RNS INSTITUTE OF TECHNOLOGY

DEPARTMENT OF CHEMISTRY
Channasandra, Bengaluru - 560 098

APPLIED CHEMISTRY FOR CS STREAM (BCHES202)

SENSORS & ANALYTICAL TECHNIQUES

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Sensors and Analytical Techniques 2024-2025

SENSORS AND ANALYTICAL TECHNIQUES

Syllabus:
Sensors: Introduction, terminologies and classification of electrochemical sensor. Electrochemical sensor
working principle and applications. Electrochemical sensor for the measurement of dissolved oxygen and
in the detection of SOx and NOx. Disposable sensor: Definition, Advantages of disposable sensors over
classical sensor. DS in detection of biomolecules – Ascorbic acid and Glyphosate.
Instrumental Methods of Analysis: Theory, Instrumentation and application of colorimetry,
potentiometry, conductometry (strong acid v/s strong base, weak acid v/s strong base and acid mixture v/s
strong base.

SENSORS
Introduction:
A sensor is a device that measures or detects a physical quantity (such as temperature, pressure, humidity,
light, sound, current, movement) or the chemical quantity (such as concentration, SRP, conductance,
absorbance). Sensors are used to convert the physical or chemical quantity into an electrical signal that can
be processed through a computer or other electronic system. Sensors are of utmost usage because of quick
analysis and detection with 99% accuracy in results.
e.g., Sensors are used in automobiles to monitor the engine performance, In medical devices for detection
of biomolecules (such as glucometer for glucose level detection), In smartphones for user friendly inputs
and orientations, etc.
Definition: Sensors are devices which “read” a physical stimulus (heat, light, sound, weight, attraction
etc.) and then convert that reading into an electrical signal output.
Terminologies of a Sensor:
Receptor: It is a device that reacts with specific and selective analyte to observe and acquire information.
Transducer: It is a device that converts one form of energy into another. It typically takes an input signal
(which can be mechanical, electrical, thermal, etc.) and transforms it into a different output signal.
Actuators: It is device that amplifies and converts a signal from a transducer into digital form. The
amplified signal can be displayed in various forms such as numeric value, graph, image etc.

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Types of sensors:
1. Electrochemical Sensors: Sensor which converts the effect of electrochemical redox reaction between
the sensor and analyte into a useful readable electrical signal.
2. Conductometric sensor: Sensor in which the analyte concentration is determined based on change in
conductance when there is reaction between the analyte and sensor.
3. Thermometric sensors: Sensor in which the analyte concentration is determined based on change in
temperature when there is reaction between the analyte and sensor.
4. Optical sensors: Sensor in which the analyte concentration is determined based on interaction of
analyte with the incident light radiation, through the phenomena such as absorbance, transmittance., etc.,

ELECTROCHEMICAL SENSORS:
Working Principle: Electrochemical Sensor are the device which measures the amount of current
produced during electrochemical reaction between analyte and the electrode surface and convert into a
useful signal . The amount of current produced is proportional to the concentration of analyte.
 Electrochemical sensors consist of working (sensing) electrode, reference electrode, counter
electrode and electrolyte.
 The working (sensing) electrode has a chemically modified surface and helps in the oxidation of
analyte. The potential at the sensing electrode varies due to continuous electrochemical reaction. If
there is lack of potential on sensing electrode, it leads to poor performance of sensor.
 To improve the performance, reference electrode is placed very close to sensing electrode. It
provides stable and constant potential at sensing electrode and support the effectiveness of the
sensor.
 Counter electrode is connected to sensing electrode for reduction reaction and completes the circuit
by providing output signal to an actuator.
 The electrolyte is chemically and physically stable. They helps to transport ions within the sensor,
contact all electrodes effectively, solubilize the reactants into products.
 Hydrophobic membrane prevents unwanted particles reaching electrode and prevents liquid
electrolyte from leaking out.
 The capillary diffusion barrier allows the inlet and outlet of the analyte molecules into the sensor.

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Applications:
1. Electrochemical sensors used for the detection of blood glucose.
2. Used for pH measurements.
3. Used to detect pesticides.
4. Used in environmental monitoring of air quality.
5. Used to detection of explosive gases and toxic vapours.
6. Used in oxygen monitoring in the medical sector.
7. Used for food quality control; gas detection in steam processed food, inert gases for packing, toxic
gases for sterilization and ammonia used in refrigeration.

ELECTROCHEMICAL SENSOR FOR THE MEASUREMENT OF DISSOLVED OXYGEN

(DO): Electrochemical DO sensors, also known as amperometry or Clark-type sensors, measure
dissolved oxygen concentration in water based on electrical current produced. Galvanic DO sensor is used
to measure the DO.
Components:

Anode: Zn, Pb or any other active metal

Cathode: Working electrode-Ag
Electrolyte: KOH, NaOH or any other inert electrolyte.
Membrane: Teflon (Oxygen-permeable membrane).

Working principle:
When galvanic DO sensor is immersed in water sample, oxygen diffuses across the oxygen- permeable
membrane at a rate proportional to the partial pressure of oxygen in the water. Molecular oxygen reduces
to hydroxide ion at cathode. Active metals undergo oxidation at anode. This reaction produces an
electrical current that is directly related to the oxygen concentration. This current is carried by the ions in
the electrolyte and runs from the cathode to the anode.
At Anode: 2Pb → 2Pb 2+ + 4e-
At Cathode: O2 + 4e- + 2H2O → 4OH-
Overall reaction: O2 + 2Pb + 2H2O → 2Pb (OH)2
The current produced is proportional to oxygen consumed and thus to the partial pressure of oxygen in the
sample. The white solid, Pb(OH)2 that is produced by this reactions is precipitated out into the electrolyte
solution. Thus, senor should be cleaned and dried before use and the working electrode should be
polished well to remove any oxide layer and increase its surface area.

ELECTROCHEMICAL GAS SENSORS FOR NOX AND SOX:

Electrochemical gas sensors - are devices interacts electrochemically with the analyte gas of interest and
producing an electrical signal proportional to the analyte gas concentration.
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Working Principle:
Gas-permeable membrane is used to regulate the gas flow into the sensor. Its selectivity allows only the
analyte gas to pass and also acts as a barrier to prevent leakage of the electrolyte from the interior of the
sensor. Hydrophobic porous membranes are used with aqueous electrolytes.

Reference electrode: Ag/AgCl electrode placed close to working electrode and is used to maintain fixed
constant voltage near the working electrode.
Counter Electrode: Pt, is used to complete the circuit.
Working Electrode: Pt coated with Nafion (polytetrafluoroethylene) with carries the redox reaction of
analyte.
The working and reference electrode are connected to a battery through the ammeter.
Electrolyte: Sulphuric acid is used. Electrolyte should be a good ionic conductor, and chemically and
physically stable under operating conditions of sensor. It facilitates the cell reaction and carries the ionic
charge across the electrodes.
Working of Electrochemical gas sensors for the detection of NOx and SOx:
The following steps are involved in the working of a typical electrochemical gas sensor:
 The diffusion of gas analyte through capillary diffusion barrier and reach the membrane. The
hydrophobic membrane allows only the selective gas molecules to interact with the sensing electrode.
 On the surface of sensing electrode, the gas is either oxidised or reduced.
 The number of electrons lost or gained at the sensing electrode results in the change in current or
resistivity at the open circuit, which is a measure of concentration of the gas molecules.
 The reactions are as follows:
NO + 2e- → ½ N2 + O2-
NO2 + 2e- → NO + O2- O2 + e- → O2 -
O2 - + 2SO → 2SO2 + e-

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DISPOSABLE SENSORS (DS):

Definition: Disposable sensors are low cost and easy to use sensing devices intended for short term or
rapid single point measurements. They convert physical, chemical, or biological changes in their
environment to an analytical signal.
Advantages of disposable sensors over classical sensor:
1. They are low cost, flexibility of their design, great reproducibility of the process.
2. They are biodegradable and sustainable.
3. They provide digitized chemical and biological information.
4. They have short duration of analysis and fast response time (Rapid testing).
5. They are typically cheaper than classical sensors (Cost-effective).
6. They do not require calibration or maintenance (Convenient).
7. They can help to reduce the risk of cross contamination in medical and food safety applications.
(Hygienic).
DISPOSABLE SENSORS (DS) IN THE DETECTION OF BIOMOLECULES : (Ascorbic Acid)
Detection of Ascorbic Acid:
Chemical name of Vitamin-C, a water-soluble vitamin is Ascorbic acid, commonly derived from green
vegetables, fruits and other dietary supplements. It improves the immune system. It enables collagen
synthesis, which is required for the bones, teeth, skins, cartilages etc.,
Components of the Sensor:
 It is comprising of three disposable electrodes: working, counter electrodes and a reference electrode.
Each one includes a contact or terminal, a section, and an active area.
 All the electrodes have been manufactured by silk screen printing with conductive material ink on a
plastic polyester (PET) sheet.
 The active surfaces of the counter electrode and working electrode have been printed with a conductive
ink of C (MWCNT) and modified with gold nano particles.
 The active surface of the reference electrode has been printed with an Ag/AgCl ink.
Working:
 The electrochemical sensor can catalyse the two-electron electro catalytic oxidation and hydrogen
dissociation of AA to dehydro-ascorbic acid in the presence of oxygen in solution.
 The MWCNT acts as electron transfer mediators promoting the electron transfer between AA
molecules and the matrix interface increases the electro catalytic oxidation of AA during
electrochemical detection and transduce their presence into measurable signals.
 The electric current or voltage produced is proportional to the concentration of the ascorbic acid.

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HO
HO
O O O O
HO
HO 2H 2e
HO OH
O O
Ascorbic Acid (AA) Dehydroascorbic acid

DISPOSABLE ELECTRODES IN THE DETECTION OF PESTICIDES

Detection of Glyphosate:
One of the most commonly used pesticides is glyphosate. Glyphosate has the ability to attach to the soil
colloids and degraded by the soil microorganisms. As glyphosate is a herbicide, the pesticide was used
more intensively. As a consequence of the heavy use of glyphosate, residues of this compound are
increasingly observed in food and water. Recent studies reported a direct link between glyphosate and
chronic effects such as teratogenic and tumorigenic.
Components: The sensor is a silicon-based chip comprising of three electrodes system. It is fabricated by
electro deposition technique.
Working electrode: A gold electrode of 4mm diameter coated with 200nm thickness gold nanoparticles.
Counter electrode: A gold electrode of 4mm diameter coated with 20nm thickness gold nanoparticles.
Reference electrode: Ag/AgCl.
Electrolytes are added to increase the conductivity of the solution and minimize the resistance between
the working and counter electrode.
Working:
 The electrochemical detection is based on the oxidation of glyphosate on gold working electrode.
 A potential of 0.78V is applied on working electrode, there is a interaction between analyte and
electrode surface.
 Glyphosate oxidizes on the working electrode brings a change in current in the electrolyte medium.
 The change in the current is a measure of concentration of glyphosate.

Glyphosate Amino methyl Glyoxylate

Phosphonic acid

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ANALYTICAL TECHNIQUES
COLORIMETRY:
It is a device that used to measure and quantifies the absorbance of coloured compound in the solution at
particular wavelength.
Principle: This method is based on Beer-Lamberts law. When monochromatic light falls on a
homogeneous medium, a portion of incident light is absorbed by the medium and remainder is transmitted.
The extent of absorption depends on the concentration of the solution and thickness of the medium.
Beer – Lambert’s law: Absorbance is directly proportional to concentration and thickness of the medium.
A = εCt
Where „A‟ = absorbance, „C‟ = concentration of the solution „t‟ = thickness of the medium and „ε‟ = molar
absorptivity coefficient.
Estimation of Copper by Colorimetry
Instrumentation:
1. Light source: Tungsten lamp
2. Slit: It minimize unwanted light.
3. Lens: It gives parallel beam of radiation
4. Filter: It provides the desired wavelength range of 620nm. Where Cupraammonium sulphate solution
gives the maximum absorbance.
5. Cuvette: Cuvette which holds the sample solution for analysis.
6. Photocell detector: It is used to convert transmitted light signal into electrical signal.
7. Recorder: It is used to read the electrical signal directly as absorbance.

Procedure: A series of standard solutions of CuSO4 is prepared by adding ammonia solution and diluted
to the definite volume by using colorimetry water.
CuSO4 + 4NH3 + H2O------------------------->[Cu(NH3)4 SO4 · H2O]
(Cuprammonium sulphate)
1. 2, 4, 6, 8 and 10ml of CuSO4 solution is taken in five different 25ml volumetric flasks.
2. 2.5ml of NH4OH is added to all the flasks and made up to the mark using Colorimetry water.
3. Blank solution is prepared by taking 2.5ml of NH4OH and made up to the mark with
Colorimetry water in 25ml standard volumetric flask.
4. To the given test solution of CuSO4, 2.5ml of NH4OH is added and made up to the mark with
Colorimetry water in 25ml standard volumetric flask.
5. Filter is set to 620nm and absorbance (optical density) of the blank solution is made zero.
6. Absorbance of all the prepared standard solutions and test solution is noted.

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Applications:
1. Colorimetric determination of the d-metals like Nickel, Cadmium, etc.,
2. Used in soil testing for analysis of soil and plant nutrients.
3. Used in food testing laboratories to check concentration of chemical parameters.
4. Used in clinical laboratory for analysis of biomolecules such as glucose.

POTENTIOMETRY:
Potentiometry is the met hod of estimation of substances in solution by observing sudden change in
potential of the cell at equivalence point.

Principle: Potentiometry principle is based on Nernst equation. The relation between electrode potential
and metal ion concentration is given by the Nernst equation:
E = E0 + 0.0591 log [Mn+]
𝑛

As, the metal ion concentration increases, the potential also increases.

Determination of Iron using potentiometric sensors:

Instrumentation : A potentiometer consists of a reference electrode, an indicator
electrode and a device for measuring the potential. The indicator electrode responds
rapidly to the changes in the potential due to the concentration changes of the
analyte. A simple arrangement of potentiometric titration is shown in Figure.

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Procedure and working:

Burette : Standard K2Cr2O7 solution.
Accessories: Digital potentiometer attached with calomel and platinum electrodes.
Beaker : Given ferrous ammonium sulphate (FAS) solution + 1 t.t. of dil.H 2SO4 +
magnetic bead for stirring. Place the electrodes inside the beaker containing FAS solution
and note down the potential. Add K2Cr2O7 solution from the burette in increments of
0.5ml, with constant stirring and measure the potential after each addition. After a sudden
jump of potential, record 8-10 more readings.
 Initially, the potential of Pt electrode is dependent on the concentration of Fe 2+
ions in the denominator. As the amount of K2Cr2O7 is added to the solution,
gradually, Fe2+ ions gets oxidized to Fe3+ increasing its concentration. As a
result, the potential of the electrode increases depending on their ratio of
respective ions.
E = E° + 0.0591 log [Fe3+]
1 [Fe2+]
 When there is no Fe2+ions in the solution, there is abrupt increase of potential
with addition of potassium dichromate. This indicates the equivalence point of
the titration. The sudden jump in the potential value at the Pt electrode is also
due to developed potential as a result of the redox reaction Cr6+ to Cr3+ in
the solution.
E = E° + 0.0591 log[Cr6]
6 [Cr3+]
 After the end point there is gradual increase in potential since concentration of
Cr6+ ion increases. Determine the equivalence point of titration by p lo t t ing
∆E/ ∆V versus volume of K2Cr2O7. The redox reaction for the above
equations can be written as:
K2Cr2O7 + 7H2SO4 + 6FeSO4 → K2SO4 + Cr2(SO4)3 + 3Fe2(SO4)3 + 7H2O

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CONDUCTOMETRY: Conductometric estimation is an analytical method where unknown

substance is estimated upon reading the conductance of the solution, upon every incremental
addition of titrant when there is sudden change in the conductance value equivalence point is
reached and determined graphically.

Theory: Ohm‟s law states that the current I (ampere) flowing through a conductor is directly
proportional to the applied potential, E (volt) and inversely proportional to the resistance R
(ohms) of the conductor.

V=IR
Specific conductance of an electrolyte solution is the conductance of the solution present
between two parallel electrodes of 1cm2 area of cross section and 1cm apart.

Instrumentation: A simple arrangement of conductometric titration is shown in Figure. It

consists of two platinum electrodes each of unit area of cross section placed unit distance
apart. The electrodes are dipped in the electrolytic solution taken in a beaker. It is connected
to a conductivity bridge.
Procedure: The titrant is added from a burette and the solution is stirred. The conductance is
measured after the addition of the titrant at intervals of 0. 5ml.The end point is determined by
plotting conductance against the volume of titrant added.

Application:

a) Conductometric titration of Strong acid with a strong base:

Consider the titration of HCl against NaOH.
NaOH + HCl → NaCl + H2O
The conductance initially decreases till complete neutralization of the HCl takes place. This is
due to the replacement of highly mobile H+ ion by the Na+ ion. After complete neutralization
of the HCl, further addition of NaOH raises the conductance sharply. This is due to increase
Sensors & Analytical Techniques RNSIT 2024-25

in the concentration of the OH - ions. A plot of conductance (ohm-1) against the volume of
NaOH (cm3) gives a graph as shown in Figure. The point of intersection of the curve gives
the equivalence point.

b) Conductometric titration of Weak acid with strong base:

Consider the titration of acetic acid against NaOH.
CH3COOH + NaOH → CH3COONa + H2O
The conductance will be initially low since acetic acid is a weak electrolyte. When NaOH is
added to the acetic acid, the sodium acetate formed is highly ionized and the conductance
increases. After complete neutralization of the acetic acid, further addition of NaOH raises
the conductance sharply. A plot of conductance (ohm-1) against the volume of NaOH (cm3)
gives a graph as shown in Figure. The point of intersection of the lines gives the equivalence
point.

c) Conductometric titration of Mixture of acids (strong and weak) with strong base:
Consider the titration of mixture of HCl and acetic acid against strong base NaOH.

HCl + NaOH → NaCl + H2O

CH3COOH + NaOH → CH3COONa + H2O

HCl being stronger acid than CH3COOH will get titrated first. The titration of CH3COOH
will start only after HCl is completely neutralized.

During the titration of HCl verses NaOH, the conductivity decreases due to replacement of
H+ ions with Na+ ions. After neutralization of HCl, the neutralization of CH3COOH will start

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and the conductivity increases to small extent till its neutralization is complete due to the
sodium acetate formed is highly ionized. After neutralization of CH 3COOH, the conductance
rapidly rises with further additions of NaOH. This is due to increase in the concentration of
the OH- ions. A plot of conductance (ohm-1) against the volume of NaOH (cm3) gives a graph
as shown in Figure. The point of intersection of the lines gives the equivalence point V 1 and
V2.

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QUESTION BANK
1. Define sensor. Explain the terminologies of a sensor.
2. Explain the working principle of electrochemical sensor.
3. Explain the application of electrochemical sensor in dissolved oxygen detection.
4. Give the applications of electrochemical sensor.
5. Explain the application of electrochemical sensor in detection of SOx and NOx.
6. Explain the working principle of electrochemical gas sensor in detection of Nox.
7. What are disposable sensors? List the advantages of DS over classical sensor.
8. Explain the detection of ascorbic acid using the electrochemical sensor.
9. Describe the application of disposable sensor in pesticide detection.
10. Discuss the Cu estimation using colorimetric method.
11. What is potentiometry? Explain the principle, instrumentation and working of
potentiometric sensor in iron estimation.
12. Briefly explain the estimation of acid mixture by conductometry method.
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13. Write a short note on the estimation of strong acid by conductometric method.
14. Write a note on the estimation of weak acid by conductometric method.
15. Explain the principle, instrumentation and application of conductometric sensor in acid
mixture estimation.

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