UNIT IV CHEMICAL SENSOR 9

Sensors, sensor science and technology, types of sensors. Chemical Sensors - characteristics of a
chemical sensor, elements of chemical sensors. Electro chemical sensors – voltammetry,
potentiometric sensors, amperometric sensors, polarization techniques.

1. Sensors, sensor science and technology

2. Sensor Characteristics & Types of Sensors
3. Chemical sensors
4. Breathalyzer: Chemistry of breathalyzer Breathalyzer sensors Characteristics of a
Chemical Sensor

5. Electrochemical sensors, Principles, Characteristics of electrochemical sensors &

Application of electrochemical sensors

6. Voltammetry, Current In Voltammetry, Sign Conventions The types of voltammetry

7. Cyclic voltammetry, The Three Electrode System & Instrumentation
8. Differential pulse voltammetry – Polarography & Definition of Electric Polarization
9. Potentiometric sensor, Classification & Application. Amperometry andt its Application.

A sensor is a device that produces an output signal for the purpose of sensing a physical
phenomenon.

Sensors are practical devices and, as such, activities are both fundamental and applied.
Also, understanding sensor devices requires some knowledge of a variety of academic
areas. This leads to a very interdisciplinary field populated by physicists, chemists,
engineers, biologists and biochemists, materials scientists, electrochemists, and others.

Sensors science and engineering is relevant to virtually all aspects of life including safety,
security, surveillance, monitoring, and awareness in general. Sensors are central to
industrial applications being used for process control, monitoring, and safety. Sensors are
also central to medicine being used for diagnostics, monitoring, critical care, and public
health.
A bubble and block diagram illustrating the contributing fields of sensor science

The five fundamental senses of the human body are touch, sight, hearing, smell, and taste.
To understand and perceive the world around us, the detecting organs connected to each
sense transmit data to the brain. However, in addition to the basic five senses, humans also
possess additional senses that are essential for survival. These lesser-known senses
include balance and spatial awareness. This is how the human senses function.

For a long-term vision that includes intelligent systems that are self-monitoring, self-
correcting and mending, and self-modifying or morphing, similar to sentient humans, the
seed technologies are now being developed. The development of a system's ability to see
(photonics), feel (physical measures), smell (electronic noses), hear (ultrasonics),
think/communicate (smart electronics and wireless), and move (sensors integrated with
actuators) is advancing quickly, pointing to an exciting future for sensors.

Sensor Characteristics:
The static accuracy of a sensor indicates how much the sensor signal correctly represents
the measured quantity after it stabilizes (i.e. beyond the transient period.)
Important static characteristics of sensors include sensitivity, resolution, linearity, zero drift
and full-scale drift, range, repeatability and reproducibility.

 Resolution is the smallest amount of change in the input that can be detected and
accurately indicated by the sensor.

 Linearity is determined by the calibration curve. The static calibration curve plots the
output amplitude versus the input amplitude under static conditions. Its degree of
resemblance to a straight line describes the linearity.

 Drift is the deviation from a specific reading of the sensor when the sensor is kept at
that value for a prolonged period of time. The zero drift refers to the change in sensor
output if the input is kept steady at a level that (initially) yields a zero reading.
Similarly, the full -scale drift is the drift if the input is maintained at a value which
originally yields a full scale deflection. Reasons for drift may be extraneous, such as
changes in ambient pressure, humidity, temperature etc., or due to changes in the
constituents of the sensor itself, such as aging, wear etc.
  The range of a sensor is determined by the allowed lower and upper limits of its input
or output. Usually the range is determined by the accuracy required. Sometimes the
range may just be determined by physical limitations. Example: a pocket ruler.

 Repeatability is defined as the deviation between measurements in a sequence when

the object under test is the same and approaches its value from the same direction
each time. The measurements have to be made under a short enough time duration
so as not to allow significant long term drift. Repeatability is usually specified as a
percentage of the sensor range.

 Reproducibility is the same as repeatability, except it also incorporates long time

lapses between subsequent measurements. The sensor has to be operation between
measurements, but must be calibrated. Reproducibility is specified as a percentage
of the sensor range per unit of time.

The dynamic characteristics of a sensor represent the time response of the sensor system.
Knowledge of these is essential to fruitfully use a sensor. Important common dynamic
responses of sensors include rise time, delay time, peak time, settling time percentage error
and steady-state error. Rise time is the time it takes a sensor to pass between 10% to 90%
of the steady state response.

 Delay time is the time it takes to reach 50% of the steady state value for the first time.
 Peak time is the time it takes to reach the maximum reading for the first time for a
given excitement.
 Settling time is the time it takes the sensor to settle down to within a certain
percentage of the steady state value.
 The percentage overshoot is a measure of the peak minus the steady state value,
expressed as a percentage of the ssv.
 Steady-state error is the deviation of the actual steady-state value from the desired
value. It can be corrected by calibration.
 Two other terms are used to describe sensor behavior, and shall be described here.
These are accuracy and precision.
 The accuracy of a system is the difference between the actual and the measured
value. The distinction between accuracy and resolution is important. While resolution
is the smallest change in measurement value that can be indicated, the accuracy is
determined by the actual indication of the sensor and the real value of the measured
entity. Thus while resolution depends solely on the sensor hardware, the accuracy is
a function of the sensor hardware as well as the measurement environment and
other extraneous factors that modify the sensor behavior.
 The precision is a statistical measure. It is usually indicated by the standard deviation
(or variance) of a set of readings of the sensor for the same input. The distinction
between accuracy and precision is clarified by the following figure.
Illustration of Accuracy and Precision. The center of the target represents the desired 'true'
value.

Future of sensor technology

Sensors can improve the world through diagnostics in medical applications; improved
performance of energy sources like fuel cells and batteries and solar power; improved health
and safety and security for people; sensors for exploring space and the known university;
and improved environmental monitoring.

The human senses in their COMETMAN environment

'Technology push' and 'market pull' are combining to direct modem and future
instrumentation towards miniaturisation, distribution and intelligence.

There is a growing interplay between a range of technologies:

 micro-electronics/micro-computers (smart devices, intelligent systems),

 semi-conductor/solid-state,
 opto-electronics/laser and fibre optics,
 acoustics/ultrasonics,
 micromechanics,
 nanometrology,
 thin- and thick film technologies, with supporting modelling,
 materials science,
 signal information processing and
 learning systems.

The technical opportunities for integrated systems are great; the demands are immense for
instrumentation to provide safer, more accurate and reliable operation, and to meet
requirements for measurement of inaccessible or difficult physical, chemical and biological
variables.

As a consequence of the competitive need of industry to be highly efficient and quality

conscious, manufacturing metrology now increasingly requires automatic inspection
methods off-line, in-cycle and in-line, and utilising micro-electronics, computer (hardware
and software) and novel optical techniques. Suitable sensing techniques, sensors and
transducers are essential to this developing situation. Improvements and advances in all
fields require improved and new sensors, and notably in the following industries: aerospace,
automotive, food, pharmaceutical, medical, chemical, energy, environment and transport
industries. It will be evident that the technical scope for instrumentation is immense. At
present, over 100 properties can be detected by sensors and almost 200 technology areas
are being applied to sensor developments. In the mid1980s, over 100,000 commercially
available sensors were identified worldwide.

Types of Sensors

There are many different types of sensors, the main categories are;

 Position Sensors
 Pressure Sensors
 Temperature Sensors
 Force Sensors
 Vibration Sensors
 Piezo Sensors
 Fluid Property Sensors
 Humidity Sensors
 Strain gauges
 Photo Optic Sensors
 Flow and Level Switches
These categories can all be split further into subcategories for example, within position
sensors there are the following types;

 Contacting
 Non-contacting
 Rotary
 Linear

And these types of sensors can be split even further, within non-contacting you have the
following types of sensors;

 Hall effect
 Capacitive
 Eddy Current
 Ultrasonic
 Laser
 Proximity

By splitting one category – Position Sensors it is clear to see that the number of sensors
present in today’s world is so vast that one blog post could not cover every type of sensor.
However, here is an overview of different types of sensors Variohm can offer.
Chemical sensors

Chemical sensors have a chemical or molecular target to be measured.

A chemical sensor is a device that measures and detects chemical qualities in an analyte
(the scientific term for a chemical substance being observed) and converts the sensed
chemical data into electronic data. Chemical sensors are used in myriad applications, such
as medical, automotive, nanotechnology and home detection systems (i.e. carbon monoxide
detectors).

Classification of chemical sensors based on sensing objects.

There are many different types of chemical sensors—which are specifically designed for
their intended functions)—but they all share two components: receptors and transducers.
The receptor is the component of the chemical sensor that comes into physical contact with
the analyte. Depending on the sensor, the receptor interacts with the analyte in distinct
ways. For instance, some receptors trigger chemical reactions with the analyte as a whole,
while others can single out specific molecules. The latter (sensors that target molecules in
an analyte) are referred to as more “selective.”

The chemical sensor is an analyzer that responds to a particular analyte in a selective and
reversible way and transforms input chemical quantity, ranging from the concentration of a
specific sample component to a total composition analysis, into an analytically electrical
signal, as depicted in below Figure. The chemical information may originate from a chemical
reaction by a biomaterial, chemical compound, or a combination of both attached onto the
surface of a physical transducer toward the analyte. The chemical sensor subject is an
emerging discipline formed by the multidisciplinary study among chemistry, biology,
electricity, optics, mechanics, acoustics, thermology, semiconductor technology,
microelectronics technology, and membrane technology.
Schematic diagram of a sensor that produces an electrical output in response to the
presence of an input quantity.

Chemical Sensor Diagram

The second component held in common with all chemical sensors is the transducer.
Transducers are responsible for intaking the chemical information of the interaction between
the receptor and analyte and converting it into corresponding electrical information. This
information is then sent to a computer or a mechanical component. The transducer may
increase or decrease resistance, trigger an audible alarm, or present the data on a screen
(interface).

Breathalyzer:

A perfect example of a commonly used chemical sensor in action is a breathalyzer. When

people consume alcohol, they exhale an amount of alcohol molecules directly proportional to
the amount they drink. A breathalyzer is a chemical sensor that is specifically designed to
measure a person's blood alcohol content (BAC), often to determine whether or not they are
safely capable of driving a vehicle. When the alcohol molecules interact with the receptor,
they encounter another chemical substance contained in the receptor (namely: sulfuric acid,
potassium dichromate, silver nitrate and water). This triggers a chemical reaction, and when
the chemical difference between the two chambers (one not affected by the reaction) is
perceived, an electric signal is produced and it indicates via screen or needle the suspect’s
BAC.

A breathalyzer or breathalyser (a portmanteau of breath and analyzer/analyser) is a device

for estimating blood alcohol content (BAC), or to detect viruses or diseases from a breath
sample.
The name is a genericized trademark of the Breathalyzer brand name of instruments
developed by inventor Robert Frank Borkenstein in the 1950s

The most standard alcohol breath test is performed using a breathalyzer. This device is
made up of two vials composed of a photocell indicator and a series of chemicals that work
together to calculate blood alcohol concentration (BAC). A mouthpiece is attached to the
breathalyzer, that allows the suspect to blow into the device. During a routine breath test, the
breath passes through the vessel to the measurement component of the detector and
collects into a vial containing sulfuric acid, potassium dichromate, silver nitrate, and water.

Chemistry of breathalyzer
A photocell system is then applied to compare the amount of unreacted potassium
dichromate left in the vial to the amount of the same chemical used to oxidize ethanol, which
will provide a measurement of alcohol content from the breath sample. The photocell system
bases its alcohol content measurement on the absorption of light by the potassium
dichromate. The amount of light absorbed by this chemical will be proportional to the amount
of alcohol in the sample cell.

Comparing the reference sample in the breathalyzer and the suspect sample generates an
electrical current that moves a needle on an indicator meter. One of the main problems with
this test is that it consumes the chemicals in the reaction vessel, implying a constant need to
calibrate the device and replenish it with the right amount of chemicals to oxidize ethanol so
that an accurate reading of alcohol concentration can be produced.

When the user exhales into a breath analyzer, any ethanol present in their breath is oxidized
to acetic acid at the anode:

C2H5OH(g) + H2O(l) → CH3COOH(l) + 4H+(aq) + 4e−

At the cathode, atmospheric oxygen is reduced:

O2(g) + 4H+(aq) + 4e− → 2H2O(l)

The overall reaction is the oxidation of ethanol to acetic acid and water.

C2H5OH(l) + O2(g) → CH3COOH(aq) + H2O(l)

Preparing the acidified dichromate mixture

 Wearing disposable nitrile gloves and eye protection, weigh out into a beaker
sufficient potassium dichromate crystals to half-fill the U-tube (about 30 g).
 Add dilute sulfuric acid (2 M) to the crystals in the beaker, in the ratio 1 cm3 of acid to
10 g of dichromate. Mix thoroughly, using a glass rod or spatula, to produce
moistened crystals of potassium dichromate.
 Half-fill the U-tube with the crystals, tapping the tube gently to pack them down.
 Place ethanol in the conical flask to such a depth that the longer of the glass tubes is
below the surface of the ethanol and the shorter one is not. Fit the longer tube with a
sterile mouthpiece consisting of a short length of clean glass tubing attached by
means of rubber tubing.
 Attach a plastic sandwich bag to the large, one-holed, rubber bung by gathering the
neck of the bag around the bung and binding it tightly with a cable tie or using thread.
Model an early ‘breathalyser’ test using acidified potassium dichromate in this demonstration
featuring the same reaction with ethanol
Procedure
1. Ensure the plastic bag is deflated at the start. Before connecting the flask to the U-tube,
blow air by mouth through the ethanol so that the air in the flask is saturated with ethanol
vapour.
2. Connect the conical flask, U-tube and plastic bag as shown in the diagram, and place a
white background behind to make the colour changes easier to see. A sample of unreacted
potassium dichromate(VI) is useful for comparison as the reaction proceeds.
3. Blow gently into the ethanol-containing flask so that the air bubbles steadily through the
ethanol, passes over the acidified potassium dichromate(VI), and into the plastic bag.
4. The dichromate(VI) crystals in the arm of the U-tube nearest the ethanol will turn brown.
This is caused by a mixture of unreacted orange crystals and a green chromium(III)
compound, a product of the reaction. The quantities of reagents are such that one bagful of
air will not be sufficient to complete the reaction.
5. To produce a complete change from orange to green, remove the bag, and connect a filter
pump in its place so that air containing ethanol vapour is drawn slowly over the crystals for
several minutes, until sufficient green colour is visible.
6. Disconnect the U-tube and remove the stoppers. Pass it round the class for the students
to smell the products of the reaction. Compare with the smells of small samples of ethanal
and ethanoic acid solution, both possible products of the reaction, by passing around
specimen tubes containing a wooden splint or filter paper strip dipped into the relevant liquid.

The reaction could also be demonstrated in a test tube before or after the ‘breathalyser’
demonstration. Advanced students may carry out the test tube reaction themselves as part
of their study of the properties of alcohols.

Depending on the wider context of the lesson, this could be a suitable opportunity to discuss
the dangers of drinking and driving, although modern ‘breathalysers’ use electronic methods
to detect and measure alcohol concentration.

When users exhale into a breathalyzer, traces of ethanol react with sulfuric acid and
potassium dichromate. These are then oxidized into chromium sulfate and acetic acid. The
silver nitrate in the vial catalyzes this chemical reaction:
2 K2Cr2O7 [Potassium dichromate] + 3 CH3CH2OH [Ethyl alcohol] + 8 H2SO4 [Sulfuric acid] +
2 Cr2(SO4)3 [Chromium sulfate Green]+ 2 K 2SO4 [Potassium sulfate] + 3CH3COOH [Acetic
acid]+ 11 H2O

The ionic equations for the reactions occurring are:

1. For oxidation of ethanol to ethanal:

Cr2O72– + 3C2H5OH + 8H+ → 2Cr3+ + 3CH3CHO + 7H2O

2. For oxidation of ethanol to ethanoic acid:

2Cr2O72– + 3C2H5OH + 16H+ → 4Cr3+ + 3CH3COOH + 11H2O

Breathalyzer sensors
 Photovoltaic assay: The photovoltaic assay, used only in the dated photoelectric
intoximeter, is a form of breath testing rarely encountered today. The process works
by using photocells to analyze the color change of a redox (oxidation-reduction)
reaction. A breath sample is bubbled through an aqueous solution of sulfuric acid,
potassium dichromate, and silver nitrate. The silver nitrate acts as a catalyst, allowing
the alcohol to be oxidized at an appreciable rate. The requisite acidic condition
needed for the reaction might also be provided by the sulfuric acid. In solution,
ethanol reacts with the potassium dichromate, reducing the dichromate ion to the
chromium (III) ion. This reduction results in a change of the solution's color from red-
orange to green. The reacted solution is compared to a vial of non-reacted solution
by a photocell, which creates an electric current proportional to the degree of the
color change; this current moves the needle that indicates BAC.[45] Like other
methods, breath testing devices using chemical analysis are prone to false readings.
Compounds that have compositions similar to ethanol, for example, could also act as
reducing agents, creating the necessary color change to indicate increased BAC.

 Infrared spectroscopy: Infrared breathalyzers allow a high degree of specificity for

ethanol. Typically evidential breath alcohol instruments in police stations will work on
the principle of infrared spectroscopy.

 Fuel cell: Fuel cell gas sensors are based on the oxidation of ethanol to
acetaldehyde on an electrode. The current produced is proportional to the amount of
alcohol present. These sensors are very stable, typically requiring calibration every 6
months, and are the type of sensor usually found in roadside breath testing devices.

 Semiconductor: Semiconductor gas sensors are based on the increase in

conductance of a tin oxide layer in the presence of a reducing gas such as vaporized
ethanol.[46] They are found in inexpensive breathalyzers and their stability is not as
reliable as fuel cell instruments.

Characteristics of a Chemical Sensor

The term ‘chemical sensor’ stems not merely from the demand for artificial sensing organs.
Indeed, chemical expertise was necessary to design chemical sensors. Such expertise is the
subject of analytical chemistry in its modern, instrumental form. Initially, chemists hesitated
to deal with sensors, but later their interest in them grew. The field of chemical sensors has
been adapted and is now largely considered a significant subdiscipline of analytical
chemistry

The attribute of reversibility is considered important by many authors. It means that sensor
signals should not ‘freeze’ but respond dynamically to changes in sample concentration in
the course of measurement.

The following characteristics of chemical sensors are generally accepted. Chemical sensors
should:
 Transform chemical quantities into electrical signals,
 Respond rapidly,
 Maintain their activity over a long time period,
 Be small,
 Be cheap,
 Be specific, i.e. they should respond exclusively to one analyte, or at least be
selective to a group of analytes.

The above list could be extended with, e.g., the postulation of a low detection limit, or a high
sensitivity. This means that low concentration values should be detected. Classification of
sensors is accomplished in different ways. Prevalent is a classification following the
principles of signal transduction (IUPAC 1991).

The following sensor groups result:

 Optical sensors, following absorbance, reflectance, luminescence, fluorescence,
refractive index, optothermal effect and light scattering
 Electrochemical sensors, among them voltammetric and potentiometric devices,
chemically sensitized field effect transistor (CHEMFET) and potentiometric solid
electrolyte gas sensors Electrical sensors including those with metal oxide and
organic semiconductors as well as electrolytic conductivity sensors
 Mass sensitive sensors, i.e. piezoelectric devices and those based on surface
acoustic waves
 Magnetic sensors (mainly for oxygen) based on paramagnetic gas properties
 Thermometric sensors based on the measurement of the heat effect of a specific
chemical reaction or adsorption which involves the analyte
 Other sensors, mainly based on emission or absorption of radiation Alternative
classification schemes do not follow the principles of transduction but prefer to follow
the appropriate application fields or receptor principles. In this way is the large and
important group of biosensors defined.

Elements of Chemical Sensors

The functions of a chemical sensor can be considered to be tasks of different units. This is
expressed typically in statements like the following (IUPAC 1999): Chemical sensors usually
contain two basic components connected in series: a chemical (molecular) recognition
system (receptor) and a physicochemical transducer. In other documents, additional
elements are considered to be necessary, in particular units for signal amplification and for
signal conditioning. A typical arrangement is outlined in Fig.
In the majority of chemical sensors, the receptor interacts with analyte molecules. As a
result, its physical properties are changed in such a way that the appending transducer can
gain an electrical signal. In some cases, one and the same physical object acts as receptor
and as transducer. This is the case e.g. in metallic oxide semiconductor gas sensors which
change their electrical conductivity in contact with some gases.
Conductivity change itself is a measurable electrical signal. In mass sensitive sensors,
however, receptor and transducer are represented by different physical objects. A
piezoelectric quartz crystal acts as transducer. The receptor is formed by a sensitive layer at
the crystal surface. The latter is capable of absorbing gas molecules. The resulting mass
change can be measured as a frequency change in an electrical oscillator circuit.
Receptor: The receptor function is fulfilled in many cases by a thin layer which is able to
interact with analyte molecules, catalyse a reaction selectively, or participate in a chemical
equilibrium together with the analyte.
Transducer: Today, signals are processed nearly exclusively by means of electrical
instrumentation. Accordingly, every sensor should include a transducing function, i.e. the
actual concentration value, a non-electric quantity,must be transformed into an electric
quantity—voltage, current or resistance.
 Energy-Conversion Transducers The principle of energy conversion means that
electrical energy is produced by the sensor. Many of these kinds of sensors are able
to operate without external supply voltage.
 Limiting-Current Transducers Voltage sources can reach a limiting state if they are
short circuited.
 Resistive Transducers In many cases, electrically conducting materials change their
conductivity (or, in other words, their resistivity) when environmental properties
change.
ELECTROCHEMICAL SENSORS

Electrochemical sensors are made on the basis of ion conduction. According to the
formation of their electrical characteristics, electrochemical sensors can be divided into
potential sensors, conductivity sensors, electricity sensors, polarographic sensors, and
electrolytic sensors. Electrochemical sensors are mainly used to analyze gas, liquid, or solid
components dissolved in liquids, the measurement of liquid pH, conductivity, and oxidation-
reduction potential.
With the development of electronic technology and detection technology, various types of
sensors are increasingly used in various industries. Sensors based on electrochemical
principles have been widely used in the detection of harmful gases in chemical, coal,
environmental protection, and health departments. Because electrochemical sensors can
respond to a variety of harmful gases and are simple in structure and low-cost, they have
shown an important position in the detection of harmful gases.

Principles of electrochemical sensors

The so-called electrochemical sensor means that when the measured gas enters the sensor,
an electrochemical reaction occurs inside it, thereby converting the measured gas side
content into a current (or voltage) signal output. However, even if the sensor is in clean
ambient air, the output signal of the sensor is often not zero. Normally, this kind of current
signal is called a background current or initial current. This is a randomly changing signal,
and its instability is firstly affected by temperature changes and secondly related to the
action time. The value is sometimes tens of times larger than the detected signal. Therefore,
eliminating the influence of the sensor background current is an important part of improving
the measurement accuracy, and we must pay attention to it.

There are many ways to eliminate the influence of the background current of the
electrochemical sensor. In some pocket-sized and portable harmful gas detectors, hardware
compensation methods are usually used, that is, an appropriate compensation circuit is
added to the detection circuit of the sensor.

The electrochemical sensor works by reacting with the measured gas and generating an
electric signal proportional to the gas concentration. A typical electrochemical sensor
consists of a sensing electrode and a counter electrode and is separated by a thin
electrolytic layer.

Electrochemical sensor structure diagram

The gas first reacts with the sensor through the tiny capillary-shaped opening, then the
hydrophobic barrier layer, and finally reaches the electrode surface. Using this method can
allow an appropriate amount of gas to react with the sensing electrode to form a sufficient
electrical signal while preventing electrolytes from leaking out of the sensor.

The gas diffused through the barrier reacts with the sensing electrode, and the sensing
electrode can adopt an oxidation mechanism or a reduction mechanism. These reactions are
catalyzed by electrode materials designed for the gas being measured.

Through the resistor connected between the electrodes, a current proportional to the
concentration of the gas to be measured will flow between the positive electrode and the
negative electrode. The gas concentration can be determined by measuring this current.
Because of the electric current generated in this process, electrochemical sensors are often
called current gas sensors or micro fuel cells.

In practice, due to the continuous electrochemical reaction on the surface of the electrode,
the potential of the sensing electrode cannot be kept constant. After a long period of time, it
will cause the performance of the sensor to degrade. In order to improve the performance of
the sensor, a reference electrode was introduced.

The reference electrode is installed in the electrolyte, adjacent to the sensing electrode. A
fixed stable constant potential acts on the sensing electrode. The reference electrode can
maintain this fixed voltage value on the sensing electrode. No current flows between the
reference electrodes. The gas molecules react with the sensing electrode and the counter
electrode is measured at the same time. The measurement result is usually directly related
to the gas concentration. The value of the voltage applied to the sensing electrode can make
the sensor target the target gas.

Composition of electrochemical sensors

The electrochemical sensor contains the following main components:

A. Breathable membrane (also called hydrophobic membrane): The breathable membrane

is used to cover the sensing (catalytic) electrode, and in some cases, it is used to control the
molecular weight of the gas reaching the electrode surface. Such barriers are usually made
of low-porosity Teflon films. This type of sensor is called a coated sensor. Alternatively, it
can be covered with a high-porosity Teflon film, and the molecular weight of the gas
reaching the electrode surface can be controlled with a capillary tube. This type of sensor is
called a capillary sensor. In addition to providing mechanical protection for the sensor, the
membrane also has the function of filtering out unwanted particles. In order to transmit the
correct gas molecular weight, the correct membrane and capillary pore size must be
selected. The pore size should allow a sufficient amount of gas molecules to reach the
sensing electrode. The pore size should also prevent leakage or rapid drying of the liquid
electrolyte.

B. Electrode: The choice of electrode material is very important. The electrode material
should be a catalytic material that can perform semi-electrolytic reactions over a long period
of time. Generally, electrodes are made of precious metals, such as platinum or gold, which
react effectively with gas molecules after catalysis. Depending on the design of the sensor,
the three electrodes can be made of different materials to complete the electrolysis reaction.

C. Electrolyte: The electrolyte must be able to carry out the electrolysis reaction and
effectively transfer the ionic charge to the electrode. It must also form a stable reference
potential with the reference electrode and be compatible with the materials used in the
sensor. If the electrolyte evaporates too quickly, the sensor signal will weaken.

D. Filter: Sometimes a scrubber filter is installed in front of the sensor to filter out unwanted
gas. The selection of filters is limited, and each filter has a different degree of efficiency. The
most commonly used filter material is activated carbon. Activated carbon can filter out most
chemical substances, but not carbon monoxide. By choosing the right filter material, the
electrochemical sensor can have a higher selectivity for its target gas.

Characteristics of electrochemical sensors

There are many ways to manufacture electrochemical sensors, ultimately depending on the
gas to be detected and the manufacturer. However, the main characteristics of the sensors
are very similar in nature. Here are some common characteristics of electrochemical
sensors:

1. On a three-electrode sensor, a jumper wire is usually used to connect the working

electrode and the reference electrode. If it is removed during storage, it will take a long time
for the sensor to remain stable and ready for use. Some sensors require a bias voltage
between the electrodes, and in this case, the sensor is shipped with a nine-volt battery-
powered electronic circuit. It takes 30 minutes to 24 hours for the sensor to stabilize and
three weeks to continue to remain stable.

2. Most toxic gas sensors require a small amount of oxygen to maintain normal function.
There is a vent hole on the back of the sensor for this purpose. It is recommended to
perform a recheck with the manufacturer in applications where a non-oxygen background
gas is used.

3. The electrolyte of the battery in the sensor is a water solvent, which is isolated by a
hydrophobic barrier, which has the function of preventing the leakage of the water solvent.
However, like other gas molecules, water vapor can pass through a hydrophobic barrier.
Under conditions of high humidity, prolonged exposure may cause excessive moisture
accumulation and cause leakage. In low humidity conditions, the sensor may dry out. The
sensor designed to monitor high-concentration gas has a lower porosity barrier to limit the
molecular weight of the gas passing through, so it is not affected by humidity. Like the
sensor used to monitor low-concentration gas, this sensor has a higher porosity barrier and
allows gas molecules to flow freely.

Advantages and disadvantages of electrochemical sensors

1. Advantages of electrochemical sensors
The use of electrochemical sensors can accurately measure some odors, analyze proteins,
and can also be used for new drug development and disease treatment. These are all
possible. And the detection speed is relatively fast, very simple, convenient. The most
important thing is that the cost is relatively low, and it can be used in conjunction with other
technologies, so electrochemical sensors have become a research hotspot. Electrochemical
sensors are useful in many aspects, such as medicine and industrial analysis.

2. Disadvantages of electrochemical sensors

The main disadvantage of electrochemical sensors is that they have a short lifespan. They
usually need to be replaced every one to three years. Of course, this is not all of them. It
also depends on the brand and the environment in which it is used. If the protection is good,
the lifespan can be extended. of. Also, some brands use electrolytic solutions. If you use an
electrolytic solution, you need to replenish it regularly, which is a bit troublesome. However,
there are many advantages of electrochemical sensors, so there are still many people who
will buy electrochemical sensors.

Application of electrochemical sensors

1. Humidity sensor
Humidity is an important indicator of the air environment. There is a close relationship
between the humidity of the air and the heat of evaporation of the human body. When in an
environment of high temperature and high humidity, the human body feels stuffy due to the
difficulty of evaporating water from the human body. When in an environment of low
temperature and high humidity, the heat dissipation process of the human body is intense.
The most suitable temperature for the human body is 18~22℃, and the relative humidity is
35%~65%RH. In environmental and sanitation monitoring, it is often used to measure air
humidity with instruments such as wet bulb thermometers and hygrometers, hand-operated
wet thermometers, and ventilation and humidity thermometers. In recent years, a large
number of literature reports using sensors to measure air humidity. The sensor used to
measure relative humidity is coated with piezoelectric quartz crystal, which is made of small
quartz crystal by photolithography and chemical etching technology. The AT-cut 10MHZ
quartz crystal is coated with 4 substances, which has a high humidity Quality sensitivity. The
crystal is a resonator in an oscillating circuit. Its frequency changes with quality. Choosing an
appropriate coating, the sensor can be used to determine the relative humidity of different
gases. The sensor's sensitivity, response linearity, response time, selectivity, Hysteresis,
and service life depend on the nature of the coating chemicals.

2. Nitrogen oxide sensor

Nitrogen oxide is the general term for a gas mixture composed of various oxides of nitrogen,
often expressed as NOX. Among nitric oxide, the chemical stability of different forms of nitric
oxide is different. The normal air is nitric oxide and nitrogen dioxide with relatively stable
chemical properties. Their hygienic significance is more important than other forms of nitric
oxide. In environmental analysis, nitrogen oxide generally refers to nitrogen monoxide and
nitrogen dioxide. The standard method for monitoring nitric oxide is the naphthalene
ethylene diamine hydrochloride colorimetric method. The sensitivity of the method is
0.25ug/5ml. The method conversion coefficient is affected by the composition of the
absorption liquid, the concentration of nitrogen dioxide, the gas recovery rate, the structure
of the absorption tube, the coexisting ions, and the temperature. The influence of various
factors is not completely unified. Sensor measurement is a new method developed in recent
years. It is reported in the literature that a new type of gas-sensitive microsensor is obtained
by combining a microelectronic integrated circuit with interdigitated gate electrode field-effect
transistors and chemically active electron beam evaporation phthalocyanine bronze film,
which can selectively detect mg/m3 level of dioxide Nitrogen and Diphenylene Methyl
Phosphonate (DIMP).

3. Hydrogen sulfide gas sensor

Hydrogen sulfide is a colorless combustible gas with a special rotten egg odor. It is irritating
and suffocating and is harmful to the human body. Colorimetry and gas chromatography are
mostly used to determine hydrogen sulfide in the air. The measurement of air pollutants
whose content is often as low as mg/m3 is a major application of gas sensors. However, in a
short period of time, semiconductor gas sensors cannot meet the sensitivity and selectivity
requirements for monitoring certain pollutant gases. The silver-doped thin-film sensor array
is composed of four sensors. Through the universal analysis device based on library titration
and the signal of the semiconductor gas sensor array, the concentration of sulfur dioxide and
hydrogen sulfide are recorded at the same time.

4. Sulfur dioxide sensor

Sulfur dioxide is one of the main substances that pollute the air. The attempt to detect sulfur
dioxide in the air is a regular task of air inspection. Sensors are used to monitor sulfur
dioxide. From shortening the detection time to lowering the detection limit, it shows great
advantages. A solid polymer is used as an ion-exchange membrane. One side of the
membrane contains the internal electrolyte of the counter electrode and the reference
electrode, and the other side is inserted with a platinum electrode to form a sulfur dioxide
sensor. The sensor is installed in a flow cell and oxidizes sulfur dioxide at 0.65V. The batch
indicates the amount of sulfur dioxide. The sensing device has high current sensitivity and
good stability. Its response time is short and the background noise is low. The linear range is
0.2mmol/L, the detection limit is 8*10-6mmol/L, and the signal-to-noise ratio is 3. The sensor
can not only measure sulfur dioxide in the air but also measure sulfur dioxide in liquids with
low conductivity. The gas-sensitive coating of the organic modified silicate thin film sulfur
dioxide gas sensor is made by the sol process and spin technology. It has good
reproducibility and reversibility for the determination of sulfur dioxide. The response time is
less than 20S. The sympathy is small, and it is less affected by temperature and humidity.

Liquid based electrode system:

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.

In most electrochemical sensors, an electrode surface is used as the site of the reaction.6
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.6

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).

The direct electrooxidation of NO in solutions follows a 3 step reaction. The ΔE for the
overall process is +0.5V vs. a Ag/AgCl reference electrode.

NO→NO++e− ………….(1)

NO++OH−→HNO2…………..(2)

HNO2+H2O→NO−3+2e−+3H+…………….(3)

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

Biosensors are defined as sensors that use biomolecules and/or structures to measure
something with biological significance or bioactivity. More appropriately, biosensors target a
biomolecule of interest for measurement. The biosensor can usually be considered a subset
of chemical sensors because the transduction methods, sometimes referred to as the sensor
platforms, are the same as those for chemical sensors. Chemical sensor arrays with
instrumentation, having popular names like the electronic nose or electronic tongue,5 have
been constructed to address chemically complex analytes like taste, odor, toxicity, or
freshness.
Voltammetry

Broadly speaking, voltammetric techniques can be categorised as being either sweep type
or polarography-like. The former refers to methods like cyclic voltammetry where the solution
is not stirred after each set potential, and the latter refers to techniques where it is. Other
types of voltammetry modify these methods, for example, with the use of a rotating
electrode.

Current In Voltammetry
When we oxidize an analyte at the working electrode, the resulting electrons pass through
the potentiostat to the auxiliary electrode, reducing the solvent or some other component of
the solution matrix. If we reduce the analyte at the working electrode, the current flows from
the auxiliary electrode to the cathode. In either case, the current from the redox reactions at
the working electrode and the auxiliary electrodes is called a faradaic current. In this
section we consider the factors affecting the magnitude of the faradaic current, as well as the
sources of any non-faradaic currents.

Sign Conventions
Because the reaction of interest occurs at the working electrode, we describe the faradaic
current using this reaction. A faradaic current due to the analyte’s reduction is a cathodic
current, and its sign is positive. An anodic current results from the analyte’s oxidation at
the working electrode, and its sign is negative.

Influence of Applied Potential on the Faradaic Current

− −
As an example, let’s consider the faradaic current when we reduce Fe(CN)36 to Fe(CN)46 at
−
the working electrode. The relationship between the concentrations of Fe(CN)36 , the
−
concentration of to Fe(CN)46 , and the potential is given by the Nernst equation
−
[Fe(CN)46 ]x=o
𝐸 = + 0.356 V − 0.05916log −
[Fe(CN)36 ]x=o
− −
where +0.356V is the standard-statepotential for the [Fe(CN)36 ]⁄[Fe(CN)46 ] redox couple,
− −
and x=0 indicates that the concentrations of Fe(CN)36 and Fe(CN)46 are those at the surface
of the working electrode. We use surface concentrations instead of bulk concentrations
because the equilibrium position for the redox reaction
− −
[Fe(CN)36 ] (𝑎𝑞 ) + 𝑒 − ⇌ [Fe(CN)46 ](𝑎𝑞)

is established at the electrode’s surface.

−
Let’s assume we have a solution for which the initial concentration of [Fe(CN)36 ] is 1.0 mM
−
and that [Fe(CN)46 ] is absent. Figure shows the ladder diagram for this solution.
 − −
Ladder diagram for the [Fe(CN)36 ]⁄[Fe(CN)46 ] redox half-reaction.

If we apply a potential of +0.530 V to the working electrode, the concentrations

− −
of [Fe(CN)36 ] and [Fe(CN)46 ] at the surface of the electrode are unaffected, and no faradaic
−
current is observed. If we switch the potential to +0.356 V some of the [Fe(CN)36 ] at the
−
electrode’s surface is reduced to [Fe(CN)46 ] until we reach a condition where
− −
[Fe(CN)36 ]𝑥=0 = [Fe(CN)46 ] 𝑥=0 = 0.5 𝑚𝑀

If this is all that happens after we apply the potential, then there would be a brief surge of
faradaic current that quickly returns to zero, which is not the most interesting of results.
− −
Although the concentrations of [Fe(CN)36 ] and [Fe(CN)46 ] at the electrode surface are 0.50
mM, their concentrations in bulk solution remains unchanged.

Because of this difference in concentration, there is a concentration gradient between the

solution at the electrode’s surface and the bulk solution. This concentration gradient creates
−
a driving force that transports [Fe(CN)46 ] away from the electrode and that transports
− −
[Fe(CN)36 ] to the electrode. As the [Fe(CN)36 ] arrives at the electrode it, too, is reduced to
−
[Fe(CN)46 ]. A faradaic current continues to flow until there is no difference between the
− −
concentrations of [Fe(CN)36 ] and [Fe(CN)46 ] at the electrode and their concentrations in
bulk solution.
 −
Schematic diagram showing the transport of [Fe(CN)46 ] away from the electrode’s surface
−
and the transport of [Fe(CN)36 ] toward the electrode’s surface following the reduction of
− −
[Fe(CN)36 ] to [Fe(CN)46 ].

Although the potential at the working electrode determines if a faradaic current flows, the
magnitude of the current is determined by the rate of the resulting oxidation or reduction
reaction. Two factors contribute to the rate of the electrochemical reaction: the rate at which
the reactants and products are transported to and from the electrode—what we call mass
transport—and the rate at which electrons pass between the electrode and the reactants and
products in solution.

The types of voltammetry gives more information on the advantages, disadvantages, and
applications of each technique.

Sweep type methods

o Cyclic voltammetry
o Linear sweep voltammetry
o Staircase voltammetry

Polarography like methods

o Conventional polarography
o Normal pulse voltammetry
o Chronoamperometry
o Reverse pulse voltammetry
o Differential pulse voltammetry
o Squarewave pulse voltammetry

Other types of voltammetry

o Rotated electrode voltammetry

o Stripping voltammetry
o Ultramicroelectrodes
o Electrode impedance spectroscopy
o Alternating current polarography
o Alternating current voltammetry
o Ultramicroelectrodes

Cyclic voltammetry remains the most widely used voltammetric technique due to its speed,
range of uses, and the ease with which the data can be analysed.

Cyclic voltammetry
Cyclic Voltammetry
In the voltammetric techniques consider to this point we scan the potential in one direction,
either to more positive potentials or to more negative potentials. In cyclic voltammetry we
complete a scan in both directions. Figure a shows a typical potential-excitation signal. In
this example, we first scan the potential to more positive values, resulting in the following
oxidation reaction for the species R.
R⇌O+ne−R⇌O+ne−
When the potential reaches a predetermined switching potential, we reverse the direction of
the scan toward more negative potentials. Because we generated the species O on the
forward scan, during the reverse scan it reduces back to R.
O+ne−⇌RO+ne−⇌R
Cyclic voltammetry is carried out in an unstirred solution, which, as shown in Figure, results
in peak currents instead of limiting currents. The voltammogram has separate peaks for the
oxidation reaction and for the reduction reaction, each characterized by a peak potential and
a peak current.

Details for cyclic voltammetry. (a) One cycle of the triangular potential-excitation signal
showing the initial potential and the switching potential. A cyclic voltammetry experiment can
consist of one cycle or many cycles. Although the initial potential in this example is the
negative switching potential, the cycle can begin with an intermediate initial potential and
cycle between two limits. (b) The resulting cyclic voltammogram showing the measurement
of the peak currents and peak potentials.

The peak current in cyclic voltammetry is given by the Randles-Sevcik equation

𝑖𝑝 = (2.69 × 105 )𝑛3⁄2 𝐴𝐷1⁄2 𝑣 1⁄2 CA

where n is the number of electrons in the redox reaction, A is the area of the working
electrode, D is the diffusion coefficient for the electroactive species, νν is the scan rate,
and CA is the concentration of the electroactive species at the electrode. For a well-behaved
system, the anodic and the cathodic peak currents are equal, and the ratio ip,a/ip,c is 1.00.
The half-wave potential, E1/2, is midway between the anodic and cathodic peak potentials.

𝐸𝑝,𝑎 + 𝐸𝑝,𝑐
𝐸1/2 =
2
Scanning the potential in both directions provides an opportunity to explore the
electrochemical behavior of species generated at the electrode. This is a distinct advantage
of cyclic voltammetry over other voltammetric techniques. Figure 11.4.15 shows the cyclic
voltammogram for the same redox couple at both a faster and a slower scan rate. At the
faster scan rate, 11.4.15 a, we see two peaks. At the slower scan rate in Figure 11.4.15 b,
however, the peak on the reverse scan disappears. One explanation for this is that the
products from the reduction of R on the forward scan have sufficient time to participate in a
chemical reaction whose products are not electroactive.

The Three Electrode System

Although in principle cyclic voltammetry (and other types of voltammetry) only requires two
electrodes, in practice it is difficult to maintain a constant potential and make sure that the
resistance measured is the one across the working electrode-solution interface. Passing the
necessary current can make both difficult, while also passing current to counteract the redox
events at the working electrode. As a result, a three electrode system is often used to
separate the role of referencing the potential applied and balance the current produced.

Three electrode cell as used in cyclic voltammetry with an Ossila Potentiostat

To measure and control the potential difference applied the potential of the working
electrode is varied while the potential of reference electrode remains fixed by a
electrochemical redox reaction with a well-defined value.

To keep the potential fixed, the reference electrode must contain constant concentrations of
each component of the reaction, such as a silver wire and a saturated solution of silver ions.
Importantly, minimal current passes between the reference and working electrodes. The
current observed at the working electrode is completely balanced by the current passing at
the counter electrode, which has a much larger surface area.

The electron transfer between the redox species at the working electrode and counter
electrode generates current that is carried through the solution by the diffusion of ions. This
forms a capacitive electrical double layer at the surface of the electrode called the diffuse
double layer (DDL). The DDL is composed of ions and orientated electric dipoles that serve
to counteract the charge on the electrode.

The measured current response is dependent on the concentration of the redox species (the
analyte) at the working electrode surface, and is described by a combination of Faraday’s
law and Fick’s first law of diffusion:

Where id is the diffusion-limited current, A is the electrode area, D0 is the diffusion coefficient
of the analyte and (∂C0/∂x0) is concentration gradient at the electrode surface.
The product of the diffusion coefficient and concentration gradient can be thought of as the
molar flux (mol·cm-2·s-1) of analyte to the electrode surface.

Voltammetry is a category of electroanalytical methods used in analytical chemistry and

various industrial processes. In voltammetry, information about an analyte is obtained by
measuring the current as the potential is varied. The analytical data for a voltammetric
experiment comes in the form of a voltammogram which plots the current produced by the
analyte versus the potential of the working electrode.
 Linear potential sweep

Three-electrode setup: (1) working electrode; (2) auxiliary electrode; (3) reference electrode

Instrumentation
A CV system consists of an electrolysis cell, a potentiostat, a current-to-voltage converter,
and a data acquisition system. The electrolysis cell consists of a working electrode, counter
electrode, reference electrode, and electrolytic solution. The working electrode’s potential is
varied linearly with time, while the reference electrode maintains a constant potential. The
counter electrode conducts electricity from the signal source to the working electrode. The
purpose of the electrolytic solution is to provide ions to the electrodes during oxidation and
reduction. A potentiostat is an electronic device which uses a dc power source to produce a
potential which can be maintained and accurately determined, while allowing small currents
to be drawn into the system without changing the voltage. The current-to-voltage converter
measures the resulting current, and the data acquisition system produces the resulting
voltammogram.

Applications
Cyclic Voltammetry can be used to study qualitative information about electrochemical
processes under various conditions, such as the presence of intermediates in oxidation-
reduction reactions, the reversibility of a reaction. CV can also be used to determine the
electron stoichiometry of a system, the diffusion coefficient of an analyte, and the formal
reduction potential, which can be used as an identification tool. In addition, because
concentration is proportional to current in a reversible, Nernstian system, concentration of an
unknown solution can be determined by generating a calibration curve of current vs.
concentration.
Differential pulse voltammetry

Differential pulse voltammetry (DPV) (also differential pulse polarography, DPP) is a

voltammetry method used to make electrochemical measurements and a derivative of linear
sweep voltammetry or staircase voltammetry, with a series of regular voltage pulses
superimposed on the potential linear sweep or stairsteps. The current is measured
immediately before each potential change, and the current difference is plotted as a function
of potential. By sampling the current just before the potential is changed, the effect of the
charging current can be decreased.

By contrast, in normal pulse voltammetry the current resulting from a series of ever larger
potential pulses is compared with the current at a constant 'baseline' voltage. Another type of
pulse voltammetry is squarewave voltammetry, which can be considered a special type of
differential pulse voltammetry in which equal time is spent at the potential of the ramped
baseline and potential of the superimposed pulse.
 Electrochemical cell: The system of this measurement is usually the same as that of
standard voltammetry. The potential between the working electrode and the
reference electrode is changed as a pulse from an initial potential to an interlevel
potential and remains at the interlevel potential for about 5 to 100 milliseconds; then
it changes to the final potential, which is different from the initial potential. The pulse
is repeated, changing the final potential, and a constant difference is kept between
the initial and the interlevel potential. The value of the current between the working
electrode and auxiliary electrode before and after the pulse are sampled and their
differences are plotted versus potential.
 Uses: These measurements can be used to study the redox properties of extremely
low concentrations of chemicals because of the following two features: 1) in these
measurements, the effect of the charging current can be minimized, so high
sensitivity is achieved and 2) only faradaic current is extracted, so electrode
reactions can be analyzed more precisely.
 Characteristics: Differential pulse voltammetry has these characteristics: 1) reversible
reactions have symmetric peaks, and irreversible reactions have asymmetric peaks,
2) the peak potential is equal to E1/2r-ΔE in reversible reactions, and the peak
current is proportional to the concentration, 3) The detection limit is about 10−8 M
Polarography

The important voltammetric technique to be developed—polarography—uses the dropping

mercury electrode shown in Figure as the working electrode. As shown in Figure, the current
is measured while applying a linear potential ramp.

Three examples of mercury electrodes: (a) hanging mercury drop electrode, or HMDE; (b)
dropping mercury electrode, or DME; and (c) static mercury drop electrode, or SMDE

Details of normal polarography: (a) the linear potential-excitation signal, and (b) the resulting
voltammogram.
Although polarography takes place in an unstirred solution, we obtain a limiting current
instead of a peak current. When a Hg drop separates from the glass capillary and falls to the
bottom of the electrochemical cell, it mixes the solution. Each new Hg drop, therefore, grows
into a solution whose composition is identical to the bulk solution. The oscillations in the
current are a result of the Hg drop’s growth, which leads to a time-dependent change in the
area of the working electrode. The limiting current—which also is called the diffusion
current—is measured using either the maximum current, imax, or from the average
current, iavg. The relationship between the analyte’s concentration, CA, and the limiting
current is given by the Ilkovic equations

imax=706nD1/2m2/3t1/6CA=KmaxCA
iavg=607nD1/2m2/3t1/6CA=KavgCA
where n is the number of electrons in the redox reaction, D is the analyte’s diffusion
coefficient, m is the flow rate of Hg, t is the drop’s lifetime and Kmax and Kavg are constants.
The half-wave potential, E1/2, provides qualitative information about the redox reaction.

Polarography is used extensively for the analysis of metal ions and inorganic anions, such
as IO−3 and NO−3 . We also can use polarography to study organic compounds with easily
reducible or oxidizable functional groups, such as carbonyls, carboxylic acids, and carbon-
carbon double bonds.

Definition of Electric Polarization

Electric polarization is a part of the study of classical electromagnetism. If one has to define
electric polarisation, it can be said that electric polarization (or polarization density or just
polarization) is a vector field that defines the density of permanent or induced electric dipole
moments in a dielectric material. Polarization is said to be completed when the dielectric is
placed in an external electric field and gains an electric dipole moment.

Thus dielectric and polarization definition can be stated as ‘the electric dipole moment
induced per unit volume of the dielectric material.’ It also explains the response of material
on the applied electric field and how the material changes the electric field. It can be thus
used to calculate the forces that come out due to these interactions.

It is also compared with magnetization which measures the relative response of a material to
a magnetic field in magnetism. The unit for measurement is coulombs per square meter and
polarization is represented by a vector P.

Dielectric Polarization SignificanceThe displacement of bound charged elements of dielectric

material occurs due to the external electric field application. These elements cannot freely
move around the material because they are bound to the molecules. Elements with a
negative charge are displaced opposite and those with a positive charge move towards the
field. An electric dipole moment is formed though the molecules are neutral in charge. Let’s
say that a volume element ∆V in the material with a dipole moment ∆p, the polarization
density P can be described as
Potentiometric sensor
A potentiometric sensor is a type of chemical sensor that may be used to determine the
analytical concentration of some components of the analyte gas or solution. These sensors
measure the electrical potential of an electrode when no current is present.

Principle
The signal is measured as the potential difference (voltage) between the working electrode
and the reference electrode. The working electrode's potential must depend on the
concentration of the analyte in the gas or solution phase. The reference electrode is needed
to provide a defined reference potential.

Classification of sensors

Potentiometric solid state gas sensors have been generally classified into three broad
groups.

 Type I sensors have an electrolyte containing mobile ions of the chemical species in the
gas phase that it is monitoring. The commercial product, YSZ oxygen sensor, is an
example of type I.
 Type II sensors do not have mobile ions of the chemical species to be sensed, but an
ion related to the target gas can diffuse in the solid electrolyte to allow equilibration with
the atmosphere. Therefore, type I and type II sensors have the same design with gas
electrodes combined with metal and an electrolyte where oxidized or reduced ions can
be electrochemically equilibrated through the electrochemical cell.
 In the third type of electrochemical sensor, auxiliary phases are added to the electrodes
to enhance the selectivity and stability. Type III sensors make the electrode concept
even more confusing. With respect to the design of a solid state sensor, the auxiliary
phase looks as part of the electrode. But it cannot be an electrode because auxiliary
phase materials are not generally good electrical conductor. In spite of this confusion,
type III design offers more feasibility in terms of designing various sensors with different
auxiliary materials and electrolytes.

Applications
Potentiometers are rarely used to directly control significant amounts of power (more than a
watt or so). Instead they are used to adjust the level of analog signals (for example volume
controls audio equipment), and as control inputs for electronic circuits. For example, a light
dimmer uses a potentiometer to control the switching of a TRIAC and so indirectly to control
the brightness of lamps.

Preset potentiometers are widely used throughout electronics wherever adjustments must be
made during manufacturing or servicing.

User-actuated potentiometers are widely used as user controls, and may control a very wide
variety of equipment functions. The widespread use of potentiometers in consumer
electronics declined in the 1990s, with rotary incremental encoders, up/down push-buttons,
and other digital controls now more common. However they remain in many applications,
such as volume controls and as position sensors.

 Audio control: Low-power potentiometers, both slide and rotary, are used to control
audio equipment, changing loudness, frequency attenuation, and other
characteristics of audio signals.
 The 'log pot', that is, a potentiometer has a resistance, taper, or, "curve" (or law) of a
logarithmic (log) form, is used as the volume control in audio power amplifiers, where
it is also called an "audio taper pot", because the amplitude response of the
human ear is approximately logarithmic. It ensures that on a volume control marked 0
to 10, for example, a setting of 5 sounds subjectively half as loud as a setting of 10.
There is also an anti-log pot or reverse audio taper which is simply the reverse of a
logarithmic potentiometer. It is almost always used in a ganged configuration with a
logarithmic potentiometer, for instance, in an audio balance control.
Potentiometers used in combination with filter networks act as tone
controls or equalizers.
In audio systems, the word linear, is sometimes applied in a confusing way to
describe slide potentiometers because of the straight line nature of the physical
sliding motion. The word linear when applied to a potentiometer regardless of being a
slide or rotary type, describes a linear relationship of the pot's position versus the
measured value of the pot's tap (wiper or electrical output) pin.
 Television: Potentiometers were formerly used to control picture brightness,
contrast, and color response. A potentiometer was often used to adjust "vertical
hold", which affected the synchronization between the receiver's internal sweep
circuit (sometimes a multivibrator) and the received picture signal, along with other
things such as audio-video carrier offset, tuning frequency (for push-button sets) and
so on. It also helps in frequency modulation of waves.
 Motion control: Potentiometers can be used as position feedback devices in order
to create closed-loop control, such as in a servomechanism. This method of motion
control is the simplest method of measuring the angle or displacement.
 Transducers: Potentiometers are also very widely used as a part
of displacement transducers because of the simplicity of construction and because
they can give a large output signal.
 Computation: In analog computers, high precision potentiometers are used to scale
intermediate results by desired constant factors, or to set initial conditions for a
calculation. A motor-driven potentiometer may be used as a function generator, using
a non-linear resistance card to supply approximations to trigonometric functions. For
example, the shaft rotation might represent an angle, and the voltage division ratio
can be made proportional to the cosine of the angle.
Amperometry
The final voltammetric technique we will consider is amperometry, in which we apply a
constant potential to the working electrode and measure current as a function of time.
Because we do not vary the potential, amperometry does not result in a voltammogram.

One important application of amperometry is in the construction of chemical sensors. One of

the first amperometric sensors was developed in 1956 by L. C. Clark to measure dissolved
O2 in blood. Figure shows the sensor’s design, which is similar to a potentiometric
membrane electrode. A thin, gas-permeable membrane is stretched across the end of the
sensor and is separated from the working electrode and the counter electrode by a thin
solution of KCl. The working electrode is a Pt disk cathode, and a Ag ring anode serves as
the counter electrode. Although several gases can diffuse across the membrane, including
O2, N2, and CO2, only oxygen undergoes reduction at the cathode

O2(g)+4H3O+(aq)+4e−⇌6H2O(l)

with its concentration at the electrode’s surface quickly reaching zero. The concentration of
O2 at the membrane’s inner surface is fixed by its diffusion through the membrane, which
creates a diffusion profile similar to that in Figure. The result is a steady-state current that is
proportional to the concentration of dissolved oxygen. Because the electrode consumes
oxygen,the sample is stirred to prevent the depletion of O 2 at the membrane’s outer surface.
The oxidation of the Ag anode is the other half-reaction.

Ag(s)+ Cl−(aq)⇌AgCl(s)+e−

Clark amperometric sensor for determining dissolved O2. The diagram on the right is a
cross-section through the electrode, which shows the Ag ring electrode and the Pt disk
electrode.

Quantitative Applications

Voltammetry has been used for the quantitative analysis of a wide variety of samples,
including environmental samples, clinical samples, pharmaceutical formulations, steels,
gasoline, and oil.
 Selecting the Voltammetric Technique: The choice of which voltammetric technique
to use depends on the sample’s characteristics, including the analyte’s expected
concentration and the sample’s location. For example, amperometry is ideally suited
for detecting analytes in flow systems, including the in vivo analysis of a patient’s
blood or as a selective sensor for the rapid analysis of a single analyte. The
portability of amperometric sensors, which are similar to potentiometric sensors, also
make them ideal for field studies. Although cyclic voltammetry is used to determine
an analyte’s concentration, other methods described in this chapter are better suited
for quantitative work.

 Pulse polarography and stripping voltammetry frequently are interchangeable. The

choice of which technique to use often depends on the analyte’s concentration and
the desired accuracy and precision. Detection limits for normal pulse polarography
generally are on the order of 10–6 M to 10–7 M, and those for differential pulse
polarography, staircase, and square wave polarography are between 10–7 M and
10–9 M. Because we concentrate the analyte in stripping voltammetry, the detection
limit for many analytes is as little as 10–10 M to 10–12 M. On the other hand, the
current in stripping voltammetry is much more sensitive than pulse polarography to
changes in experimental conditions, which may lead to poorer precision and
accuracy. We also can use pulse polarography to analyze a wider range of inorganic
and organic analytes because there is no need to first deposit the analyte at the
electrode surface.

 Stripping voltammetry also suffers from occasional interferences when two metals,
such as Cu and Zn, combine to form an intermetallic compound in the mercury
amalgam. The deposition potential for Zn . is sufficiently negative that any Cu2+ in
the sample also deposits into the mercury drop or film, leading to the formation of
intermetallic compounds such as CuZn and CuZn2. During the stripping step, zinc in
the intermetallic compounds strips at potentials near that of copper, decreasing the
current for zinc at its usual potential and increasing the apparent current for copper. It
is possible to overcome this problem by adding an element that forms a stronger
intermetallic compound with the interfering metal. Thus, adding Ga3+ minimizes the
interference of Cu when analyzing for Zn by forming an intermetallic compound of Cu
and Ga.