Computer Science Engineering Stream (Chemistry group) 1 Course Title: Chemistry

for CSE Course Code: 22CHEE12/22 CIE Marks 50 Course Type

(Theory/Practical/Integrated) Integrated SEE Marks 50 Total Marks 100 Teaching
Hours/Week (L:T:P: S)* 2:2:2:0 Exam Hours 03+02 Total Hours of Pedagogy 40
hours Theory + 10-12 Lab slots Credits 04

MODULE 1:
Sensors and energy Systems (8hr) Sensors: Introduction,
Working principle and applications of conductometric sensors, Electrochemical sensors,
Thermometric sensors, and Optical sensors. Sensors for the measurement of DO.
Electrochemical sensors for the pharmaceuticals, surfactants, hydrocarbons, electrochemical
gas sensors for SOx, 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 dots sensitized solar cells (QDSSC’s)- Principle,
Properties and Applications.
SENSORS

Definition of sensor
Electrochemical sensors are made up of three essential components: a receptor that binds the
sample, the sample or analyte, and a transducer to convert the reaction into a measurable
electrical signal. In the case of electrochemical sensors, the electrode acts as the transducer.

working principle and applications of conductometric sensors,

Conductometric detection

 Conductometric detection is based on measurement of specific conductance of an

analyte and is preferable because it can be applied for detection of both electroactive
and electroinactive species.
 The conductivity electrodes can either be in contact with the solution or insulated using
a thin layer. Conductivity detection is mostly associated with
capillary electrophoresis (CE).
 In contact-mode conductivity measurement, the electrodes are in direct contact with
the sample. Although better contact with sample results in good sensitivity and lesser
response time, it is accompanied with the increased risk of degradation of electrodes
and contamination of sample.
  Conducting polymers are also used for conductance-based detection. They are organic
conjugated compounds with an extended π-orbital system allowing movement of
electrons from one end to other.
 Conducting polymers have unique electrical and optical properties that can be tuned by
reaction with redox active agents. Commonly used conducting polymers are polyaniline,
polyacetylene, polypyrrole, polyfluorine, etc.

Working of conductometric sensor

Fabrication and Surface Modification of Electrodes
 Interdigital electrodes (IDE) were screen-printed on a glass substrate (microscope slide)
to fabricate an interdigital transducer (IDT).
 Screen-printed interdigitated gold electrode-based sensor systems have been used for
variety of analytes
 The desired structure of interdigital electrodes was fabricated on the substrate via
screen printing with commercial gold paste.
 The electrode structure was designed by photo lithography.
 All organic components present in gold paste were removed by heating at 500 °C for 4
h. The advantage of this procedure is based on the robustness of the gold layers.
 The pattern and dimensions of the IDEs structure on transducer surface is shown
in Figure 1.

 IDT was fabricated by screen printing IDE of gold on glass substrate. IDT was coated
with sensitive layer and LCR meter was used to measure resistance of sensitive layer by
placing it in glass cell filled with electrolyte solution.
 The prepared transducer was cooled down to room temperature, then washed in an
ultrasonic water bath for 5 min and dried.
 The IDT was placed in a boiling mixture of chloroform and ethanol (1:1 v/v) for at least
10 min for washing.
 Afterwards, IDT was treated with hot lithium hydroxide solution (0.2 mM) for 10 min,
rinsed with distilled water and dried.
  Then, IDT was dipped in a solution of 3-aminopropyl-triethoxysilane in ethanol for 1–2
min followed by rinsing with ethanol. The silanized structure was cured for 10 min at
110 °C.
 A mixture of monomers, cross-linker, and template was heated at 70 °C until its gelation
point which is called as pre-polymer. This pre-polymer was applied to transducer
surface to form a rigid layer after complete polymerization.

Application conductometric sensor

1. DNA Detection

 AuNP (nano particles)-based genosensor designs for the detection of DNA hybridization.
 Both assay formats were based on a magnetically induced direct electrochemical
detection of the AuNP tags on a magnetic graphite–epoxy composite electrode.
 The first assay is based on the hybridization between two single-strand, biotin-
modified DNA probes: a capture DNA probe and a target DNA related to the breast
cancer gene.
 The second assay is based on hybridization between three DNA strands: a biotin-
modified capture DNA probe, a target DNA related to the cystic fibrosis gene, and a
DNA signaling probe modified with AuNPs via biotin–streptavidin conjugation.
2. Advanced Nanoparticle-Based Biosensors for Diagnosing Foodborne Pathogens
 The relationship between conductance and bioreceptor techniques is the basis for
developing conductometric detection performed using a conducting polymer.
 The conducting polymer acts as an electrochemical transducer to convert biological
signals into electrical signals. Examples of conducting polymers are polyaniline,
polythiophene, polyacetylene,
 Few applications of conductometric biosensors have been reported for the detection of
foodborne pathogens. Developed a direct-charge transfer conductometric biosensor to
detect Bacillus cereus in numerous food samples.
 In their study an electronic signal was generated by electron charge flow aided through
conductive polyaniline combined with the principle of a sandwich IA.
 The biosensor could decrease LOD to 35–88 CFU/mL B. cereus in food samples and only
took 6 min to complete. The biosensor was selective to B. cereus only used.
Application of conductometric sensor
1. Aptamer Technology for the Detection of Foodborne Pathogens and Toxins
2. Advanced Nanoparticle-Based Biosensors for Diagnosing Foodborne Pathogens
3. Microfluidic electrochemical devices for pollution analysis.
4. It is used for DNA Detection

Electrochemical sensors
Definition:
Electrochemical sensors are made up of three essential components: a receptor that binds the
sample, the sample or analyte, and a transducer to convert the reaction into a measurable
electrical signal. In the case of electrochemical sensors, the electrode acts as the transducer.

Electrochemical sensors are a class of sensors in which the electrode is the transducer
element. These devices are now found in a wide range of commercial applications.

Working principle and application of electrochemical sensors

 Electrochemical sensors are powerful analytical tools due to their superior sensitivity
and selectivity, quick response period, simplicity in operation, and miniaturization.
 The fundamental concept in the detection of analytes by electrochemical.
sensors involves the measurement of electric current generated by chemical reactions
in the electrochemical system.
 The reactions which occur at the interface of the surface of an electrode between the
recognition element, and the target/binding analyte generate an electrical double layer
and thus this potential is measured after transforming these chemical reactions into this
measurable electrochemical signal by a recognition element, and a transducer of the
sensor.
  An electrochemical sensor mainly consists of two main components, one is chemical
recognition system responsible for recognizing the analyte species and the other is a
physicochemical transducer that converts chemical interactions into electrical signals
that could be detected and displayed easily by modern electrical instruments.
 The electrochemical sensors can be classified based on the electroanalytical technique
employed to measure the chemical interactions into the main classes such as
conductometric, voltammetric, and potentiometric.
 One of the recent trends in the development of electrochemical sensors is to
use nanomaterials leading to substantial enhancement of their performance with
respect to sensitivity, selectivity, and rate of detection.
 A large number of nanomaterials, including carbon nanostructures (e.g., graphite and
CNTs), metal and metal oxide NPs, QDs, silica NPs, and other NPs, have been
investigated for their applications as electrochemical sensors.

Diagrammatic representation of the working principle of an electrochemical sensor

  Electrochemical sensor’s working mechanism involves the interaction of the target
analyte material with the electrode surface and bringing the desired change as a
consequence to a redox reaction, which generates an electrical signal that can be
transformed to explore the nature of the analyte species
 The nanomaterial electrode surface can be remarkably transformed by the process of
functionalization which can be executed by the attachment of biomolecules such as
aptamers, peptides, and antigen/antibody that functions as the specific chemical
recognition element.


Conclusions
Application Electrochemical sensors

 Electrochemical sensors are considered attractive tools to determine important

molecules or biomarkers that are used for the diagnosis of diseases and disorders.
 They are used for the monitoring of toxic levels of different substances in food quality
and environmental control.
 The biosensor application areas of these sensors extend to medical and biomedical
applications, process control, bioreactors, quality control, agriculture, bacterial and viral
diagnosis, industrial wastewater control.
  Technological advances have directly affected functionalized nanomaterial’s-
based electrochemical sensor depended on point-of-care diagnostics in a positive way.
 These self-testing or near-patient testing have provided reliable, low-cost, rapid
analyses when combined with electrochemical methodology.

Working principle and Thermometric sensors,

What is the Temperature Sensor?

Temperature sensors are simple devices that sense the degree of cold or heat and transform
it into a simple unit. But, do you ever think about how the temperature of the soil, land
boreholes, great concrete dams, or houses is detected? Well, this is done by using some of the
particular temperature sensors.

A thermocouple is another common example of them. Thermocouple, or briefly T/C, is

constructed from two different metals that produce an electrical output voltage in direct
relation with the temperature modification.

Temperature Sensor Working

 The fundamental working of this sensor is based on the voltage in its diode. The
temperature variation is directly related to the resistance of this diode.

 The resistance of the diode is detected and transformed into simple and readable
values of temperature such as Fahrenheit, Kelvin, or Centigrade and demonstrated in
meaningful formats instead of readout values.
  These temperature sensors are employed to sense the internal temperature of various
structures like power plants

 In addition, some devices have a type of vibrating wire in the structure of the sensor
that operates on the principle of stress variations followed by temperature
modifications.

 They fundamentally include a magnetic wire which has high tensile strength. Two
sections are set to dissimilar metals that any variation in temperature influences the
tension in the wire directly and, therefore, its main frequency of vibration.

 In modern and high-tech temperature sensors, the basic metal is aluminum because
aluminum has a greater coefficient of a thermal effect than steel. As the temperature
sign is transformed into frequency, the readout values utilized for other vibrating
sensors can also be used to control the temperature.

Temperature Sensors Formula

The frequency related to the temperature is also proportional to the tension ‘σ’ in the
wire, can be described as follows:

f = 1/2 * [σg/ρ] / 2L (Hz)

Where:

σ = tension of the wire

ρ = density of the wire

L = length of wire

g = acceleration due to gravity

Types of Temperature Sensor

1. Thermostats

A thermostat is a contact type sensor containing a bi-metallic section constructed from two
different metals such as aluminium, nickel, tungsten, or copper.
The main principle of thermostats is based on the difference in the linear expansion
coefficient of the metals. Therefore, it forces them to generate a mechanical movement due
to heat rise.

2. Thermistors

Thermally sensitive resistors or briefly thermistors are particular sensors because of the
modification of their physical appearance due to the change in the temperature. The
thermistors are constructed from ceramic substances like oxides of particular metals covered
with glass. It will allow them to form simply.

Some thermistors are NTCs and have a negative temperature coefficient but there are a lot of
thermistors that have a positive temperature coefficient. They are introduced as PTCs, and
their resistance increases by increasing the temperature.

3. Resistive Temperature Detectors

RTDs are temperature sensors that are constructed from precise conducting metals like
platinum covered in a coil. The electrical resistance of an RTD modifies due to the
temperature variations.
3. Thermocouples

The thermocouple is one of the most popular temperature sensors because of its wide
temperature range, accuracy, sensitivity, reliability, and simplicity.

A thermocouple generally includes two sections of dissimilar metals, such as constantan and
copper, combined by welding. One of these sections, introduces as the Cold junction, has a
particular temperature while the other one, introduced as the Hot junction, is for the
measuring process.

Temperature Sensor Applications

 There are various kinds of temperature sensors, and the most common method to
classify their application depends on the way of connection, which contains contact and
non-contact sensors. Contact sensors like thermistors and thermocouples are directly
related to the target they want to measure, while the non-contact sensors detect the
thermal radiation emitted by the heat source.

 The main application of these temperature sensors is in hazardous locations like nuclear
power plants.

 Temperature sensors identify the heat of hydration in concrete structures in

geothermal control. They can also be employed to control the migration of seepage or
groundwater.
  One of the most usual methods of using them is in curing the concrete. It has to be
warm in order to construct and cure appropriately. The seasonal modification causes
structural expansion and changes its overall volume.

 The temperature sensors are employed for verifying model suppositions that will
improve more economical and safer construction.

 They can detect rock temperatures in order to identify storage tanks of liquid gasses
and the ground freezing process.

 Temperature sensors can also be used in land boreholes and reservoirs and to measure
water temperatures.

 They are employed to interpret temperature in dams to reduce stress in volume

variations and control the temperature variations on other installed instruments like
curing concrete.

Advantages of Temperature Sensors

Temperature Sensors have some advantages in comparison with other practical instruments.

 Temperature sensors are low-cost, precise, and extremely reliable in repeated

experiments
 They are desirable for both embedded and surface mount applications.
 They have a faster response time because of the lower thermal mass.
 The vibrating wire type is normally full-interchangeable. It means that one indicator can
be used for all sensors. It also has a particular technology for verifying long-term
stability, simple and fast output.
 They have some indicators that are suitable for direct temperature presentation. So,
they can be used for remote detecting and data logging.
 Their temperature probes have precise linearity and low hysteresis.
working principle and applications Optical sensors

Optical sensors
Definition:
 Optical sensors have two basic methods, to obtain sensor data from target molecules
that are label-based and label-free methods.
 Optical devices use special transducers like SPR (Surface plasmon resonance),
interferometers, gratings, and refractometers.
 Optical sensors are divided into several subclasses such as resonance, dispersion,
reflection, refraction, phosphorescence, infrared absorption, Raman scattering,
fluorescence, and chemiluminescence.
 Optical sensors for sensing of biological and chemical analytes are a rapidly growing
area with potential applications in many important fields such as medical diagnostics,
food analysis, environmental monitoring, agriculture, security, genomics, and
proteomics.

Optical Sensors working principle

 Optical sensors use visible or ultraviolet light to interrogate sensors for analysis. Optical
sensors can be represented in general terms as a wavelength-selectable light source,
the sensor material itself interacting with analytes, and a light detector (Fig. 1).

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

1. Ambient Light Sensors

 Mostly we have seen this sensor on our mobile handsets.

 It will extend the battery life and enables easy-to-view displays that are optimized for
the environment.

Ambient Light Sensors

2. Biomedical Applications
 Optical sensors have robust applications in the biomedical field. Some of the examples
Breath analysis using tunable diode laser, Optical heart-rate monitors an optical heart-
rate monitor measures your heart rate using light.
 A LED shines through the skin, and an optical sensor examines the light that reflected
back. Since blood absorbs more light, fluctuations in light level can be translated into
heart rate. This process is called as photoplethysmography.
3.Optical Sensor Based Liquid Level Indicator

 Optical Sensor Based Liquid Level Indicator consist of two main parts an infrared LED
coupled with a light transistor, and a transparent prism tip in the front.

 The LED projects an infrared light outward, when the sensor tip is surrounded by air the
light reacts by bouncing back with-in the tip before returning to the transistor.

 When the sensor is dipped in liquid, the light disperses throughout and less is returned
to the transistor. The amount of reflected light to the transistor affects output levels,
making point level sensing possible

Optical Level Sensor

Sensors for the measurement of DO

 Dissolved oxygen (DO) is one of the most critical elements to measure in cell culture
and also one of the most often overlooked.

 This oversight is for a variety of reasons ranging from lack of knowledge to the intrusive
nature of traditional DO probes.

 However, for most cell culture conditions, there is a simple solution found in optical DO
sensors.

 Though the technology was invented in the late 1990s, it was not until very recently
that it became affordable enough to be used at large scale and available for any bio
manufacturing team.

 When it comes down to the minute details of laboratory cell culture there are really
only two types of DO sensors, electrochemical and optical.
  Electrochemical DO sensors are most often referred to as Clark electrodes after Leland
Clark, who invented the technology in 1962. And the optical sensor, developed almost
four decades later, is named as you might assume for its reliance on optics.

Optical dissolved oxygen sensors working

 Optical DO sensors are made of two parts, a sensor spot and a fibre optic reader. The
sensor spot is attached to the interior of a cell culture vessel and contains a fluorescent
dye suspended in a hydrogel.

 The sensor spot is the only part of the system that comes in contact with cells or media.

 The external reader is connected to a computer or data hub and is responsible for
sending and receiving optical signals to the sensor spot.

 Optical DO sensors measure the DO concentration of liquid media or air based on the
quenching of luminescence in the presence of oxygen.

 Since oxygen affects both the intensity and the lifetime of the luminescence, either may
be used to measure DO.

There are three methods of measuring optical dissolved oxygen:

MAGNITUDE DOMAIN MEASURES THE PEAK OF LUMINESCENCE.
LIFETIME DOMAIN MEASURES THE DECAY RATE OF LUMINESCENCE.
PHASE DOMAIN MEASURES THE PHASE DIFFERENCE OF THE ENTIRE SIGNAL.

 Optical DO sensor technology was developed from the principle that DO quenches the
luminescence associated with chemical dyes in the sensor.

 The fluorescent dye exhibits an excitation maximum around 455nm, and an emission
wavelength of approximately 613nm.

 The fiber optic reader emits a blue light that excites the fluorophore which emits light
back at the higher wavelength.

 In the presence of oxygen, the fluorescence is quenched, and a higher level of oxygen
leads to lower emission intensities.
  This quenching also leads to changes in decay time which is the property that most
readers use to determine DO levels.

 The reader measures DO by emitting the blue light that causes the sensing element to
luminesce and then the computer translates the signal decay.

 Lifetime domain-based sensors have some advantages over magnitude domain sensors
and are the more common type of optical DO sensor on the market.

 They have better long-term accuracy and stability and are not as susceptible to
leaching, dye degradation, or signal drift.

What are the advantages of optical DO sensors?

1. NO FLOW REQUIRED
Because optical sensors do not consume oxygen there is no need for a steady replenishment
of oxygen at the tip of the sensor. This allows for the use of optical sensors in static cell
culture.
2. MINIMAL MAINTENANCE
The optical sensor spot is the only part of the device that comes in contact with cells or media
and they are designed to be single use, affordable, and disposable. Since there is no
membrane to replace and no cathode to take care of, regular maintenance is measured in
months or years rather than days or weeks.
3. NO NEED FOR CALIBRATION
High quality optical DO sensors come pre-calibrated and do not need to be adjusted before
use. This limits any possible down-time during experiments.
4. SHORT RESPONSE TIME
Optical sensors have a response rate similar to optical probes but since there is no need for
daily calibration, they have a greater lifetime of measurements.

What are the disadvantage of optical DO sensors?

1. SENSOR SPOT SENSITIVITY

Optical sensor spots are small, delicate, and must be handled with care. Exposure to high
concentrations of alcohols or certain organic compounds can also cause damage.

2. ENTRY COST
While the lifetime cost of optical DO sensors is lower than other types of probes because of
replacement and maintenance, the initial cost is usually higher than electrochemical probes.

3. NEW TECHNOLOGY
Despite having been discovered more than 20 years ago, optical sensor technology is still
relatively new to the market and many users are not familiar with how they work.

Electrochemical sensors for the pharmaceuticals

 An overview of the electrochemical sensors and biosensors developed for the analysis
of diclofenac.
 Carbon based-electrodes are the most investigated electrodes in diclofenac analysis.
 Carbon nanotubes and graphene-based composites are the most efficient modifiers for
diclofenac detection.
 Constructed biosensors allowed the detection of diclofenac at picomolar levels.
 Carbon nanotube-based electrochemical diclofenac sensors

 Electrochemical sensors, in particular, are a class of chemical sensors in which an

electrode is used as a transducer element in the presence of an analyte.
 Modern electrochemical sensors use several properties to detect various parameters in
our everyday lives, whether physical, chemical, or biological parameters.
 Carbon nanotubes (CNTs) have been increasingly employed in many areas including
fabrication of fast responsive sensitive sensors.
 Generally, two types of CNTs have been reported in literature namely multi-walled
carbon nanotubes (MWCNT)
Several types of electrodes have been modified with CNTs for the purpose of
electrochemical DCF determination, as illustrated.
1. Carbon electrodes improved diclofenac sensitivity using an edge-plane pyrolytic
graphite electrode (EPPGE) coated with single walled carbon nanotubes.
2. Under the optimum conditions, the detection limit was 0.82 nM which was 10 times
lower than that observed at bare pyrolytic graphite electrode.
3. Furthermore, the electrode also provides high selectivity in the presence of an excess
concentration of different interfering molecules and good recoveries in human blood
plasma and urine samples.
4. Functionalized CNT (fCNT) were also used for the construction of electrochemical
sensors for the determination of DCF.
5. The use of MWCNTs produced a significant improvement over the results obtained with
bare GCE with a detection limit of 0.1 μM.
6. It was discovered that diclofenac was irreversibly oxidized at +555 mV when the sweep
was initiated in the positive direction.
7. In the second cycle, two reversible couples are observed consisting of two cathodic
peaks and two anodic peaks.
8. The modified electrode was applied for electrochemical detection of DCF in
environmental water samples without sample pretreatment steps.
9. Good results were obtained with a linear range of 0.1–10 nM and a limit of detection
value of 28 pM.
10.MWNTs–dihexadecyl hydrogen phosphate (DHP) film coated GCE was also used for the
determination of diclofenac. It was discovered that the oxidation of diclofenac is a
totally irreversible process with no peak appeared on the reverse sweep.
11.By combination of CNTs with other materials, the performance of the modified
electrode can be significantly enhanced.
12.Some studies have shown that the combination of CNTs with metal or metal
oxide nanomaterial’s can increase electrochemically active sites and accelerate electron
transfer kinetics.
Electrochemical sensors for the surfactants

 The two promising electrochemical sensor constructed using carbon paste electrode
modified with Octyl phenol ethoxylate surfactant (OPEMCPE) and carbon paste
electrode modified with Sodium lauryl sulfate (SLSMCPE).
 The electrochemical characterization of Anthrone (ANT) was studied at the surface of
OPEMCPE with supporting electrolyte of pH 7.0 in 0.1 M phosphate buffer (PBS) and
also at the surface of SLSMCPE with supporting electrolyte of pH 7.5 in 0.1 M PBS by
using cyclic voltammetry (CV) and differential pulse voltammetry (DPV).
 The OPEMCPE and SLSMCPE exhibited an efficient electrocatalytic activity towards ANT
than the bare carbon paste electrode (BCPE).
Working method

Instrumentation
 Cyclic voltammetry and Differential pulse voltammetry conducted with an
electrochemical analyser with the standard three-electrode cell to complete the circuit
and connected to the personal desktop for control and storage of data.
 carbon paste electrode, OPEMCPE and SLSMCPE served as a working electrode, the
platinum electrode and an aqueous saturated calomel electrode employed as an
auxiliary electrode and reference electrode.
Chemicals and reagents required
 Anthrone (ANT),
 Sodium Lauryl Sulphate (SLS),
 graphite, Silicon oil, Octyl Phenol Ethoxylate, Acetone.
 Stock solution prepared using distilled water. 0. 1 M Phosphate buffer solutions (PBS)
with pH 7 and 7.5 adjusted with intermixing suitable amount of 0. 1 M disodium
phosphate and 0. 1 M monosodium phosphate and used as a supporting electrolyte.
OPEMCPE and SLSMCPE electrode preparation
 Graphite powder was blended with silicon oil with the proportion of 70:30 (w/w)
thoroughly in an agate mortar until attaining the homogeneous paste.
 The obtained paste further tightly packed into the cavity of 3 mm in
diameter Teflon tube and smoothened on the filter paper for the smooth surface and
thus obtained was BCPE.
 The 10 µL of OPE from the prepared stock solution is immobilized on the surface of the
carbon paste electrode by drop coating method for 5 min for uniform layer of OPE on
the bare carbon paste electrode then the electrode was rinsed with distilled water to
eradicate the unreacted residue of surfactants the obtained electrode designated as
OPEMCPE and the immobilization of 10 µL SLS taken from the prepared SLS stock
solution and the same procedure was carried out as mentioned for OPEMCPE,
therefore, this electrode designated as
 These modified electrodes used for the electrochemical determination of ANT.
Electrochemical sensors for the, hydrocarbons
 It is well known that, different types of combustible, toxic and health hazards materials
used in industrial processes such as H2S, NOx, H2 are the source of risk.
 Therefore, it is important to monitor regularly the concentrations of these health
hazard materials to avoid any accidents and mishaps. Demand for these devices in
order to ensure occupational health and safety is on the rise across numerous industry
verticals such as process and manufacturing industries
 Moreover, the air pollutants detecting sensor must be stable in harmful conditions. In
this respect, industry and scientific community has been working on it to develop
various type of sensors for detecting air pollution.
 Moreover, keeping in mind the rapid increment in environmental pollution, the
commercialization of these gas sensors has become a priority area for human health.
 The classification of sensors based on their working such as infrared (IR), Metal oxide
semiconductor, electrochemical and optical (fluorescence) sensors are discussed
briefly in
 However, in this work, chemiresistive and electrochemical sensor is mainly discussed
because of their wide applications.
 In addition, oxide semiconductor based environmental sensor have been more
successfully developed at research laboratory and industrial levels. They have been
used to detect a variety of gases such as CO, H2S, NH3, SOx, NOx, etc., with varying
degree of commercial success.
These sensors are being widely used in various applications such as automotive, consumer,
commercial, industrial and environmental monitoring.
Electrochemical sensor for hydrocarbon
 Electrochemical cell for detecting gases in heavy gas dispersion system which provides
signal directly proportional to the partial pressure of gas in the atmosphere.

 Basically, electrochemical sensors used to calculate the concentration of different

analyte compounds in tested samples.

 Electrochemical sensors are widely used to detect toxic gases, such as CO, H2, SO2 and
so on.

 The less power consumption is the main advantage of electrochemical. sensor over
other available gas sensor.

 Because of aforesaid reason, commercialize environmental gas sensor adopted

electrochemical theory especially in portable instruments that contain multiple sensors.

 The usual life time of an electrochemical sensor under standard operating conditions
(25o C and within 20% of ambient pressure) is approximately one year.

 Basically, electrochemical sensors is based on a cell with a combination of two or three

electrodes which are called reference, working, auxiliary/counter electrodes and ionic
conductor between them as shown fig below.

 These electrodes be responsible for providing the surface area on which an

oxidation/reduction occurs.

 The ionic conduction of an electrolyte solution in contact with the electrodes is coupled
with the electron conduction of each electrode to provide a complete circuit for the
current.

 As an example, CO gas molecules interact with working electrode as shown

in Fig. Where oxidation of CO molecules take place on the working electrode through
chemical reaction :

CO + H2O → CO2＋ 2H+ + 2e-

Gas sensors for SOx,

 Sulfur oxides, SO2 released from thermal power stations and other industrial plants, are
gases harmful to the environment.
 It is very important to detect and control the concentrations of SOx in industrial
processes. The methods usually used to detect SOx are chemical and electrochemical,
but these methods cannot be used in situ or in constant operation.
 Recently, SOx sensors utilizing a solid electrolyte such as K2SO4 [ 1 ], Na2SO4 [2], LiSO4
[3], AgzSO4 [4], Nasicon [5], Na-flAl203 [6] and Ag-fl-Al203 [7] have been widely
studied, because this type of sensor has its own advantages:
 Continuous quantitative measurement; high selectivity and sensitivity; easy operation
and fast response; simple construction and low price.
Fig. Below Schematic of the SO2 sensor: ( I ) lead wire; (2) cement; (3) Ag- ,-alureina; (4) Ag
electrode; (5) porous Pt electrode.

Sensing mechanism
The sensor was composed of the following electrochemical cell:
Ag/ Ag-ᵱ-Alumina/ Pt, SO3, SO2, 02
The anode reaction
2Ag→2Ag++ 2e_
The cathode reaction
2Ag+ + SO3 + 1/202 + 2e- → Ag2SO4

The total reaction was

2Ag + SO3 + 1/202 → Ag2SO4
Where SO3 was produced by the reaction can be checked by sensor.
 Electrochemical gas sensors for, NOx,
ELECTROCHEMICAL SENSORS

Electrochemical sensors are made up of three essential components: a receptor that binds the
sample, the sample or analyte, and a transducer to convert the reaction into a measurable
electrical signal. In the case of electrochemical sensors, the electrode acts as the transducer.

Figure 1: Schematic illustrating the basic components of an electrochemical sensor.

 In most electrochemical sensors, an electrode surface is used as the site of the

reaction. The electrode will either oxidize or reduce the analyte of interest.
 The current that is produced from the reaction is monitored and used to calculate
important data such as concentrations from the sample.
 For instance, the nitric oxide (NO) sensor below, is a common electrochemical sensor.
NO is an important vasodilator, and monitoring its levels becomes crucial in the
diagnostics of cardiovascular complications.
 The sensor monitors the oxidation of NO as it occurs on the electrode surface. In many
instances of electrochemical sensors, the electrode surface can be modified with
catalysts, membranes, or other metals to make the electrode more sensitive and/or
more selective toward the analyte (in the instance below, the Glassy Carbon (GC)
electrode is modified with Cobalt (IV) Oxide and Platinum).

Figure 2. Nitric oxide sensor developed by the Masef research group

 The direct electro oxidation of NO in solutions follows a 3 step reaction. The Δ E for the
overall process is +0.5V vs. a Ag/AgCl reference electrode.

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

The ΔE for the overall process is +0.5V vs. a Ag/AgCl reference electrode.

The reaction for the Ag/AgCl reference electrode is the following:

AgCl+e−↔Ag+Cl- E∘+0.222V

Disposable sensors in the detection of biomolecules

and pesticides
Electrochemical Biosensors and Their Working Principle

 There are a number of analytical tools such as chromatographic methods, spectroscopic

analysis, and luminescence available.
 However, these involve discrete sampling followed by laboratory analysis.
 These are expensive, time consuming and does not provide high-resolution data.
 However, electrochemical measurements provide excellent sensitivity and selectivity,
continuous reliability and portability. Therefore, they are identified as superior
analytical tools.
Definition
The desired biomolecules such as enzyme, hormones, antibodies etc. are
immobilized via physisorption/chemisorption, which will cause an intimate contact with the
transducer. The analyte of interest will selectively bind with the biomaterial that produces the
measurable electronic response (Figure 1.1).
 Fig. 1.1 Schematic representation of working principle of
electrochemical biosensors.

Based on working principles, electrochemical sensors are classified as follows:

(a)Potentiometric biosensors (b) Amperometric biosensors (c)Conductometric biosensors (d)

Impedemetric biosensors and (e) Piezoelectric biosensors.

Application of Disposable sensors

Disposable Electrodes in the Detection of Biomolecules

 Biomolecules/biological molecules are essential organic compounds present in all the living
systems.
 They are the building blocks of the body and are responsible for maintenance and metabolic
process. The major classes of biomolecules include carbohydrates, proteins, lipids, nucleic
acids, enzymes, hormones, etc. Each class are vital in the day-to-day activities of every living
organism.
 Therefore, periodic monitoring of their levels in human systems is essential.
 Because of the absence, as well as excess, of biomolecules in human systems, people face
a number of biological disorders such as Alzheimer's disease, Parkinson's diseases,
diabetes, heart attack, pregnancy complications, osteoporosis, etc.
 This leads to a decrease in the average life-span of a living system.
 Therefore, the development of biosensors for the detection of bioanalytes is essential to find
out their levels in every human. Hence, disposable electrodes were tried for the detection of
various bioanalytes.
 As a result, it is observed that the pre-anodized SPE was found to be effective in yielding an
electrochemical signal with respect to the concentration of various bioanalytes including
ascorbic acid, uric acid and dopamine, in human blood samples.
 It is well documented that these disposable electrodes are able to produce responses against
uric acid in human blood samples in the presence of ascorbic acid.
  The results are well-correlated with the clinical serum analysis by the phosphotungstic acid
method.
 In addition, the electrodes were found to be an efficient candidate for the detection of
creatinine.
 They were further used to detect melamine, which is a poor electroactive compound. The
role of these electrodes were further extended towards glucose oxidase where the direct
electron transfer was improved.
 Disposable SPEs are also reported for their efficient electrocatalytic properties towards lactic
acid.

The Role of Disposable Electrodes in Pesticide Detection

 Besides the detection of biomolecules and food contaminants, the determination of

pesticides in soil and agro products is also vital.
 The development of agriculture and its technology began from the time of its birth. To
achieve improved cultivation, farmers started to use pesticides.
 In the past, farmers used organic manures, however later, they moved on to the use of
harmful synthetic/chemical pesticides.
 These fertilizers should only be used in minimal amounts (ppm/ppb level) but, are often used
in large quantities without caution.
 This has made agro-products unsafe for consumption where such large quantities of
synthetic pesticides are used.
 The accumulation of pesticides into the vegetables lead to a poisoning effect. These
synthetic pesticides also have a direct impact on the soil as well as the agro-products.
Continuous usage of the pesticides makes the soil uncultivable and provides poor-quality
vegetables and fruits causing a significant effect on human health.
 Pesticides in the cultivated agro-products can induce a number of diseases such as asthma,
diabetes, birth defects, reproductive dysfunction, etc. They do this by suppressing the activity
of many enzymes in the human system.
 Therefore, monitoring the level of pesticides in soil, water and cultivated agro-products is one
of the best ways to detect the abuse of pesticides.
 Enzyme modified SPEs are playing an extraordinary role in the detection of pesticides. The
immobilized enzymes interact with the substrates and leads to the formation of electroactive
species.
 Commonly affected enzymes are acetylcholinesterase (AChE), butyrylcholinesterase
(BChE), organo phosphorous hydrolase (OPH) Afterwards, the enzyme comes in to
contact with the inhibitors, and its activity is diminished.
 So, amperometric detection of pesticides depends on the reduced enzyme activity.
 The ability of the sensor platform depends on how the enzyme is immobilized.
 The methods involved in the immobilization are cross-linking, physical entrapment and sol–
gel.
 The main drawbacks associated with the methods are non-renewability of the electrode
surface and under harsh conditions, enzymes may get denatured.
 To overcome the problems researchers have been focused towards the application of
magnetic materials in pesticide sensors.
 This added an excellent improvement such as renewable electrode surface and better
microenvironment in the electrochemical sensing of pesticides.
 A platform containing hybrid core/shell biomagnetic glasses having Fe 3O4 and a silica shell
was used to immobilize AchE.
 A paraoxon sensor has been developed using SPE containing AchE.
 In addition to Fe3O4, Au containg Fe3O4 is also employed for the immobilization of AchE. The
resulting platform improves the stability of the matrix. E-coli immobilized SPEs were
successfully employed for the detection of methyl parathion.
 Cobalt phthalocyanine modified SPEs were used for the detection of organophosphate
pesticides.
Energy conversion and storage
Introduction
1. Conversion of chemical energy into electrical energy is the function involved in cells. One
of galvanic cells that convert chemical energy into electrical energy.
2. In general battery is a combination of galvanic cells neither in series (or) parallel both in
order to get the required amount of electrical energy.
3. Battery is a device which transforms chemical energy of a redox reaction into electrical
energy.
4. The conversion of chemical energy into electrical energy is the basis for the functioning of
galvanic cell.
5. Battery is a device that’s consists of two or more galvanic cells connected in series or
parallel or both which converts chemical energy into electrical energy through redox reactions.
Example: Zn-Air battery, lead acid battery, lithium batteries, etc.

Basic components of a battery

A battery consists of four major components. They are anode, cathode, electrolyte and
separator.
Diagram 7. Structure of a battery
 Anode:
The anode (-ve electrode) is oxidized during the electrochemical reaction and liberates electrons of the external
circuit.

M → Mn+ + e-
Metal
 Cathode:
The cathode (Positive electrode) is reduced during the electrochemical reaction which
accepts electrons from external circuit.
 Electrolyte:
The electrolyte which provide the medium for transfer of ions inside the cell between
the anode and cathode. The electrolyte must have good ionic conductivity and
resistance to the electrode materials.
 Separator:
The separator: the material that electronically isolates the anode and the cathode in a
battery to prevent internal short-circuiting.
Example: Cellulose, Vinyl polymer, Polyolefins
Classification of batteries

Batteries are classified

 Primary batteries
 Secondary batteries
 Reserve batteries

Primary batteries
1. In primary batteries, the chemical energy is converted into electrical energy as long as the
chemical components are active.
2. These batteries the reaction occurs only once and after that they must be discarded.
3. These batteries cannot be recharged as the chemical reactions which occur within the
primary batteries are irreversible.
Examples: Zn- air battery, Dry cell, Li- MnO2
Secondary batteries
1. Secondary batteries are those which after discharging can be recharged.
2. These batteries chemical reactions taking place are reversible
3. The redox reaction which converts chemical energy into electrical energy can be reversed
by passage of current.
4. The electric energy is stored in the form of chemical energy these batteries are also known a
storage cell.
Example: Lead storage battery, Nickel-cadmium battery, Nickel-metal hydride battery and
Lithium-ion battery.
Reserve Batteries
1. These batteries one of the components is isolated and incorporated into the battery when
required.
2. The electrolyte is the component that is isolated, but some water activated batteries contain
the electrolyte solute and water is added for activation.
3. They are used to deliver high power for relatively short periods of time in application such
as radiosondes (air borne instruments to send to meteorological information back to earth by
radio).Examples: Mg batteries activated by water (Mg-AgCl, Mg-CuCl), Zn-Ag2O batteries
etc
Sodium Battery
Construction, working and applications of modern batteries
Sodium–sulfur (NaS) Batterry
Construction,

(a) The composition of NaS batteries, sodium and sulphur are used as molten electrodes
in a liquid state

(b) The non-aqueous beta-alumina electrolyte is utilized as electrolyte and isolator.

(c) Sodium and sulphur are used as negative and positive electrodes, respectively.

(d) Long lifetime nearly 15 years, almost zero self-discharge rate i.e., 0.05%–1%,
good energy density such as 150–300 Wh/L, recyclability due to cheap battery
materials, and high energy efficiency are the main advantages of NaS batteries.

(e) This types of batteries suffer from some problems such as high operating
temperature, very corrosive nature of molten cathodes, and very high internal
resistance. So that any fracture in the electrolyte ceramic will eventually lead to flame
and battery explosion.

Working:

(a) During the discharge phenomena, Na+ ions are produced by the interface of sodium
(Na) and beta alumina, then Na+ ions pass through the solid electrolyte and are
recombined with sulphur at the anode.

(b) The reverse of this process occurs during the charging process of these batteries. In
general, the electrochemical reaction in a NaS can be described as follows

At cathode (oxidation):2Na→2Na++2e−

At anode (reduction):xS+2Na++2e−→Na2Sx

Overall: 2Na+xS→Na2Sx

Application of sodium ion battery:

 Sodium-ion batteries have shown great promise for large scale storage of renewable
energy.
 Sodium-ion batteries are cheaper and last longer than cell currently used in gadgets.
 These factors price, abundance and size, make sodium-ion batteries particularly
interesting for large scale grid storage application.
 Advantages of sodium ion battery

 Rechargeable sodium ion for energy storage.

 Easier to recycle
 Low market prices
 Capable of working at room temperature, good efficiency.
Dis advantages of sodium ion battery.
 Large ionic size Na+ which require more power to keep energy flowing.
 It takes seven days to charge in case you forget to charge it.
 Lower operating voltage.
 Need high temperature for optimal work.

Lithium ion Battery

 Diagram 9. Li-Ion battery The main attraction of Lithium as an anode material is;
a. It is the most electronegative metal in the electrochemical series.
b. It has largest amount of electrical energy per unit weight.
(But Lithium cannot be used with the traditional aqueous electrolytes;
* Corrosion, A vigorous reaction blw Li and water- Flammable H2 gas as the product)
1. Recharge lithium batteries are found in many cell phones, laptops and digital cameras,
2. They make use of lithium ions and are called lithium ion cells.
3. Lithium ion battery uses lithium intercalated metal oxide as cathode and lithium interactable
graphite as anode. Anode and cathode can insert lithium ions into their layered structures
reversible.
1. Anode: Graphite or carbon
2. Cathode: Lithium metal oxide (LiMnO2) LixCoCO2 /LixNiO2/LixMnO2
3. Electrolyte: A lithium salt such as LipF6, LiAsF6, LiClO4, LiBF4 dissolved in an organic solvent
such as ethylene carbonate dimethyl carbonate or dimethoxy ethane.
 4. Separator
Microporous polyethylene or poly propylene.
The operation of this cell does not actually involve true oxidation and reduction. The cell
reaction involves the migration of lithium ions between positive and negative electrodes.
Graphite being layered can be accommodated (or) intercalated with lithium between the atoms.
Mechanism:
During discharging Li-atoms present in the Graphite layer are oxidized and liberated electrons
and Li-ions. The electrons flow from anode to cathode through external circuit as well as Li-ions
move from anode to cathode through a separator.
At cathode Li-ions reduced to Li-atoms and are inserted into the layer structure of metal oxides.
The reverse reaction occurs during charging, the Li-ions move back to anode.
The cell can be represented as
Li ∣ Li+, C ∣ LiPF6(in ethylene carbonate) ∣ LiCoO2
The cell reaction during discharge or charging are:
At anode:

At cathode:

Overall reaction:

Reverse reaction occurs during charging. Thus, lithium ions move back and forth between anode
and cathode during charge and discharge.
It provides a potential of 3.7V
Advantages
 High energy density.
 Relatively low self-discharge.
 High cell voltage.
Applications
Cell phones Laptops LCD TV
Portable CD players.

Quantum dots sensitized solar cells

(QDSSC’s)- Principle, Properties and
Applications.
Introduction

 The solar photovoltaic market is one of the fastest developing energy

markets in the world.
 By 2030, the solar power industry will see a growth of a factor of 10.
 In order for solar energy to succeed, a new technology is required that
can provide superior efficiencies and lower the costs below standard
silicon PV panels.
 Quantum dot solar cells just might be that technology.

Definition quantum dot solar cell

 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.

 A new type of quantum dot could lead to cheaper solar cells and better
satellite communication
Construction and working Quantum dots

 Quantum dots are considered to be artificial atoms.

 Their energy levels are adjustable by altering their size, which in turn
delineates the band gap.
 The dots can be grown in a variety of sizes, allowing them to convey a
variety of band gaps without changing the underlying material or
construction.
 Sizing is achieved by varying the fusion duration or temperature.
 Because the band gap of the quantum dots can be adjusted, quantum
dots are desirable for solar cells.
 Frequencies in the far infrared that are characteristically difficult to
achieve with traditional solar cells can be obtained using lead sulfide
colloidal quantum dots.
 Half of the solar energy reaching the Earth is in the infrared region. A
quantum dot solar cell makes infrared energy as accessible as any other.
 Tiny nanocrystals—also known as quantum dots— yield 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 capitalizes 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.
 Structure and working of Quantum dot solar cell

 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.
Advantages of Quantum dot solar cells
The following are the benefits of quantum dot solar cells.

 They have a favourable power to weight ratio with high efficiency.

 The mass and area savings as well as flexibility leads to miniaturization.
 Their power consumption is low.
 There is an increase of electrical performance at low production costs.
 Their use is versatile and can be used in windows, not just rooftops.

Disadvantages of QDSC.
 There are some disadvantages of QDSC. Cadmium selenide-based
quantum dot solar cells are highly toxic in nature and require a very
stable polymer shell.
 Cadmium and selenium ions which are used in the core of quantum dots
are known to be cytotoxic.
 Quantum dot metabolism and degradation within a human body is still
chiefly unknown and studies have shown that quantum dots accumulate
in the kidney, spleen, and liver.

What is quantum dots and its application?

Quantum dots are colloidal fluorescent semiconductor Nano crystals,
roughly spherical and typically have unique optical, electronic and
photophysical properties that make them appealing in promising
applications in
 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