ATRIA INSTITUTE OF TECHNOLOGYANAND NAGAR BANGALORE 24

(Prepared by T.G.Murali M.Sc.,M.Phil B.Ed (Phd) Retd.General

Manager reputed pharma limited and Assistant professor chemistry
ATRIA)

MODULE 5: Sensors in Analytical techniques (8hr)

Electrode system:
Introduction, types of electrodes, Ion selective electrode – definition,
construction, working and applications of glass electrode. Determination of pH
using glass electrode. Reference electrode: Introduction, calomel electrode –
construction, working and applications of calomel electrode. Concentration cell
– Definition, construction and Numerical problems. Sensors: Introduction,
working principle and applications of conductometric sensors, Electrochemical
sensors, Thermometric sensors, and Optical sensors Analytical techniques:
Introduction, principle and instrumentation: Colorimetric sensors – estimation
of copper, Potentiometric sensors – estimation of iron, Conductometric
sensors – estimation of weak acid.

Ion selective electrode – definition, construction,

ION SELECTIVE ELECTRODE
Definition: “Ion selective electrode is very selective towards particular type of
ions and develop a potential proportional to the concentration of that ions. The
sensitive part of electrode is its membrane which allows the exchange of selective
++
ttions”.
Ion selective electrode (ISE) are comparatively simple membrane based
potentiometric devices which are capable of accurately measuring the
concentration of ions in solution.
Ex. Glass electrode, crystalline electrodes, Ion-exchange electrodes, Enzyme
electrodes, Alkali metal ISE.
Working mechanism of ion selective electrodes
External Solution to Membrane Internal Internal
reference analyzed standard reference
electrode (analyte) solution electrode
(Mn+) = C2 (Mn+) = C1
 According to the Nernst equation, the voltage is theoretically dependent on
the logarithms of the ionic activity.
 The ion-selective electrode works based on the principle of a galvanic cell. It
consists of a reference electrode, ion-selective membranes and voltmeter.
 The transport of ions from an area of high concentration to low concentration
through the selective binding of ions with the specific sites of membrane
creates a potential difference. This potential is measured with respect to a
stable reference electrode having a constant potential and net charge is
determined. The strength of the net charge thus measured is directly
proportional to the concentration of the selected ion.
Application of Ion-selective electrode
 Clinical chemistry: - Analysis of electrolyte such as Na+, K+ in blood, serum
etc.
 Environmental chemistry: - For the analysis of CN-, F-, NH3, NO-3, in water
and wastes samples.
 Agricultural chemistry: - For the analysis of K+, NH4+, etc, in soil and plant
sample
 Industry: – For the analysis CN- in electroplating bath.
 Pharmaceutical: For the analysis of F- and PH of the toothpaste.
 Research and education: For the measurement of PH and other types of ions I
sample.
working and applications of glass electrode
GLASS ELECTRODE
Construction Glass electrode:
1. Glass electrode is constructed by immersing Ag-AgCl internal reference
electrode in a glass bulb containing 0.1M HCl solution.
2. The glass bulb is made up of a long glass tube with a thin highly conducting
glass membrane at the bottom.
3. The glass membrane is selective to H+ ions in the solution, and is made up of
silicate glass having composition of 72% SiO2, 22% Na2O and 6 % Cao.

Diagram 4. Glass electrode

The electrode can be represented as
Ag/AgCl/0.1M HCl/Glass membrane

Working of glass electrode:

When a glass bulb containing 0.1M HCl is immersed in an acidic solution of
different concentration, a boundary potential (Eb) is developed across the gel
layers of the glass membrane.
This boundary potential (Eb) arises due to the difference is concentration of H+
ions inside and outside of the glass bulb.
𝐶2
𝐸𝑏 = 0.0591 𝑙𝑜𝑔
𝐶1
C1 = Concentration of H+ inside the bulb, is a constant, C2 = concentration H+
outside the bulb.
𝐸𝑏 = 0.0591 𝑙𝑜𝑔[𝐶2 ] − 0.0591 𝑙𝑜𝑔[𝐶1 ]
Substitute − 0.0591 𝑙𝑜𝑔[𝐶1 ] = 𝐾, a constant
Then the equation becomes
𝐸𝑏 = 𝐾 + 0.0591 𝑙𝑜𝑔[𝐶2 ] = 𝐾 + 0.0591 𝑙𝑜𝑔[𝐻+ ]
Substitute log (H+) = - pH
The final equation for Eb is obtained as
𝐸𝑏 = 𝐾 − 0.0591 𝑝𝐻
The potential of glass electrode (EG) includes contribution from 3 factors
 Boundary Potential (Eb)
 Potential of Ag-AgCl reference electrode dipped inside the bulb E Ag/AgCl
 Asymmetric potential due to slight in homogeneity of the inner and outer
surface of the glass membrane E Asy.
𝐸𝐺 = 𝐸𝑏 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝐴𝑠𝑦
𝐸𝐺 = 𝐾 − 0.0591 𝑝𝐻 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝐴𝑠𝑦
𝐸𝐺 = 𝐿 − 0.0591 𝑝𝐻
Where constant 𝐿 = 𝐾 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝐴𝑠𝑦

Determination of pH using glass electrode.

Determination of pH using glass electrode
To measure of pH of an unknown solution a glass electrode is coupled with
calomel electrode and connected to potentiometer (or pH meter for reading pH
directly)
 Diagram 5. Determination of pH
The cell formed is represented as
Hg/Hg2Cl2/KCl// solution of unknown pH/Glass electrode
The potential established at the glass electrode is higher than that of the calomel
electrode hence glass electrode is taken as cathode.
E Cell = E Cathode – E anode
E Cell = E G – E SCE
Substituting for EG
E Cell = (L- 0.0591pH) – E SCE
The above equation is arranged to obtain the expression for pH
𝐿 − 𝐸𝑆𝐶𝐸 − 𝐸𝑐𝑒𝑙𝑙
𝑝𝐻 =
0.0591

Reference electrode: Introduction, calomel electrode

– construction, working and applications of calomel
electrode.
REFERENCE ELECTRODE
 An electrode having fixed potential, which can be used as a reference to
measure the potential of another electrode.

Construction
 The saturated calomel electrode (SCE) is a reference electrode based on
the reaction between elemental mercury and mercury chloride.
 The calomel electrode consists of two glass tube. At the inside glass tube,
there is a paste of mercury and mercurous chloride (calomel) (Hg 2Cl2) at
the bottom of a narrow glass tube having a porous plug at the bottom. Pure
mercury is filled above paste and connected with platinum wire for
electrical connections. This narrow tube placed inside an outer glass tube
filled with a saturated KCl solution. KCI solution of 0.1 M or of 1 M can
also be used. The porous plug at the bottom of outer tube acts as salt bridge.

 Calomel electrodes can be represented as

 Diagram 2. Calomel electrode

Working:
Since the calomel electrode is reversible, two types of reactions are possible
depending upon the nature of another electrode with which it is coupled.
When it acts as anode, the electrode reaction is
2𝐻𝑔 + 2𝐶𝑙− → 2𝐻𝑔2 𝐶𝑙2 + 2𝑒 −
Thus, oxidation takes place when it is coupled with another electrode having
lower oxidation potential.
When it acts as cathode, the electrode reaction is
2𝐻𝑔2 𝐶𝑙2 + 2𝑒 − → 2𝐻𝑔 + 2𝐶𝑙−
Thus, reduction takes place when it is coupled with another electrode having
greater oxidation potential.
The net reversible electrode reaction
 2𝐻𝑔2 𝐶𝑙2 + 2𝑒 − ↔ 2𝐻𝑔 + 2𝐶𝑙 −
Electrode potential
2.303𝑅𝑇
𝐸 = 𝐸𝑜 − 𝑙𝑜𝑔[𝐶𝑙 − ] 2
2𝐹

𝐸 = 𝐸 𝑜 − 0.0591 𝑙𝑜𝑔[𝐶𝑙 − ] at 298 K

The electrode potential is decided by the concentration if chloride ions and the
electrode is reversible with chloride ions. At 298 K, the electrode potentials are
as follows.
0.1 M KCl electrode (0.334 V)
1 M KCl electrode (0.281 V)
Saturated KCl electrode (0.2422 V)
Applications of calomel electrode:
1. It is used as secondary reference electrode in the measurement of single
electrode potentials.
2. It is used in potentiometric quantitate analysis.

Concentration cell – Definition, construction and

Numerical problems.
ELECTROLYTE CONCENTRATION CELLS
These cells consist of identical electrodes immersed in the solutions of the
same electrolytes but with varying concentrations. Potential difference arises due
to difference in electrolyte concentration.
Components of the Concentration Cell
 Electrode
 The two electrodes are called the cathode (right side) and the anode (left side).
The anode loses electrons through oxidation reaction. The cathode gains electrons
through reduction reaction.
 Salt Bridge
The salt bridge offers the perfect solution for the separation of the two half-
cells while providing a pathway for ion transfer.
 Voltmeter
The voltmeter is used to measure the cell potential of the cell.

Construction:
The concentration cell is a type of galvanic cell where the half-cells consist
of the same substance but at different concentrations. These cells give a small
potential difference while moving towards chemical equilibrium which can be
measured using a voltmeter.

Ex: The anode consists of Cu/Cu2+(0.001M) whereas the cathode consists of

Cu2+(0.1M)/Cu. In this cell, the flow of electrons from the anode to the cathode
is due to the reduction of Cu2+ ions at the cathode into metallic copper.

Diagram 6. Concentration cell

Cell representation

Cell reaction
At anode
At cathode

Net reaction

Nernst equation for concentration cell

Nernst equation for anodic reaction:

𝑜
2.303𝑅𝑇
𝐸𝑎𝑛𝑜𝑑𝑒 = 𝐸𝑎𝑛𝑜𝑑𝑒 + 𝑙𝑜𝑔 𝐶1
𝑛𝐹
Nernst equation for anodic reaction:

𝑜
2.303𝑅𝑇
𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 + 𝑙𝑜𝑔 𝐶2
𝑛𝐹
Cell potential: When reduction potential of both electrodes is taken into account
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑟𝑒𝑑 (𝑐𝑎𝑡ℎ𝑜𝑑𝑒) − 𝐸𝑟𝑒𝑑 (𝑎𝑛𝑜𝑑𝑒)
𝑜 𝑜 2.303𝑅𝑇 𝐶2
𝐸𝑐𝑒𝑙𝑙 = (𝐸𝑟𝑒𝑑 (𝑐𝑎𝑡ℎ𝑜𝑑𝑒) − 𝐸𝑟𝑒𝑑 (𝑎𝑛𝑜𝑑𝑒)) + 𝑙𝑜𝑔
𝑛𝐹 𝐶1

In concentration cell, both electrodes are same, hence

𝑜 𝑜
𝐸𝑟𝑒𝑑 (𝑐𝑎𝑡ℎ𝑜𝑑𝑒) − 𝐸𝑟𝑒𝑑 (𝑎𝑛𝑜𝑑𝑒)= 0
2.303𝑅𝑇 𝐶2
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔
𝑛𝐹 𝐶1
Or
0.0591 𝐶2
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔 𝑎𝑡 298 𝐾
𝑛 𝐶1

Numerical problem on concentration cells

1. EMF of the cell Cu/CuSO4) // CuSO4/Cu is 0.0595V at 250C. Find X value?
It is clear that C1= 0.001M, C2 = X and n= 2
Ans:
0.0591 𝐶2
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔
𝑛 𝐶1
0.0591 𝑋
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔
2 0.001
 𝑋 = 0.103 𝑀
2. A concentration cell is constructed by dipping copper rods in 0.001M
and 0.1 M copper sulphate solutions. Calculate the EMF of cell at 298K.
Ans: Cell representation

Cell reactions
Anode (oxidation): Cu → Cu2+ + 2e-
Cathode (Reduction): Cu2+ + 2e- → Cu
Overall reaction: Cu2+ C2= 0.1 M → Cu2+ C1=0.001M
0.0591 𝐶2
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔
𝑛 𝐶1
0.0591 0.1
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔
2 0.001
E cell = 0.0591 V
3. The spontaneous galvanic cell tin/ tin ion 0.02 M// tin ion (0.06M)/Tin
develops an emf of 0.041 V at 298. Calculate the valency of Tin.
Apply Nernst equation for concentration cells
0.0591 𝐶2
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔
𝑛 𝐶1
Rearrange the equation
0.0591 𝐶2
𝑛= 𝑙𝑜𝑔
𝐸𝑐𝑒𝑙𝑙 𝐶1

0.0591 0.06
𝑛= 𝑙𝑜𝑔
0.0141 0.01
n=2
Sensors: Introduction, working principle and
applications of conductometric sensors
Conductometric detection

 Conductometric detection is based on measurement of specific

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

Working of conductometric sensor

Fabrication and Surface Modification of Electrodes
 Interdigital electrodes (IDE) were screen-printed on a glass substrate
(microscope slide) to fabricate an interdigital transducer (IDT).
 Screen-printed interdigitated gold electrode-based sensor systems have
been used for variety of analytes
 The desired structure of interdigital electrodes was fabricated on the
substrate via screen printing with commercial gold paste.
 The electrode structure was designed by photo lithography.
 All organic components present in gold paste were removed by heating
at 500 °C for 4 h. The advantage of this procedure is based on the
robustness of the gold layers.
 The pattern and dimensions of the IDEs structure on transducer surface is
shown in Figure 1.
  IDT was fabricated by screen printing IDE of gold on glass substrate. IDT
was coated with sensitive layer and LCR meter was used to measure
resistance of sensitive layer by placing it in glass cell filled with electrolyte
solution.
 The prepared transducer was cooled down to room temperature, then
washed in an ultrasonic water bath for 5 min and dried.
 The IDT was placed in a boiling mixture of chloroform and ethanol (1:1
v/v) for at least 10 min for washing.
 Afterwards, IDT was treated with hot lithium hydroxide solution (0.2 mM)
for 10 min, rinsed with distilled water and dried.
 Then, IDT was dipped in a solution of 3-aminopropyl-triethoxysilane in
ethanol for 1–2 min followed by rinsing with ethanol. The silanized
structure was cured for 10 min at 110 °C.
 A mixture of monomers, cross-linker, and template was heated at 70 °C
until its gelation point which is called as pre-polymer. This pre-polymer
was applied to transducer surface to form a rigid layer after complete
polymerization.

Application conductometric sensor

1. DNA Detection

 AuNP (nano particles)-based genosensor designs for the detection of DNA

hybridization.
  Both assay formats were based on a magnetically induced
direct electrochemical detection of the AuNP tags on a magnetic
graphite–epoxy composite electrode.
 The first assay is based on the hybridization between two single-strand,
biotin-modified DNA probes: a capture DNA probe and a target DNA
related to the breast cancer gene.
 The second assay is based on hybridization between three DNA strands: a
biotin-modified capture DNA probe, a target DNA related to the cystic
fibrosis gene, and a DNA signaling probe modified with AuNPs via biotin–
streptavidin conjugation.

2. Advanced Nanoparticle-Based Biosensors for Diagnosing Foodborne

Pathogens

 The relationship between conductance and bioreceptor techniques is the

basis for developing conductometric detection performed using a
conducting polymer.
 The conducting polymer acts as an electrochemical transducer to convert
biological signals into electrical signals. Examples of conducting
polymers are polyaniline, polythiophene, polyacetylene,
 Few applications of conductometric biosensors have been reported for
the detection of foodborne pathogens. Pal et al. developed a direct-
charge transfer conductometric biosensor to detect Bacillus cereus in
numerous food samples.
 In their study an electronic signal was generated by electron charge flow
aided through conductive polyaniline combined with the principle of a
sandwich IA.
 The biosensor could decrease LOD to 35–88 CFU/mL B. cereus in food
samples and only took 6 min to complete. The biosensor was selective
to B. cereus only used.
Electrochemical sensors
Electrochemical sensors are a class of sensors in which the electrode is the
transducer element. These devices are now found in a wide range of
commercial applications.

Working principle and application of electrochemical

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

Diagrammatic representation of the working principle of an electrochemical

sensor

 Electrochemical sensor’s working mechanism involves the interaction of

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

Conclusions
Application Electrochemical sensors

 Electrochemical sensors are considered attractive tools to determine

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

Working principle and Thermometric sensors,

What is the Temperature Sensor?

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

CLICK HERE

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

T/C, is constructed from two different metals that produce an electrical output
voltage in direct relation with the temperature modification.

Temperature Sensor Working

 The fundamental working of this sensor is based on the voltage in its

diode. The temperature variation is directly related to the resistance of
this diode.

 The resistance of the diode is detected and transformed into simple and
readable values of temperature such as Fahrenheit, Kelvin, or Centigrade
and demonstrated in meaningful formats instead of readout values.

 These temperature sensors are employed to sense the internal

temperature of various structures like power plants

 In addition, some devices have a type of vibrating wire in the structure of

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

 In modern and high-tech temperature sensors, the basic metal is

aluminum because aluminum has a greater coefficient of a thermal effect
than steel. As the temperature sign is transformed into frequency, the
readout values utilized for other vibrating sensors can also be used to
control the temperature.

Temperature Sensors Formula

The frequency related to the temperature is also proportional to the

tension ‘σ’ in the wire, can be described as follows:

f = 1/2 * [σg/ρ] / 2L (Hz)

Where:

σ = tension of the wire

ρ = density of the wire

L = length of wire

g = acceleration due to gravity

Types of Temperature Sensor

1.Thermostats

A thermostat is a contact type sensor containing a bi-metallic section

constructed from two different metals such as aluminum, 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. So,
they will be introduced as a separate group of sensors in some textbooks. We
will discuss them below completely. But there are a lot of thermistors that have
a positive temperature coefficient. They are introduced as PTCs, and their
resistance increases by increasing the temperature.

3.Resistive Temperature Detectors

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

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

A thermocouple generally includes two sections of dissimilar metals, such as constantan

and copper, combined by welding. One of these sections, introduces as the Cold
junction, has a particular temperature while the other one, introduced as the Hot
junction, is for the measuring process.

Temperature Sensor Applications

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

 The main application of these temperature sensors is in hazardous locations like

nuclear power plants.

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

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

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

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

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

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

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

Advantages of Temperature Sensors

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

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

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

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

Optical Sensors working principle

 Optical sensors use visible or ultraviolet light to interrogate sensors for
analysis. Optical sensors can be represented in general terms as a
wavelength-selectable light source, the sensor material itself interacting
with analytes, and a light detector (Fig. 1).
 What the detector monitors varies by technique (e.g., refractive index,
scattering, diffraction, absorbance, reflectance, photoluminescence,
chemiluminescence, etc.), can cover different regions of the
electromagnetic spectrum, and can allow measurement of multiple
properties.
 The focus of this article, however, is on optical sensor arrays that use
absorbance, reflectance, or fluorescence array detectors (i.e., digital
cameras or scanners).
 Colorimetry (i.e., quantitative measurement of absorbance or reflectance
spectra) is, of course, one of the oldest of analytical techniques, and
colorimetric sensors stretch back even before the beginnings of
chemistry.
 Colorimetric detection is a fairly simple technique, and the advent of
universal digital imaging has given it new and exciting possibilities.
 We will use the general term colorimetry to include simple colour (i.e.,
RGB) imaging, hyperspectral imaging (i.e., more colour channels), and
full spectrophotometry (i.e., hundreds of colour channels with nanometre
resolution).
Applications of Optical Sensors

 Application of these optical sensors ranges from computers to motion

detectors. For optical sensors to work effectively, they must be the
correct type for the application, so that they maintain their sensitivity to
the property they measure.

 Optical sensors are integral parts of many common devices, including

computers, copy machines (xerox) and light fixtures that turn on
automatically in the dark.

 And some of the common applications include alarm systems, synchros

for photographic flashes and systems that can detect the presence of
objects.

Ambient Light Sensors

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

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

Ambient Light
Sensors

Biomedical Applications
  Optical sensors have robust applications in the biomedical field. Some of
the examples Breath analysis using tunable diode laser, Optical heart-rate
monitors an optical heart-rate monitor measures your heart rate using
light.

 A LED shines through the skin, and an optical sensor examines the light
that reflected back. Since blood absorbs more light, fluctuations in light
level can be translated into heart rate. This process is called as
photoplethysmography.

Optical Sensor Based Liquid Level Indicator

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

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

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

Analytical techniques: Introduction, principle and

instrumentation: Colorimetric sensors – estimation
of copper,
Instrumental Analysis
Introduction
Analytical chemistry is the study of the separation, identification and
quantification of the chemical components of natural and artificial materials.
Analytical methods can be divided into classical and instrumental methods.
1. Classical methods (Chemical method)
Chemical method use separation such as precipitation, extraction, and distillation
and analyses the samples qualitatively by colour, odour, or melting classical
quantitively analysis is achieved by measurement of weight gravimetrically or
volumetrically.
2. Instrumental methods (Physical method)
Physical method or advanced instrument to measure physical quantities of the
analyte by relating the concentration with light absorption, fluorescence,
conductivity or Potential.
The instrumental methods have greatest advantage that it can investigate the
structure of complex organic molecules, reaction kinetics and even the
biochemistry of living cells.

Method Principle and Application

instrumentation
1.Colorimetry Light absorbance is To determine
proportional to concentration of ions
 concentration and path and molecules in
length. Beer lambert law solutions.
based visible light source
used.
2.Flame photometry Measurement of emitted To determine
radiation. No light sourceconcentration of
but only flame used. selective metals
(Na, K, etc.) in sample
3. Atomic Absorption Measurement of intensity To determine the
spectroscopy. of absorbed radiation. Light concentration of metal
source and flame. elements in samples.

4.Potentiometry It measures current/voltage To determine

between two electrodes concentration of ions in
where redox reaction take samples through redox
place titration.

5.Conductometry It measures only movement To measure conductivity

and concentration of ions. of sample solutions.
(no redox reaction)

Calorimetry
1. Simple technique used to determine the concentration of compounds in a
solution.
2. This method is used for solution which are themselves colored (or) which
gives colour with a suitable reagent.
3. The colour intensity of the solution is directly proportional to the
concentration of the solution.
Theory
This method is based on Beer- Lambert law
According to this law when a monochromatic light is passed through a
solution, part of light is absorbed by the solution. The extent of absorption
depends on the concentration of the solution and the path length of the light
trough the solution.
A = €.C.t
A →Absorbance
C →Concentration of solution.
t → path length
 € → Molar absorption coefficient which is dependent on the material
being studied.
Instrumentation
Photo electric calorimeter are made of the following components.
1. Tungsten lamp as light source
2. A filter which provides the desired wavelength range.
3. A sample cell.
4. A photocell detector.

Diagram 1: Colorimeter

1. Monochromatic light of suitable wavelength can fall on the sample cell.

2. First blank solution is taken in the sample cell and placed in the path of
light beam.
3. Its absorbance is adjusted to zero.
4. Then the analyte solution is placed in the path of light and its absorbance
is measured.
5. A plot of absorbance versus standard concentration of analyte is used to
find the unknown concentration of analyte in the samples.
Application calorimetry
1. Colorimetry is used various laboratories including clinical
laboratories for biochemical estimation.
 2. Colorimetry is used in clinical laboratories for the analysis of
biomolecules such as glucose, urea, etc.
3. Calorimetry is used soil testing laboratories for analysis of pesticides,
soil nutrients and plant nutrients.
Calorimetry is used in the estimation of copper in sample solutions.
Cu2+ ions are treated with NH3 to form a deep blue colored cupra-
ammonium complex ion.
1. From a burette add 2, 4, 6 and 8 Cm3 of given copper sulphate
solution into four separate 50 cm3 in volumetric flask.
2. From another burette add 5cm3 of ammonia to each one of them, to
the unknown solution and blank solution flask.
3. To the entire six flasks add water up to the mark. Mix well wait for
10 minutes.
4. In the colorimeter set the wavelength of light to be 620 nm.
5. Using blank solution, set absorbance of colorimeter as zero
6. Record Optical density values for all the solutions including Test.
7. Plot a graph of absorbance against volume of CuSO4. Determine the
volume of CuSO4 is unknown solution from the graph.

UNKNOWN
ABSORBANCE
UNKNOWN
VOLUME

Graph 1. OD Vs Vol of NaOH

Potentiometric sensors – estimation of iron
Potentiometer
Theory
The measurement of e.m.f. (electromotive force) to determine the concentration
of ionic species in solution is referred to as potentiometry.
The relation between electrode potential and metal ion concentration is given by
Nernst equation.
E = EO + 0.591 log Fe+2
N Fe+3
Instrumentation

Diagram 4: Potentiometer

1. Potentiometer consists of a reference electrode, and indicator electrode and a

device for measuring the potential.
2. The indicator electrode respond rapidly to the changes in the potential due to
the concentration changes of the analyte.
3. A known volume of the analyte is taken in a beaker and its potential is
determined by connecting the assembly to a potentiometer.
4. The titrant is added in increments of 0.5ml and the potential is measured each
time.
5. The equivalent point there is a sharp increase in the potential against the
volume of titrant.

Graph 3: ∆E/∆V Vs Vol of K2Cr2O7

6. Redox titration is that of ferrous ammonium sulphate (∆E/∆V) against K2Cr2O7

or KMnO4.The oxidizing agent is usually taken in the burette.
Application
1. It is used in oxidation reduction titrations to estimate the concentration of
analyte in the sample solution.
2. The potential of the electrode depends on the concentration of the substance
being oxidized or reduced.
Advantages
1. Potentiometric titrations (estimation) does not depend on color change or redox
indicator.
2. Several analyte present in the same solution can be estimated by as single
titrating solution.
Conductometric sensors – estimation of weak acid.

Conductometer
Theory
Electrolyte solution conducts current by the migration of ions under the influence
of an electric field.
E= I R
Where; I → current, R→ Resistance
Ohm’s law states that the current’ I ‘ flow through conductor is directly
proportional to the applied potential, E and inversely to the resistance R of
conductor.
The reciprocal of resistance is called the conductance. The resistance of
homogenous material of uniform cross-section with an area of ‘ a’ sq.cm and
length ‘l’ cm is given by
R= Ᵽ. l/a
Ᵽ → Specific resistance, l→ length, a → area cross- section.
Specific conductance
Specific conductance of an electrolyte solution is the conductance of the solution
present between two parallel electrodes of 1cm3 area of cross-section and 1cm
apart.
K= 1/R x l/a
Where l/a is known as the cell constant
‘R’ is the resistance of solution
K = Cell constant
Resistance
Instrumentation
1.It consists of a platinum electrode each of unit area of cross-section placed unit
distance a part.
Diagram to be passed
2. The electrodes are dipped in the electrolyte solution taken in a beaker.
3. It is connected to a conductance measuring device.
4. The titrant is added from a burette and solution is stirred.
5. The conductance is measured after the addition of the titrant at intervals of 0.5
ml.

Diagram 5: Conductometer

Application of conductometry
1. Strong acid with strong base (HCl vs NaOH)
NaOH + HCl → NaCl + H2O
1. Consider the titration of strong acid HCl with a strong base NaOH.
2. You will notice that on addition of NaOH the conductance of acid solution
decreases gradually until the acid is completely neutralized.
3. A plot of conductance against the volume of NaOH is shown in the figure.
4. The point of intersection of the two lines is the neutralization point.
5. The conductance decreases, because the small and highly mobile H+ in the
acid is gradually replaced by heavier and less mobile Na+ ions. Addition of
base beyond neutralization points increase in the number of more mobile
OH- ions and conductance increases.
 Graph 4: Conductance Vs Vol of NaOH

2. Weak acid with strong base

Consider the titration of acetic acid with a strong base NaOH. (CH3COOH versus
NaOH)
NaOH + CH3COOH → CH3COONa + H2O
Consider the titration of acetic acid with a strong base NaOH, the conductance of
weak acid solution increases until the acid is completely neutralized.
A Plot of conductance against the volume of NaOH is shown in the figure. The
point of intersection of the two lines is the neutralization point.

Graph 5: Conductance Vs Vol of NaOH

Acid mixture with a strong base (HCl and CH3COOH versus NaOH)
Consider the titration of acid mixture (HCl and CH3COOH) with strong base
NaOH
1.You will notice that on addition of NaOH the conductance of the acid mixture
solution decreases steeply. The conductance decreases steeply because the small
and highly mobile H+ ions in the strong acid is gradually replaced by heavier and
less mobile Na+ ions.
HCl + NaOH → NaCl + H2O
2.Addition of base beyond the first neutralization point leads to moderate increase
in conductance. The conductance increases moderately, because the poorly
conducting weak acid (acetic acid) is gradually converted to highly conducting
salt (Sodium acetate) until the second neutralization point.
CH3COOH + NaOH → CH3COONa + H2O
Further addition of NaOH increases number of highly mobile OH- ions. Hence
conductance increases steeply.

Graph 6: Conductance acid mixture Vs NaOH