:

When a solution containing cupric ions is treated with ammonia solution, a soluble
complex with a characteristic deep blue colour is formed.

Cu2 + 4NH3 → Cu[(NH3)4]2+ cuprammonium complex (deep blue)

The absorbance of this solution is measured at 620 nm (λ max) since the complex shows
maximum absorbance at this wavelength.

A series of standard solutions of Cu2+ are prepared and their absorbances are measured at
620 nm after treating with ammonia solution. A plot of absorbance against concentration gives a
calibration curve. The absorbance of the test solution is measured in a similar way. Its
concentration is determined for the graph.

Procedure:

Prepare 100 ml of 0.1 M solution of copper sulphate. Transfer known volumes of

standard copper sulphate solution into separate 100 ml standard flasks so as to give an
absorbance between 0.1 to 0.5. Add 5 ml of ammonia into each of these flasks and make up to
the mark with distilled water. Stopper the flasks and mix the solutions well.

Transfer a known volume of steel solution into a 100 ml flask so as to give an absorbance
between 0.1 and 0.5. Add 5 ml of ammonia and make it up to the mark with distilled water.
Stopper the flask and mix the solution well.

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Measure the absorbance of the solutions against blank ( 5 ml ammonia and water in a
standard flask) at 620 nm using a photoelectric colorimeter. By plotting calibration curve
concentration of copper (in mg/ml) against absorbance as shown in the fig. using this curve we
can determine the concentration of copper in the given sample solution.

Potentiometry:

Theory

A Potentiometric titration may be defined as a titration in which the end point is detected by
measuring the change in potential of a suitable electrode during the titration. The electrode which
responds to the change in concentration of the ion in the solution is called the indicator electrode.
The indicator electrode is combined with the reference electrode to form the cell and the e.m.f
of the so formed cell is measured during the titration The e.m.f of the cell changes gradually till
the end point and changes rapidly at very close to the end point and again the change is gradual
after the end point When e.m.f., is plotted as ordinate and the volume of titrant added as abscissa,
the point of inflection of the curve corresponds to the equivalence point or end point of the
titration

Instrumentation Potentiometric method consist of Potentiometer and two electrodes in which

one electrode is indicator electrode (eg Platinum electrode) and reference electrode

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Instrument used- potentiometer or pH meter

Electrodes – Indicator electrode eg – platinum

Reference electrode eg- calomel for potentiometer, glass electrode for pH meter

1. The solution to be titrated is taken in the beaker and titrant is taken in the micro burette.
2. Immerse the electrodes in the beaker along with stirrer
3. The electrodes are connected to the potentiometer which gives the emf values

Application in the estimation of Fe

Oxidation Reduction reactions; Estimation of amount FAS in FAS solution

FAS vs. K2Cr2O7

1. The FAS solution is taken in the beaker and K2Cr2O7 is taken in the micro burette.

2. Immerse the electrodes in the beaker along with stirrer

1. The electrodes are connected to the potentiometer which gives the emf values
2. Go on adding the titrating reagent with an in travel of 0.5 ml
3. There will be sudden jump in the emf value after adding some amount of reagent
4. carry out the experiment for five more readings
5. plot first derivative curve ΔE/ ΔV Vs volume of reagent added
6. The volume correspond to the maximum peak in the graph is called equivalence point or
end point of the reaction
9. Using formula normality and amount can be calculated.

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∆E/∆v

Volume of K2Cr2O7

Applications:
1. Colored solution can also be titrated.
2. Acid-base titration can also be done in this method.
3. In this method Oxidation-reduction titrations can also be carried out.
4. Precipitation reactions can also be carried out potentiometrically.

REVIEW QUESTIONS:

1. Explain the principle and instrumentation of Colorimetric sensors in the estimation of

copper. 7 Marks.
2. Explain the principle and instrumentation of Potentiometric sensors in the estimation of
iron. 7 Marks
3. Explain the principle and instrumentation of Colorimetric sensors in the estimation of
weak acid. 7 Marks

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