CHE Mod 1 Notes Cs
CHE Mod 1 Notes Cs
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.
Self-learning: Types of electrochemical sensor, Gas sensor - O2 sensor, Biosensor - Glucose sensors.
Sensors
Sensor is an object that detects signals from its surrounding environment and converts it to
meaningful or quantifiable information. Eyes, ears, and nose are all different types of sensors that help
you navigate your surroundings on a day-to-day basis by detecting and processing light, sound, and
smell/taste.
Conductometric sensors
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.
ductivity
Conductometric biosensors can measure the change of the specific conductance/electrical conductivity
of the analyte. 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.
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 (Figure). 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.
Electrochemical Sensors:
Principle:
• 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.
• Detection of important molecules or biomarkers that are used for the diagnosis of diseases and
disorders.
• They are used for the monitoring 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.
Thermometric Sensors
A temperature sensor is an electronic device that measures the temperature of its environment
and converts the input data into electronic data to record, monitor, or signal temperature changes. There
are many different types of temperature sensors. 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
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.
Optical sensors:
Optical sensors are electronic components designed to detect and convert incident light rays
into electrical signals. Eg: Colorimetric Sensors. Optical sensors are divided into several subclasses
such as resonance, dispersion, reflection, refraction, phosphorescence, infrared absorption, Raman
scattering, fluorescence, and chemiluminescence.
• 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. The transducer converts
intensity of absorbed light into electrical signal. The change in intensity at certain wavelength
within visible (400–800mm) range can be determined using special instrumentation.
• The relationship between the incident light intensity and the transmitted radiation is given by
the Beer-Lambert law:
𝐼0
𝐴 (𝜆) = log = 𝜀 (𝜆) ∙ 𝑑 ∙ 𝑐
𝐼
𝐼0
where 𝐴 (𝜆) = log is the absorbance at a given wavelength A, (𝐼0 and I are the incident and
𝐼
transmitted light intensities); 𝜀 is the molar absorptivity; d is the optical path through the
absorbing sample and c is the molar concentration of absorbing analyte.
• 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.
• Computers
• motion detectors.
• copy machines (xerox machines)
• light fixtures that turn on automatically in the dark.
• alarm systems
• synchro for photographic flashes
• systems that can detect the presence of objects.
The two methods for estimation of DO are optical method and electrochemical method.
(a) Optical method: 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 external reader is connected to a computer or data hub and is responsible
for sending and receiving optical signals to the sensor spot.
Working Principle
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 pressure 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.
1. Pharmaceuticals
a. for the analysis of diclofenac.
Carbon based-electrodes are the most investigated electrodes in diclofenac analysis. Carbon
nanotubes (CNTs) and graphene-based composites are the most efficient modifiers for diclofenac
detection that allowed the detection of diclofenac up to picomolar levels. CNT-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. The following are the
components:
The following are the components of the electrochemical sensor used for the detection of the
hydrocarbons-
Sulphur dioxide is one of the main substances that pollute the air. 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 attempt to
detect sulphur dioxide in the air is a regular task of air inspection.
Gas sensors detect chemicals in the gas phase. The gas sensors operate by reacting with the gas
of interest and producing an electrical signal proportional to the gas concentration. A typical
electrochemical sensor consists of: a sensing electrode (or working electrode), counter electrode
separated by a thin layer of electrolyte and a reference electrode. Gases diffuse through a membrane
to be reduced or oxidized at an electrode. Initially the gas passes through a small capillary-type opening
and then diffuses through a hydrophobic barrier, and eventually reaches the electrode surface. SOx
sensors utilizing a solid electrolyte such as K2SO4, Na2SO4, Li2SO4, Ag2SO4, Nasicon, Na-Al2O3 and
Applications:
Nitrogen oxide is the general term for a gas mixture composed of various oxides of nitrogen,
often referred as NOx. The normal air is nitric oxide and nitrogen dioxide. In environmental
analysis, nitrogen oxide generally refers to NO and NO 2. NO is an important vasodilator, and
monitoring its levels becomes crucial in the diagnostics of cardiovascular complications.
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.
The 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. The NO x 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
NO → NO+ + e-
NO+ + OH-→HNO2
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- ; Eo+0.222V
Disposable sensors: Disposable sensors are low-cost and easy-to-use sensing devices designed for
short-term or rapid single-point measurements.
• Depending on what electrochemical method is used, the current measured by the electrode or the
change in potential caused by the redox reaction occurring on the electrode, is directly proportional
to the concentration of a given sample. Example electrochemical oxidation of ascorbic acid and
oxidation of glucose.
Application of biosensors
b. Pesticides
To achieve improved cultivation in agricultural fields, farmers started to use large amount of
(more than prescribed ppm/ppb levels) harmful synthetic/chemical pesticides instead of organic
manure. These synthetic pesticides also have a direct impact on the soil as well as the agro-
products. The accumulation of pesticides into the vegetables lead to a poisoning effect. 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.
Working: 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. The following
are the components –
• 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.
Conversion of chemical energy into electrical energy is the function involved in cells. One of
galvanic cells that convert chemical energy into electrical energy. 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. Battery is a device which transforms chemical energy of a redox reaction into electrical energy.
Example: Zn-Air battery, lead acid battery, lithium batteries, etc. The following are the components of
batteries-
• 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 as (a) Primary, (b) secondary and (c) reserve batteries.
a. Primary batteries
In primary batteries, the chemical energy is converted into electrical energy as long as the chemical
components are active. These batteries the reaction occurs only once and after that they must be
discarded. These batteries cannot be recharged as the chemical reactions which occur within the
primary batteries are irreversible. Examples: Zn- air battery, Dry cell, Leclanche cell (Zn-MnO2), Li-
MnO2 battery, Magnesium cell (Mg- MnO2)
b. Secondary batteries
Secondary batteries are those which after discharging can be recharged. These batteries chemical
reactions taking place are reversible. The redox reaction which converts chemical energy into electrical
energy can be reversed by passage of current. The electric energy is stored in the form of chemical
energy these batteries are also known a storage cell. Examples: Lead storage battery, Nickel-cadmium
battery, Nickel-metal hydride battery and Lithium-ion battery.
These batteries one of the components is isolated and incorporated into the battery when required.
The electrolyte is the component that is isolated, but some water activated batteries contain the
electrolyte solute and water is added for activation. 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
Li-ion Battery
(a) cathode (positive electrode): e.g., LiCoO , LiFePO 4, Lithium manganese oxide, Nickel cobalt
aluminium, Lithium nickel manganese cobalt oxide
(b) anode (negative electrode): e.g., carbon or graphite which are contacted by an electrolyte
containing lithium ions. The electrodes are isolated from each other by a separator, typically
microporous polymer membrane, which allows the exchange of Li-ions between the two
electrodes but not electrons.
(c) Electrolyte: A lithium salt such as LiPF6, LiAsF6, LiClO4, LiBF4 dissolved in an organic solvent
such as ethylene carbonate dimethyl carbonate or dimethoxy ethane.
(d) Separator: Microporous polyethylene or polypropylene
• Li-ion batteries use a process known as intercalation, in which lithium ions are incorporated into
the structure of the electrode materials.
• Inside the cell, lithium ions move from the positive to the negative electrode during charging and
from the negative to the positive electrode as the battery is discharged.
• In this way the external energy are electrochemically stored in the battery in the form of chemical
energy in the anode and cathode materials with different chemical potentials.
• Electrons move through an external circuit in the same direction as the lithium ions, driven by an
external charger (when charging) or by the stored potential chemical energy (available to drive a
load) when the battery is discharging.
The Li-ion cell is represented as: LiLi+, C LiPF6 (in ethylene carbonate)LiCoO2
Advantages:
Disadvantages:
Applications:
a. electric-powered vehicles
b. buffer the intermittent and fluctuating green energy supply from renewable resources, such as
solar and wind
c. grid application
d. cell phones
e. powering hybrid electric vehicles (HEVs)
f. plug-in hybrid electric vehicles (PHEVs)
g. electric vehicles (EVs)
Na-ion Battery
Construction and Working:
(a) Anode materials (negative electrode): carbon-based (hard-carbon), transition metals, and their
alloy compounds.
It stores energy in the chemical bonds of anode. When battery is recharging sodium ions moves from
cathode to the anode. Meanwhile charge balancing electrons pass from the cathode through the external
circuit containing the charger and into the anode During discharge process electrons move from and
anode to external circuit, it can be used for various applications. Meanwhile, Na+ ions move from
anode to the cathode. Voltage obtained from every sodium ion cell is 3.6 V. The electrode reactions
are as follow,
The NaCoO2 cathode, like LiCoO2, is initially brought into the Na-ion cell in the discharged state, and
the cell is activated by charging first to form the Na intercalated anode and Na deintercalated cathode
in the fully charged cell.
Advantages
Disadvantages:
Applications:
a. Power backup: Data and telecom sectors heavily rely on battery powered infrastructures and
operations to drive to the global economy. Na-ion batteries can provide on demand power to
ensure safe and seamless power supply.
b. Automobiles and Transportation: In electric vehicles including electric cars and buses.
c. Grid-level applications: Na-ion batteries can help optimise the solar and wind energy to meet
grid energy storage requirements.
d. Industrial mobility: Na-ion batteries can maximize asset utilization and minimize operating
cost with constant state of readiness and powerful peak power.
Principle: Upon light irradiation, the sensitizer is photoexcited. The excited electrons of QDs are
injected into the conduction band of the TiO2. The electrons penetrate through the nanocrystalline TiO2
film to the back contact of the conducting substrate, and flow through an external circuit to the CEs.
At the CEs, the oxidized component of redox couple in the electrolyte is reduced. The oxidized form
of the sensitizer is finally regenerated by the reduced component of redox couple in the electrolyte.
The external load is connected to the cell to complete the circuit through electron migration. When the
cell is irradiated with sunlight, the potential difference between the photo-electrode (due to the Fermi
level of the electrons) and electrolyte (due to the redox potential) produces a voltage across the load,
and the solar energy conversion efficiency (η) of the cells is obtained as follow.
Jm • Vm • FF
𝜂=
𝑃
where P is the power density at the operating point, and J m and Vm represent current density and
voltage, respectively, at the actual maximum power.
(a) Photoanode: Photoanode usually consists of semiconducting metal oxide deposited on a transparent
conducting oxide substrate. Eg: Metal oxide electron-transporting/acceptor materials (TiO2, ZnO,
ZrO2, PbS-based photoanodes)
(b) QD sensitizers: To maximize the harvesting efficiency of the incident light, it should possess a high
absorption coefficient and appropriate band-gap energy. Eg: ZnS, ZnSe, Ag2S, Bi2S3, CdS, CdSe,
CdTe, InAs, In2S3, InP, PbS, PbSe, Si, Graphene, Cu-ZnS, and halides
(c) Counter electrodes (CE): transfers electrons from the external circuit into electrolyte and catalyses
the reduction reaction of the oxidized electrolytes at the electrolyte/CE interface. Eg: Noble metals
(Pt), Metal chalcogenides, Carbon materials (graphene, carbon fiber, carbon black, multiwalled
carbon nanotubes)
(d) Electrolyte: Redox electrolytes enhances the efficiency and stability of QDSSCs. It is a medium
which transfers charges between counter electrodes and photoanodes for the regeneration of
oxidized QDs. Eg: iodide/triiodide (I-/I3-) electrolyte
Advantages of QDSCCs: The following are the benefits of quantum dot solar cells.
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.
Applications: