APPLIED CHEMISTRY

STUDY MATERIAL

FOR THE STUDENTS OF I/II SEM. B.E.

(BIT AUTONOMOUS SCHEME - 2024)
For CS, AIML, DS, ICand IS Branches

Dr. N. Suresha.
[Link]., [Link]., [Link]., Ph.D.
Department of Chemistry
Bangalore Institute of Technology, B`lore
Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, [Link]., [Link],. [Link]., Ph.D. BIT, B`lore

Module-II
Sensors and Analytical Techniques
Syllabus
[Sensors: Introduction,Types of sensors. Working principle of Electrochemical sensors. Electrochemical sensors for
the detection of pharmaceuticals (Diclofenac) and hydrocarbons (1-hydroxy pyrene). Electrochemical gas sensors for
Dissolved oxygen. Electrochemical gas sensors for detection of toxic gasses (NO 2, SO2). Disposable sensors in the
detection of biomolecules (Ascorbic acid) and pesticides (Glyphosate).

Sensors in Analytical techniques: Working principle and instrumentation of Optical Sensor (Colorimetric sensor)
and its application in the estimation of Copper. Working principle and instrumentation of Potentiometric sensors and
its application in the estimation of Iron. Principle and instrumentation of Conductometric sensors and its application
in the estimation of weak acid].

Sensors:
Sensors are devices used to detect the presence of chemical or biological species and to monitor
physical parameters like temperature, humidity, etc. There are different types of sensors like gas
sensors, chemical sensors and biological sensors, developed for various applications.

Electrochemical sensors: Electrochemical sensor is a device which converts the information

associated with electrochemical reactions (the reaction between an electrode and analyte) into an
applicable qualitative or quantitative signal. They are mainly divided into three types:
potentiometric, conductometric and amperometric/voltammetric sensors.

Working of a sensor: The basic components of a sensor are;

i. Receptor: It is a sensing element made of chemical or biological molecule, capable of

interacting with the analyte and producing analytical signal proportional to the
concentration of analyte.
ii. Transducer: It is electronic device capable of converting analytical signal into electrical
signal.
iii. Processor: It processes the electrical signal and transmits into a readable or measurable
form.
iv. Detector: It detects the reading in various forms such as digits, graph, image, etc. to
display on screen.

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Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, [Link]., [Link],. [Link]., Ph.D. BIT, B`lore

Properties: Sensors are -

 selectively sensitive to particular type of chemical species (analyte).

 have ability to interact with the exceptionally small concentrations of analyte and send
signal.
 increased sensitivity, high accuracy and fast response.
 available in compact design.
 have ability to expand previous and existing analytical detection range.
 cost effective and eco-friendly.

Applications: Electrochemical sensors have been used in-

 in military and defence applications for the detection of explosives or toxic gases.
 to detect various polluting chemicals in the atmosphere.
 in biomedical applications for early detection of disease, toxins.
 to monitor physical parameters such as temperature, humidity, etc.
 to monitor glucose in blood.
 to study neurotransmitters in brain for understanding neurophysiology.
 in food industry to determine the quality and freshness of food samples.
 in agriculture to detect soil humidity, pesticide/insecticide residues and nutrient
requirements.

Electrochemical Sensor for the measurement of Dissolved Oxygen (DO):

Dissolved oxygen is a key measure of water quality relied upon in various applications.
In industrial water treatment, dissolved oxygen levels can be an indicator of water quality issues
that lead to corrosion of equipment. In aquaculture, fish transport and aquarium applications,
dissolved oxygen is monitored to ensure that aquatic species have enough oxygen in their habitat
to survive, grow and reproduce.

The concentration of dissolved oxygen in water can be monitored continuously using a dissolved
oxygen sensor. The working of dissolved oxygen sensor depends on the type of sensor used.
Commercially available dissolved oxygen sensors are of 2 types:

1. Electrochemical dissolved oxygen sensors: They measure dissolved oxygen concentration in

water based on the electrical current produced. There are two types of electrochemical DO
sensors:

i. Galvanic dissolved oxygen sensor: They consist of two polarized electrodes Zn as an

anode and Ag as cathode and an electrolyte solution such as NaOH. The electrodes and
electrolyte solution are isolated from the sample by a thin, semi-permeable membrane.

ii. Polarographic dissolved oxygen sensors: They consist of a silver anode and gold
cathode and an electrolyte solution such as KCl. The electrodes and electrolyte solution
are isolated from the sample by a thin, semi-permeable membrane.

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Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, [Link]., [Link],. [Link]., Ph.D. BIT, B`lore

2. Optical dissolved oxygen sensors: They measure dissolved oxygen concentration in water
based on quenching of luminescence in the presence of oxygen. They can measure either the
intensity or the lifetime of the luminescence as oxygen affects both.

Measurement of dissolved oxygen by DO sensor:

Working principle: In an electrochemical DO sensor, dissolved oxygen diffuses from the water
sample across an oxygen permeable membrane into the sensor. Wherein, the oxygen undergoes a
chemical reduction reaction producing an electrical signal. This signal can be read by a dissolved
oxygen instrument.

Procedure:
Anode: Ag
Cathode: Au/Pt – (inert electrode)
Electrolyte: KCl solution

Electrochemical DO sensors consist of two polarized electrodes, an anode and a cathode, in an

electrolyte solution. The electrodes and electrolyte solution are isolated from the sample by a thin,
semi-permeable membrane. Dissolved oxygen diffuses across the membrane at a rate proportional
to the partial pressure of oxygen in the water. The dissolved oxygen is then reduced at the cathode
resulting in the production of an electrical current that is directly related to the oxygen
concentration. This current is carried by the ions in the electrolyte and runs from cathode to
anode. As this current is proportional to the partial pressure of oxygen in the sample, it can be
calculated by the following equation:

4.F .Pm (t ) . [Link] 2

id 
d
id = current produced
F = Faraday’s constant = 96500 C/mol
Pm(t) = permeability of the membrane as a function of temperature
A = surface area of cathode
pO2 = partial pressure of oxygen
d = membrane thickness
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Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, [Link]., [Link],. [Link]., Ph.D. BIT, B`lore

Electrode reactions:
Anode reaction: 4Ag → 4Ag+ +4e–
4Ag+ + 4KCl → 4AgCl + 4K+

Cathode reaction: O2 + 4e– + 2H2O → 4OH–

4OH– + 4K+ → 4KOH

Overall reaction: O2 + 2H2O + 4KCl + 4Ag → 4AgCl + 4KOH

Electrochemical Sensor for pharmaceuticals:

Pharmaceuticals are simple/complex organic molecules essential to combat ill-health. After usage,
they enter into ecosystem through waste and cause adverse effects on living organisms even if
they present at low concentration. Therefore, to monitor the presence of these pharmaceuticals in
the ecosystem, development of reliable, stable, low cost, rapid analytical tool is required. There
are several methods for the purpose, but electrochemical sensors are the best option for the
detection of pharmaceuticals.

Determination of Diclofenac (DF):

Diclofenac (DF) is a non-steroidal anti-inflammatory drug used for the treatment of headache,
mild migraine, muscle pain, dental pain, rheumatoid arthritis and osteoarthritis. DF has no side
effects when taken in the proper doses but an overdose can cause adverse effects on the human
body. Moreover, the presence of diclofenac in ecosystems directly affects the health of living
organisms, even if it is present at trace. Electrochemical sensing methods have been commonly
used to detect DF.

Working Principle: DF sensor consists of a working or sensing electrode such as nano

structured carbon coated with gold nano particles (or iron oxide nano particles) and a counter
electrode which are separated and immersed in an aqueous solution of acids or neutral solution.
When the DF molecule comes in contact with the sensing electrode, DF is oxidized to, 2,6-
dichloroaniline and 2-(2-hydroxyphenyl) acetate by the loss of an electron and H+ at a potential of
0.6V. Proton and electron react with 2-(2-hydroxyphenyl) acetate on counter electrode producing
2-(2-hydroxyphenyl) ethanalate. The current thus produced from the reaction is monitored and
used to calculate the concentrations of DF.

Electrode Reactions:

On working electrode:

OH -
NH2
O Cl Cl
-
O + H2O e + H+ + +
NH O
OH
Cl Cl

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Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, [Link]., [Link],. [Link]., Ph.D. BIT, B`lore

On counter electrode:
-
O -
-
O
+ e + H+
O
OH OH
OH

Electrochemical sensor for hydrocarbons:

Like oxides of nitrogen, carbon and sulphur, the presence of hydrocarbons in the atmosphere is
also dangerous. Among hydrocarbons, polycyclic aromatic hydrocarbons (PAH) are persistent
organic pollutants widely found in the atmosphere, water, soil and food. The incomplete
combustion of coal, gas, wood, garbage and tobacco results in the formation of PAH. PAHs can
enter the human body through respiration, diet and contact. They are known to be carcinogenic.
After entering the body, some PAHs are metabolized into hydroxyl PAHs (OH-PAHs). Hence
human exposure to PAHs is an important factor to reveal their toxicity and carcinogenic risk.
Therefore, it is essential to develop an analytical technique to monitor the presence of
hydrocarbons in the ecosystem. Electrochemical sensor is one of the best techniques.

Determination of 1-hydroxypyrene (OHP):

1-hydroxypyrene belongs to the class of polycyclic aromatic hydrocarbons. If its concentration is

beyond the limit, it will affect the life of both plant and animal lives causing asthma, cancer,
bronchitis, [Link] sensing methods have been widely used to detect OHP.

Working Principle: The 1-hydroxypyrene sensor consists of glassy carbon electrode coated
with chromium containing metal organic framework as the working electrode, Ag/AgCl as the
reference electrode and a platinum wire as the counter electrode which are separated and
immersed in 0.05M phosphate buffer (pH 2.0) containing 0.2M NaCl solution.1-
hydroxypyrene is electro-oxidized to several hydroxylated species and then hydroquinone by
losing 2e− and 2H+ when a constant potential of 0.7 V is applied. The current produced from these
reactions is directly proportional to the concentration of analyte is monitored and used to calculate
the concentration of 1-hydroxypyrene.

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Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, [Link]., [Link],. [Link]., Ph.D. BIT, B`lore

Electrochemical sensor for Gaseous analyte:

Electrochemical gas sensor is an amperometric type sensor, used to determine the concentration
of gaseous analyte like air pollutants such as COx, NOx, SOx, leakage of chemicals in industries
such as cyanides, etc. It consists of a membrane, reference electrode, working electrode and
counter electrode dipped in an electrolyte solution. The designing of gas sensor depends on the
type of gaseous analyte to be detected.

The main components of gas sensors are;

i. Filter: It allows only the analyte of interest to enter inside the sensor.
ii. Membrane: It is a hydrophobic semi permeable membrane which regulates the inflow of
gaseous analyte. Its pores structure will not wet by water molecules of electrolyte helps the
easy diffusion of gas on to the working electrode surface.
iii. Electrodes: Reference, working and counter electrodes. The selection of receptor on
working electrode depends on the type of gaseous analyte to be detected.
iv. Electrolyte: Acidic, basic or neutral solution having good ionic conductivity is used as an
electrolyte for better transport of ionic species. It must be physically and chemically more
stable.

Working principal:

i. Diffusion: Gas diffused trough the filter and then through the membranes onto the
working electrode surface.
ii. Adsorption: Gas adsorbed on the working electrode surface.
iii. Reaction: Oxidation or reduction reaction takes place on working electrode surface by
losing or gaining electrons.
iv. Flow of electrons: Electrons will flow through the external circuit.
v. Electrical signal: Electrical signal is generated depending on the concentration of
analyte.
vi. Processing: Processing of electrical signal and its transmission into a readable form.
vii. Desorption: Desorption and removal of products from the electrolyte.
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Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, [Link]., [Link],. [Link]., Ph.D. BIT, B`lore

Electrochemical gas sensors to determine NOx;

Nitrogen oxide is the general term for a gas mixture composed of different oxides of nitrogen,
often expressed as NOx. Monitoring NO level becomes essential in the diagnosis of
cardiovascular problems since NO is a key vasodilator.

Working Principle: The working principal of all electrochemical gas sensors is same but the
selection of receptor to be coated on working electrode and the use of electrolyte are different.
They depend on the type of gas to be detected.

For the detection NO, sensor consists of a working electrode (WE) such as glassy carbon
surface modified with cobalt(IV) oxide catalyst and platinum counter electrode (CE) to make it
more sensitive to NO and a Ag/AgCl electrode as a reference electrode (RE) which are
separated and immersed in an aqueous solution of acids or bases. When NO gas comes in
contact with the sensing electrode it gets oxidized and oxygen gets reduced on cathode. The
current thus produced from the reaction is monitored and used to calculate the concentrations of
NO.

Electrode reaction: NO in solutions is directly electro oxidized in three steps:

NO → NO+ + e-
NO+ + OH- → HNO2
HNO2 + H2O → NO3- + 2e- + 3H+

For the detection NO 2, sensor consists of a working electrode (WE) such as Au, Pt/Nafion and
platinum counter electrode (CE) to make it more sensitive to NO and a Ag/AgCl electrode as a
reference electrode (RE) which are separated and immersed in an aqueous solution of 10 M
H2SO4. When NO2 gas comes in contact with the sensing electrode it gets reduced to NO. The
current thus produced from the reaction is monitored and used to calculate the concentrations of
NO2.

Reaction: NO2 + 2H+ + 2e-→NO + H2O

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Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, [Link]., [Link],. [Link]., Ph.D. BIT, B`lore

Electrochemical gas sensors to determine SOx:

SOx is the generic term for a gas mixture composed of sulphur and oxygen of which sulphur
dioxide (SO2) is naturally present in the atmosphere at very low concentrations but can be
harmful at higher concentrations. The major source of sulfur dioxide pollution is the
combustion of coal and petrol containing sulfur. Sensors are used to monitor sulfur dioxide.

Working Principle: SO2 gas sensor consists of a hydrophobic membrane, Au/Nafion sensing
electrode, counter electrode and the reference electrode with 0.5 M H2SO4 as electrolyte. SO2 gas
molecules diffuse through the semi permeable membrane into the sensing electrode and undergo
oxidation producing sulfur trioxide (SO3) as well as protons and electrons. Protons and electrons
reduce oxygen on the counter electrode producing water. The current thus produced from the
reaction is monitored and used to calculate the concentrations of SO2.

Electrode Reactions:

On working electrode: SO2 + H2O → SO3 + 2H+ + 2e-

On counter elecrode: ½ O2 + 2H+ + 2e- → H2O

Electrochemical Biosensor:

Biosensors are the devices used to detect biomolecules like nucleic acids, hormones, glucose, etc.
Various biosensors are used for industrial, agricultural and clinical applications.

The main component in biosensor is bio-receptor which is capable of interacting with the bio-
analyte. The bio-receptor is an immobilized biological molecule like enzyme, hormones, nucleic
acids, etc. which is selectively and sensitively interacts with the analyte and produces analytical
signal. This analytical signal is detected and converted into a readable electrical signal by a
transducer as shown below.

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Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, [Link]., [Link],. [Link]., Ph.D. BIT, B`lore

Disposable sensors (DS):

Disposable sensors are low-cost, easy-to-use sensing devices designed for short-term or rapid
single-point measurements. They are low cost, stable, reliable, smaller, lighter, easy to use, time
saving, highly selective and sensitive and highly advantageous over classical sensors. These types
of disposable sensors are extensively required for the analysis of samples from industrial,
agricultural and clinical fields.

Disposable biosensor consists of reference, working and counter electrodes which are coated on a
special type of paper strip by using screen printing technology. This strip is inserted into a
portable meter to monitor and measure the signal.

Advantages of DS over Classical sensors:

 Cost-effective: Disposable sensors are typically cheaper than classical sensors.

 Convenient: Disposable sensors do not require calibration or maintenance.
 Hygienic: Disposable sensors can help reduce the risk of cross contamination in medical
and food safety applications.

 Portable: Because disposable sensors are typically smaller and lighter than classical
sensors.

 Rapid testing: Disposable sensors can provide results quickly, allowing for faster decision-
making.

 Reduced waste: Because disposable sensors are designed to be used once and then
discarded.
Disposable sensor for biomolecule:

Monitoring of biomolecules like hormones, vitamins, nucleic acids, lipids, carbohydrates, etc., is
very essential because any imbalance in these would cause health issues like diabetic, asthma,
heart attack, birth complications, etc. There are several disposable sensors developed for the
analysis. The receptor on working electrode may be enzyme modified or non-enzyme modified.
Considering the dis-advantages of enzyme modified sensors, such as fabrication and poor
stability, non-enzyme biosensors have attracted increasing research interest in recent years.

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Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, [Link]., [Link],. [Link]., Ph.D. BIT, B`lore

DS for the detection of Ascorbic acid:

Ascorbic acid (AA) is the key biomolecule in the physiological process of human metabolism. It
is an important water-soluble vitamin (Vitamin C) in forming collagen, a protein that gives
structure to bones, muscles and blood vessels. It is a potent reducing and antioxidant agent that
regulates fighting against bacterial infections as well as detoxifying reactions. Abnormal levels of
AA will lead to some disorders and diseases, such as mental illness, scurvy and anemia.
Therefore, it is essential to establish a sensitive tool to detect AA.

Working Principle: AA sensor consists of a gassy carbon working electrode (GCE), platinum
counter electrode and Ag/AgCl reference electrode, printed on paper strip using screen printing
technology. The enzyme, ascorbate oxidases immobilized on GCE is used as working electrode.
When AA comes in contact with the working electrode, it get oxidizes to dehydroascorbic acid by
losing electrons and dehydroascorbic acid further hydrolyses to form 2,3-diketogulonic acid. The
magnitude of electric current generated from reaction is directly correlated with the
concentrations of AA, which is monitored and used to calculate the concentration of AA.

Electrode reaction:

HO HO
O O O O + -
HO HO + 2H + 2e
HO OH O O
Ascorbic acid Dehydroascorbic acid
H2 O

HOH 2 C H
HO HO
H O
HO
O O
2,3-diketo gulonic acid

Disposable sensor for Pesticides:

With the intension of getting good yield and to protect crop, farmers have started using verities of
pesticides. They need to be used in very low concentrations. But without proper knowledge they
have been using in large amounts. This resulted in the accumulation of traces of these pesticides
in soil, water and air. The entry of these pesticides into the human blood system may cause
asthma, cancer, birth problems, etc. Therefore there is a need for developing a low cost, reliable,
sensitive enzyme modified screen printed disposable sensors to detect pesticides.

DS for the detection of Glyphosate:

Glyphosate is one of the most widely used herbicides with applications in agriculture, forestry,
industrial weed control, lawn, garden and aquatic environments. Glyphosate has the capacity to
bind to soil colloids and be degraded by soil microorganisms. Nowadays glyphosate residues are
becoming more common in food and water as a result of extensive usage of this chemical.
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Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, [Link]., [Link],. [Link]., Ph.D. BIT, B`lore

Glyphosate has the potential to stimulate hormone-dependent malignancies in humans and is

highly carcinogenic even at low concentrations. Therefore, it is essential to design a low cost,
reliable, rapid and sensitive tool for the detection of glyphosate.

Working Principle: Glyphosate disposable sensor consists of a carbon paste

electrode/graphite oxide paste electrode as a working electrode, platinum as counter electrode
and Ag/AgCl as reference electrode, printed on polymer paper strip using screen printing
technology. The enzyme, glycine oxidase is capable of selectively oxidizing glyphosate into
amidomethylphosphonic acid. The enzyme, glycine oxidase is immobilized on platinum-
decorated laser-induced graphene (LIG) electrode and is used as working electrode. When
glyphosate comes in contact with the working electrode, it get oxidizes to
amidomethylphosphonic acid with loss of electrons and protons. The current thus produced from
the reaction is monitored and used to calculate the concentrations of glyphosate.

Electrode reaction:

- O
-
OH O O O
O HO
P NH P NH2 + H
O HO O
HO
Glyphosate Amidomethylphosphonic acid Glyoxylate

Sensors in Analytical techniques:

Analytical techniques are the methods used for the qualitative and quantitative analysis of
chemical species present in the sample. Volumetry and gravimetry are classical methods used for
the quantitative determinations. Now a day, there are several analytical techniques like
Colorimetry, Potentiometry, Conductometry, etc., used for the analysis of chemical species.

Advantages of analytical techniques:

 Time saving – Analysis time has been reduced from several hours or days to even minutes.
 Accuracy - Improvement in accuracy of results by eliminating errors introduced due to
personal bias.
 Sensitivity - Highly sensitive to analyte present in the sample.
 Less amount of sample – Micro amounts of sample is enough for analysis.

1. Colorimetric Sensor:
Colorimetric sensors are electronic components designed to detect and convert incident light rays
into electrical signals.

Colorimetry is used for the determination of concentration of a substance present in its solution.
This method is used for colored solutions or solutions which produce color on treating with
suitable reagent.

Theory: When a monochromatic light of intensity (I0) is passed through a transparent medium, a
part of it is absorbed (Ia) by the species and electrons get excited from lower energy level to
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Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, [Link]., [Link],. [Link]., Ph.D. BIT, B`lore

higher energy level, some part is reflected (Ir) and remaining is transmitted (It). So intensity of
incident light is equal to the sum of Ia, Ir and It.
i.e. I0= Ia + Ir+ It
For a glass-air interface Ir is negligible and therefore, I0 = Ia + It
It/Io = T is called transmittance, log 1/T = log I0/It is called the absorbance or optical density. The
relationship between absorbance (A), concentration, (c) (expressed in mol/dm3) and path length,
(t) (expressed in cm) is given by Beer-Lambert’s law. Beer`s law states that amount of radiation
absorbed by solution is directly proportional to the concentration (c) of species in the solution.
Lambert`s law states that amount of radiation absorbed by solution is directly proportional to
path length (t) of the solution. i.e.
I
A  log 0   .c.t
It
Where ‘ɛ’ is the molar extinction coefficient and is a constant for a given substance at a given
wavelength. If ‘t’, the path length is kept constant, then, A  C. Hence the plot of absorbance
against concentration gives a straight line (calibration curve).

Instrumentation:

Source: tungsten filament or sodium vapor lamp is used as a source of light.

Filter: a device used to obtain monochromatic light of required wavelength.
Sample tube: cuvette to hold the sample usually made of glass or quartz cell.
Photocell: converts the emitted light into electrical signal.
Detector: detects the light radiation absorbed by solution.
Recorder: records the numerical value.

Application: For the estimation of Copper:

When a solution of cupric ions is treated with ammonia, deep blue colored complex is formed.
The color intensity is depends on concentration of copper ions.

Cu2+ + 4NH3 → Cu(NH3)42+ (Deep blue)

Procedure:
1. Prepare a stock solution of CuSO4 by dissolving 1g in 250 ml of water.
2. Transfer 2.5, 5.0, 7.5 and 10.0 cm3 of the solution into separate, labelled 50 ml standard
flasks.
3. Add 5 ml of 1:1 ammonia solution to each of above solutions and also to the test solution,
make up to the mark with ion exchange water and mix well.
4. Prepare a blank solution by dissolving 5 ml ammonia in 50 ml std. flask and use this
solution to set the colorimeter to ZERO at 620 nm.
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5. Measure absorbance to all the solutions at 620 nm.

6. Draw a calibration curve by plotting absorbance versus concentration of copper (mg/ml).
7. Using the calibration curve, determine the volume of copper sulphate in the test solution
and calculate the amount of copper (mg/ml) in the test solution.

[Link] Vol.
CuSO4 Absorbance
of
NH3
Blank 5 0
2.5 5
5.0 5
7.5 5
10 5
TS 5

Calculation:

249.6 g of CuSO45H2O contains 63.55 g of Cu2+

63.55
⸫ 1 g of CuSO45H2O contains = = 0.2545 g of Cu2+
249.6
2+
250 ml contains = 0.2545 g of Cu
⸫ 1 ml contains = 1.018 mg of Cu2+
Volume of CuSO4 in test solution = ml
Concentration of Cu in test solution= Volume of T S x 0.02mg/ml.

Result: Concentration of Cu2+intestsolution = mg/ml

2. Potentiometric sensors:
Potentiometric sensor is a device used to determine the concentration of analyte by measuring the
change in potential of reacting system. It is based on Nernst equation, which gives the relationship
between metal ion concentration (Mn+) and electrode potential (E).

Theory: Redox titrations can be carried out potentiometrically using platinum-calomel electrode
combination. For the reaction,

Reduced form → Oxidized form + n electrons

the potential is given by the Nernst equation,

0.0591 [oxidizedform]
E  E0  log
n [reducedform]
Where, 𝐸𝑜is the standard potential of the system.
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The potential of the system is thus depends on the ratio of the concentration of the oxidized to that
of the reduced species. As the reaction proceeds, the potential changes more rapidly at the vicinity
of the end point of the titration. This may be followed potentiometrically and a plot of change in
potential against volume of titrant (titration curve) is characterized by a sudden change of
potential at the equivalence point also called endpoint.

Instrumentation:

A potentiometer consists of a reference electrode and an indicator electrode (sensor) and a device
to measure the change in potential during the reaction. Calomel electrode is commonly used as
reference electrode and platinum electrode as indicator electrode. The indicator electrode
responds rapidly to the changes in the potential with respect to the concentration of analyte, which
is converted to electrical signal and displayed as numerical value on potentiometer.

Application: Estimation of FAS using K2Cr2O7 solution.

Procedure:
i. Pipette out 25.0 cm3of FAS solution into a beaker. Add two test tube of dil. H2SO4.
ii. Immerse the reference-indicator electrodes assembly in the solution and connect them to
the potentiometer.
iii. Note down the emf of the cell before the addition of titrant from the burette.
iv. Now add 0.5 ml of K2Cr2O7 from the semi micro burette. Allow the solution to mix well
and measure the potential. Continue the procedure till a sudden rise in emf of the cell is
observed. Take about 5-6 more readings and tabulate the reading as mentioned be low.
v. Determine the end point by plotting ∆E/∆V versus volume of K2Cr2O7 as shown in the
figure.
vi. From end point, find the normality of FAS and calculate amount of FAS/dm3.

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Vol. ofK2Cr2O7 Emf ∆E /∆V

E (mv) (mv/ml)
(V) ml

0
0.5
1.0
1.5
2.0
,
,

Calculation:
N K 2Cr2O7 xVK 2Cr2O7 0.5 xVe
Normality of FAS   =a
VFAS 25
Weight of FAS per liter = Normality x Equivalent weight of FAS (392)

Result: Weight of FAS per liter = a x 392 g/dm3.

3. Conductometric sensor:
It is used to determine the end point of acid-base titration by observing the change in specific
conductance of solution.

Theory: The principle underlying conductometric titration is the replacement of ions of particular
conductivity by ions of different conductivity during titration. It is based on Ohm`s law, which
states that the current (I) flowing through a conductor is directly proportional to the applied
potential (E) and inversely proportional to the resistance (R).
i.e. I= E/R or E = IR
The reciprocal of resistance is called conductance.
1 a
i.e. C = 1/R = x Ω-1 or mho or Siemens
 l

l l
⸫ R =    , where ρ is specific resistance, is called cell constant
a a
The reciprocal of specific resistance is called specific conductance ‘  ’
1l l
i.e.  =   or C  
Ra a
Specific conductance is defined as the conductance of the solution which is placed between two
electrodes of 1cm apart and having unit area of cross section.
The conductance of a solution is depends on temperature, number of the ions and their mobility.

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Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, [Link]., [Link],. [Link]., Ph.D. BIT, B`lore

Instrumentation:

It consists of two platinum electrodes each of unit area of cross section placed unit distance apart.
The electrodes are dipped in the electrolyte solution taken in a beaker and connected to a
conductance measuring device.

Applications: Conductometric titrations are used to

1. Estimate mixture of weak acid and strong base
2. Estimate the concentration of colored or turbid solutions which cannot be titrated using
indicators.
3. Estimate weak acids or bases where no suitable indicators are available.
4. Estimate very dilute solutions.

Ex. Estimation of weak acid (CH3COOH) using strong base (NaOH).

CH3COOH +NaOH→ CH3COONa +H2O

Initially conductance is very low because acetic acid is a weak electrolyte. When NaOH is added to
the acid, the salt formed is highly ionized and hence conductance increases. On complete
neutralization of the acid, further addition of base leads to an increases in the number of OH-ions.
Hence the conductance increases sharply.
A plot of conductance against the volume of base added is shown in the figure. The point of
intersection of two curves gives the neutralization point.

Procedure:
i. Pipette out 50 ml of acetic acid into a beaker.
ii. Immerse the conductometric sensor in the solution and connect them to the
conductometer.
iii. Note down the conductivity of the solution before the addition of NaOH from the burette.
iv. Now add 0.5 ml of NaOH from the semi micro burette. Allow the solution to mix well
and measure the conductance. Continue the procedure till the acid is completely
neutralized. Take about 5-6 more readings after neutralization and tabulate the reading as
mentioned below.
v. Determine the neutralization point by plotting conductance versus volume of NaOH as
shown in the figure.
vi. From end point, find the normality of CH3COOH and calculate amount of
CH3COOH/dm3.
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Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, [Link]., [Link],. [Link]., Ph.D. BIT, B`lore

Vol. of NaOH conductance

(V) ml

0
0.5
1.0
1.5
2.0
,
,

Calculation:
N NaOH xVNaOH 0.5 xVe
Normality of CH3COOH   = ‘a’
VCH3COOH 50
Weight of CH3COOH per liter = Normality x Equivalent weight of CH3COOH (60)
= ‘a’ x 60
Result: Weight of CH3COOH per liter = ………… g/dm3.

QUESTION BANK

1. What are sensors? Discuss the working principle and any four applications of electrochemical
sensor.
2. Describe the working principle and any four applications of conductometric sensor
(conductometry) and optical sensor (colorimetry).
3. What is electro chemical sensor? Explain the measurement of dissolved oxygen (DO) using
sensor.
4. Illustrate the detection of diclofenac and hydro carbons (PAH'S) with electro chemical
oxidation sensor.
5. What are disposable sensors? Explain the detection of ascorbic acid and glyphosate using
disposable sensor.
6. What are electrochemical gas sensors? Apply the principle of gas sensor to detect NOx and
SOx.
7. Discuss the principle and instrumentation of colorimetric sensor.
8. Elucidate the application of colorimetric sensor for the estimation of copper with model graph.
9. Describe the principle and instrumentation of potentiometric sensor.
10. Explain the principle and instrumentation of conductometric sensor.
11. Discuss the application of potentiometric sensor for the estimation of iron with model graph.
12. Describe the application of conductometric sensor for the estimation of weak acid with model
graph.

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