Dept of Chemistry, CMR Institute of Technology BCHES102/202

Module 1: Sensors and Energy systems

Sensors:

Introduction, working, principle and applications of Conductometric sensors,

Electrochemical sensors,

Thermometric sensors (Flame photometry) and Optical sensors (colorimetry).

Sensors for the measurement of dissolved oxygen (DO).

Electrochemical sensors for the pharmaceuticals.

Electrochemical gas sensors for SOx and NOx. Disposable sensors in the detection of biomolecules and pesticides.

Energy Systems:

Introduction to batteries, construction, working and applications of Lithium ion and Sodium ion batteries.

Quantum Dot Sensitized Solar Cells (QDSSC’s)- Principle, Properties and Applications.

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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

Sensors
A sensor is a detection device that can sense the measured data and convert it into electrical signals or other
required forms of information output according to particular rules, in order to meet the requirements of data
transmission, processing, storage, and display, as well as recording and control.
Sensors enable objects to have senses such as touch, taste, and smell, and they gradually become alive as a
result of their evolution. Thermal elements, photosensitive elements, gas-sensitive elements, force-sensitive elements,
magnetic-sensitive elements, humidity-sensitive elements, sound-sensitive elements, radiation-sensitive elements,
color-sensitive elements, and taste-sensitive elements are the ten categories according to their basic sensing functions.
Sensors are frequently categorized based on their functioning principle, input data, and application scope.
They may be loosely split into three types based on their diverse functioning principles:
1) Physical sensor – Sensors built with the physical qualities of specific transforming components and the special
physical properties of certain functional materials are known as physical sensors.
2) Chemical sensor – Chemical sensors convert the composition and concentration of inorganic and organic
chemical compounds into electrical signals using the electrochemical reaction concept.
3) Biological sensor - It's a sensor that detects and measures biochemical compounds using biologically active
chemicals.

Electrochemical sensors for the detection of Pharmaceuticals (diclofenac):

Electrochemical detection occurs at the interface between an analyte (diclofenac) of interest and the working electrode to
which a potential is applied with respect to the reference electrode, while the corresponding current is measured.
Different sensors are developed for the detection of Diclofenac such as:
1. Potentiometric sensor (low sensitivity)
2. Electrochemical sensor with unmodified
carbon electrode
3. Electrochemical sensor with modified carbon
electrode
4. Bio-sensor

Components of disposable screen-printed Carbon paste electrode for diclofenac detection (Three electrode sensor):

Working electrode: Carbon Paste with MWCNT or Graphene

Counter Electrode: Carbon Paste with MWCNT or Graphene
Reference Electrode: Ag/AgCl

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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

Working:

• The electrochemical oxidation of DCF on carbon-based sensor at pH 7.0 is reversible reaction.

• Oxidation of Diclofenac occurs at carbon electrode to release electrons to form radical intermediates and followed by
hydrolysis of radical intermediate species.
• The products formed are 2,6- dichloroaniline and 2-2(-hydroxyphenyl) acetic acid.
• Reactions on the electrode cause the current to flow.
• The intensity of this current is a function of the number of oxidized / reduced molecules.

Products: 2,2 Hydroxy-Phenyl-Acetic Acid and 2,2 Dichloroaniline

Significance of SOx and NOx:

The major contributors to traditional air pollution are NOx, SOx, and H2S while NH3 and Volatile organic compounds are of
increasing concern recently. Traditional air quality monitors based on mass spectroscopy, infra-red spectroscopy and gas
chromatography are expensive and not suitable for large scale deployment. Electrochemical gas sensors provide a cheap
alternative option for widespread air quality monitoring.
Electrochemical gas sensors for NOx:
Chemiresistive sensors based on graphene and its derivatives have been used to
measure NOx
Chemiresistive sensors measure the change in resistance upon exposure to analyte
gases and can detect toxic gases at very low concentrations.
In general, the response obtained in a chemiresistive sensor is
Reactions:

The concentration of electrons decreases due to the reaction between the electrons in the sensing materials and NOx gas, as
shown and resistance offered by e- decreases and current increases.
“Higher the concentration of NOx, lesser would be the resistance”
𝑅% = ((𝑅o − 𝑅g) ⁄ 𝑅o) ∗ 100
R% is the reported sensor response

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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

Ro is the resistance in dry clean air (Back ground Correction)

Rg is the new resistance observed under analyte gas

Electrochemical gas sensors for SOx: The sulfur dioxide sensor works on the electrochemical principle.
It works based on the diffusion of SO2 gas into the sensor.
Initially SO2 oxidizes to produce oxygen free radical and converted to
molecular oxygen.
Electrons are consumed from sensor for the reduction of O2 and number
of electrons decreases on the electrode surface.
Resistance of the electrode is a function of concentration of SO2.
Reaction:

𝑅% = ((𝑅o − 𝑅g) ⁄ 𝑅o) ∗ 100

R% is the reported sensor response
Ro is the resistance in dry clean air (Back ground Correction)
Rg is the new resistance observed under analyte gas

Disposable sensors:
Disposable sensors are low-cost and easy-to-use sensing devices designed for short-term or rapid single-point
measurements.
Advantages of disposable sensors:

• They transduce physical, chemical, or biological changes in their environment to an analytical signal.
• Disposable sensors are biodegradable and sustainable
• They have a short duration of analysis and fast response times.
• It provide digitized chemical and biological information.
• Prevents the contamination of samples.
• Detection of biomolecules using biosensor

Disposable sensor for detection of ascorbic acid:

It is comprising three disposable electrodes: Working electrode, auxiliary or counter electrode and reference electrode. Each
one includes a contact or terminal, a section and an active area. All electrodes have been manufactured by silkscreen printing
with conductive material ink on a plastic polyester (PET) sheet.

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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

The active surfaces of the counter electrode and working electrode have been printed with a conductive ink of C (MWCNT)
and modified with gold nanoparticles.
Active surface of the reference electrode has been printed with an Ag/AgCl ink.
Working:

• The electrochemical sensor can catalyze the two-electron electro catalytic oxidation and hydrogen dissociation of AA
to L-dehydroascorbic acid in the presence of oxygen in solution.
• The carboxyl MWCNTs act 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.

UPAC Name of Ascorbic Acid: (5R)-[(1S)-1,2-Dihydroxyethyl]-3,4-dihydroxyfuran-2(5H)-one

Detection of Glyphosate by electrochemical oxidation method:
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 led to the appearance of resistant species, 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 tetrogenic, tumorigenic.

Electrochemical Sensor for Glyphosate Detection:

The sensor is a silicon- based chip comprising of three-electrode system.
It is fabricated by electro deposition technique.

Working Electrode: A gold electrode of 4 mm diameter coated with 200nm thickness gold nanoparticles
Counter electrode: A gold electrode of 4 mm diameter coated with 20nm thickness gold nanoparticles
Reference Electrode: Ag/AgCl/Cl-

Electrolytes are added to increase the conductivity of the solution and minimizes the resistance between the working and
counter electrode.

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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

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.

Conductometric Sensors:
Conductometric sensors are two electrode devices, measures the electrical conductivity in sample solution
between two electrodes.
Principle:
The basic principle of conductometric detection involves a reaction that can change the concentration of ionic
species. This reaction leads to changes in electrical conductivity or current flow. In this method, two inert metal
electrodes are used. The ions or electrons produces during an electrochemical reaction may change the conductivity
or resistivity of the solution.
Working:
The conductivity is result of dissociation an electrolyte, into ions. The migration of
the ions is induced by an electrical field. When a potential difference is applied to the
electrode, there is an electrical field within the electrolyte, so the positively charged
ions move towards cathode and negatively charged ions are move towards anode.
Thus, the current in the electrolyte is caused by the ion movement towards the
electrodes where the ions are neutralized and isolated as neutral atoms (or molecules).
This chemical change is recognized by working electrode and transducers converts
this chemical change into electrical signal.
Applications:
➢ Detection of changes in ion concentration in chemical solutions
➢ Monitoring of changes in the pH of a solution.
➢ Detection of specific ions or analytes in environmental monitoring, food quality control and medical
diagnostics.
➢ Monitoring the process control and industrial applications where changes in ion concentration are critical.

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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

Optical sensors:
Optical sensors are electronic components designed to detect and convert incident light rays into electrical signals.
Example: Colourimetric Sensors
Principle: When a sample solution is interacted with a light of suitable wavelength, certain quantity of light is
absorbed by the analyte solution and it is observed by a sensor and transducer converts intensity of absorbed light
into electrical signal.

Working: A monochromatic light is made to pass through analyte solution where certain quantity of light is absorbed
and it is a function of concentration of analyte. The change in the intensity of light is detected by photodetector
(sensing). The light source generates an intense and stable radiation signal needed to probe an optical property of the
molecular recognition element in the sensor. The amount of absorbance is governed by Beer-lamberts law.
Applications:
Optical sensors are widely used in a variety of applications due to their high sensitivity, fast response times, and
ability to work in harsh environments. Here are a few common applications of optical sensors:
• Medical Equipment
• Environmental Monitoring
• Communication Systems
• Industrial Process Control
• Automotive
• Consumer Electronics
• Security and Surveillance

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

Electrochemical DO sensors, also known as amperometric or Clark-type sensors, measures dissolved oxygen
concentration in water based on electrical current produced.
Example: Galvanic Sensor

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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

Galvanic Sensor is a Electrochemical sensor, which is used to measure DO

Components:
Cathode : W orking electrode-Ag
Anode : Zn, Pb or any other active metal
Electrolyte: KOH, NaOH or any other
inert electrolyte
Membrane: Gas permeable membrane (Teflon)

Working:
• The difference in potential between the anode and the cathode should be at least 0.5V.
• DO sensor is immersed in water sample.
• Oxygen molecule diffuses across the oxygen-permeable membrane (Teflon) and the rate of diffusion is
proportional to the concentration of oxygen in the water.
• Molecular Oxygen reduces to OH- at cathode.
• 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.
Reactions:

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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

Working principle of thermometric sensor

Thermometric sensor
A temperature sensor is a device, typically, a thermocouple or resistance temperature detector, that provides
temperature measurement in a readable form through an electrical signal.
Working principle of thermometric sensors
The working principle of a thermometric sensor is based on the concept that the physical properties of materials
change with temperature. They are composed of two dissimilar metals that generate an electrical voltage or resistance
when a temperature change occurs by measuring the voltage across the diode terminals.
• Thermocouples
In this case, when there is a temperature gradient between the measuring junction
and reference junction, a voltage is generated. The magnitude of this voltage
depends on the temperature difference between the two junctions and the types of
metals used in the thermocouple.

• Resistance temperature detector (RTD)

Here, the electrical resistance of certain metals (mainly used platinum,
copper and Nickel) changes with temperature. When the temperature of
the RTD changes, the electrical resistance of the material changes in a
repeatable manner. This change in resistance is then correlated to the
temperature using calibration curves.

Applications
• Used for verifying design and construction.
• Used to measure the temperature rise during the process of curing concrete.
• They can measure rock temperatures near liquid gas storage tanks
• It can measure water temperatures in reservoirs and boreholes.
• They can also be used to study the temperature effect in the instruments.

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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

Energy Systems
Galvanic cell: Galvanic cell is a device which converts chemical energy into electrical energy through a
spontaneous redox reaction.
Battery: It is a device consisting of two or more galvanic cells connected in series or parallel or both.
Principle components of a battery are:
1. An anode where oxidation occurs.
2. A cathode where reduction occurs.
3. An electrolyte, which is ionically conducting.
4. A separator to separate anode and cathode compartments.

The batteries are classified as

1. Primary battery or primary cells: The batteries in which the cell reaction is not completely reversible are called
primary batteries. They are also referred to as irreversible batteries. They are not rechargeable and once discharged
have no further electrical use. They have no cycle life.
Eg; dry cell or Zn-MnO2 Cell, Li-MnO2 battery.
2. Secondary battery: The batteries in which the cell reaction is reversible are referred to as secondary batteries.
Secondary batteries after discharge can be recharged electrically to their original condition by passing electric current
through them in the direction opposite to that of discharge current. They are also referred to as storage batteries or
accumulators. They have cycle life.
Eg: Lead – acid battery, Ni – Cd battery
3. Reserve Batteries: The batteries, which may be stored in an inactive state and made ready for use by activating
them (by adding an electrolyte, another cell component) prior to application are referred to as reserve batteries. In
these batteries, a key component is separated from the rest prior to activation and hence the batteries are capable of
long – term storage.
Eg: Magnesium water activated batteries, zinc –silver oxide batteries etc.
Advantages:
• Unlimited shelf life if properly packed.
• High reliability of performance.
• Variety of design options.

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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

Lithium – Ion Batteries:

The batteries in which lithium ions are used instead of lithium metal and movement of lithium ion takes place
through the electrolyte from one electrode to another electrode are called lithium-ion batteries. In general the battery
consists of soluble lithium intercalated carbon/graphite is used as anode. The cathode material is made up of lithium
liberating compounds.
e.g., Lithium cobalt oxide (LiCoO2) battery.
Construction and working principle
During discharging lithium ions are dissociated from the anode and
migrate through electrolyte to cathode. During charging, lithium from cathode
material is ionized and moves towards the anode. At the same time the electrons
travel through external circuit. The discharge and charge reactions are given
below,
Anode: Lithium intercalated graphite layer having thin copper foil.
Cathode: Lithium cobalt oxide layer having aluminium foil as current collector.
Electrolyte: Li salts ie., LiCl, LiBr, LiAlCl4 dissolved in propylene carbonate and 1,2 dimethoxy ethane.
Representation: Graphite/LiPF6 in organic solvent/LiCoO2

Advantages:
• High energy density.
• Long life
• High cell voltage
• Wide range of operating temperature (-200 to 400 C)
Applications: Li-ion batteries are used in cardiac pacemakers, laptops, cell phones and aerospace applications.

Sodium-ion battery
Sodium-ion batteries (SIBs) are energy conversion and storage devices that use sodium-ions to shuttle
positive charge between the anode & cathode in order to convert electrical energy to chemical energy and vice versa.
Construction and working principle
Anode: Hard carbon is used as the “standard” anode material in SIB, which stores sodium-ions at a low potential.
Cathode: cathode material is layered oxides (sodium metal oxide).

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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

Electrolyte: Electrolytes can be solids or liquids. The solid electrolytes are either polymeric or ceramic. Liquid
electrolytes primarily consist of mixtures of carbonate solvents such as ethylene carbonate (EC), diethyl carbonate
(DEC) or ethers such as dimethoxyethane (DME), or tetraethylene glycol dimethyl ether (TEGDME).
Separator: polymer separators such as Solupor or Celgard, or fiber-based separators such as Dreamweaver or glass
fiber.
Cell Potential: 1.85 to 3.45 V
The electrochemical cell reactions in a Na-S battery are as follows:
At anode: NaxC6 +
xNa + xe- + 6C

At cathode: Na1-xMO2 + xNa+ + xe- NaMO2

____________________________________________________________________________________

Net cell reaction: NaxC6 + Na1-xMO2 NaMO2 + 6C

SIBs generally contain two electrodes, one anode and one

cathode, both consisting of the respective active materials
coated on an aluminum foil current collector. A thin liquid-
permeable sheet called the separator is placed between the
two electrodes to keep them electrically insulated from each
other, while allowing sodium ions to move freely between
the electrodes. The anode or negative electrode, is where
the sodium is stored when the cell is in the charged state,
while the cathode or positive electrode, hosts the sodium-
ions in the discharged state. The transport of positively
charged sodium ions between the electrodes is enabled by a
solvent salt solution called the electrolyte, while electrons
move between the current collectors through an external
circuit.
Advantage:
❖ Low-cost and environmentally-friendly.
❖ Slightly lower energy density and high efficiency.
❖ Better safety characteristics.
❖ These are high rate batteries and operation at lower temperature
Disadvantage:
1) Batteries are less powerful.
2) Anode graphite absorbs too little sodium.
Application:

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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

1) Used in cellular phones and laptops.

2) In electric vehicles and power tools.

Quantum dot sensitized solar cell:

Introduction:
➢ A quantum dot solar cell (QDSC) is a solar cell that uses quantum dots as the captivating photovoltaic material.
➢ It is used to replace bulky materials such as silicon, or copper indium gallium selenide.
➢ Quantum dots have bandgaps that are adjustable through a wide array of energy levels by changing the size of the dots.
➢ Tiny nanocrystals—also known as quantum dots— yields as many as three electrons from one high energy photon of
sunlight. When today's photovoltaic solar cells absorb a photon of sunlight, the energy gets converted to at most one
electron, and the remaining energy is lost as heat.
➢ Quantum dot solar cells have the potential for solar or photovoltaic cells that reduce wasteful heat and capitalize on the
amount of the sun's energy that is converted to electricity. This is significant toward making solar energy more cost-
competitive with conventional power sources.
➢ A new type of quantum dot could lead to cheaper solar cells and better satellite communication.

Properties:

• QDs have properties intermediate between bulk semiconductors and discrete atoms or molecules.
• Their optoelectronic properties changes as a function of both size and shape.
• Larger QDs of 5-6 nm diameter emit longer wavelengths with colours such as orange or red.
• Smaller qds (2-3 nm) emit shorter wavelengths yielding colours like blue and green. However, the specific
colours vary depending on the exact composition of qds.

Construction and working of QDSC:

• Quantum dots acquire surplus photon energy, which is usually lost
to heat generation through a process called multiple exciton
generation.
• The light rays enter through the transparent electrode of a quantum
dot solar cell onto a light absorbing layer of dots in order to
generate electron hole pairs.
• The charged particles then separate and eventually travel to their
respective electrodes, producing electric current.
Mechanism:
i. Upon absorption of a photon, a quantum dot is excited from the
ground state (QDS ) to a higher energy state (QDS*)

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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

Excitation process: QDs + hv → QDs*

ii. The absorption process results in the creation of electron-hole pair
in the form of exciton. Dissociation of the exciton occurs if the
thermal energy exceeds its binding energy
Exciton dissociation: QDs* → e- + h+* (free energy)
iii. The excited electron is then injected in the conduction band of the
wide bandgap semi‐ conductor nanostructured TiO2 thin film. This process will cause the oxidation of the
photosensitizer (The QDs)
Injection process: QDs* + TiO2 → TiO2e-* + QDs+
iv. The injected electron is transported between the TiO2 nanoparticles, and then gets extracted to a load where the
work done is delivered as electrical energy.
Energy generation: TiO2e-* + C.E → TiO2 + e* (CE)

Properties:
1. QDs have properties intermediate between bulk semiconductors and discrete atoms or molecules.
2. Their optoelectronic properties changes as a function of both size and shape.
3. Larger QDs of 5-6 nm diameter emit longer wavelengths with colours such as orange or red.
4. Smaller qds (2-3 nm) emit shorter wavelengths yielding colours like blue and green. However the specific
colours vary depending on the exact composition of qds.

Quantum dots solar cell applications

▪ biological labeling,
▪ Imaging, and detection and as efficient fluorescence resonance energy transfer donors.
▪ It is used as light-emitting Diodes
▪ It is used as Photoconductors and photodectors
▪ It is used as Photovoltaic
▪ It is used in Biomedicine and environment.
▪ It is used in catalysis and others

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