CHEMICAL SENSORS

Chemical sensors are small devices that convert chemical information (concentration, activity,
partial pressure) into a measurable signal.

COMPONENTS OF A SENSOR:

Receptor or recognition element:

• It is the component that comes into physical contact with the analyte and interacts with it
chemically, biochemically or by physical processes like adsorption, ion exchange etc.

• Measurable changes in the system like absorbance, refractive index, conductivity,

temperature, mass or electrochemical are caused due to interaction between analyte and
receptor.

Transducers:

• Transducers detect and measure the changes in property produced in the receptor and
convert them into corresponding electrical information.

• This electrical signal is then amplified, and may be used to trigger an audible alarm, or an
actuator or may be processed and the data presented on a screen (interface).

TYPES OF CHEMICAL SENSORS

Depending on the transduction signal the

different types of sensors are optical,
electrochemical, thermal, mass sensitive
sensors
PERFORMANCE CHARACTERISTICS

The following are the parameters that are used to characterize the performance of chemical sensors.

Sensitivity: The change in the measurement signal per concentration unit of the analyte, i.e. the slope of
a calibration graph. Greater the slope better is the sensitivity.

Selectivity: If a sensor responds only to a group of analytes or specifically to a single analyte, irrespective
of the presence of other species in the sample, the sensor shows selective response. A high selectivity
(with minimal chances for interference) is desirable

Detection limit: The lowest concentration value of the analyte which can be detected by the sensor,
under definite conditions.

Dynamic range: the concentration range between the detection limit and the upper limiting
concentration. This is the concentration range in which the sensor shows an ideal linear response
(measured signal) to change in concentration.

Resolution: The lowest concentration difference which can be distinguished when the composition is
varied continuously. This parameter is important chiefly for detectors in flowing streams.

Response time: the time for a sensor to respond from zero concentration to a step change in
concentration. Usually specified as the time to rise to a definite ratio of the final value.

Hysteresis: the maximum difference in output when the value is approached with (a) an increasing and
(b) a decreasing analyte concentration range. It is given as a percentage of full-scale output.

Stability: the ability of the sensor to maintain its performance for a certain period of time.

Life cycle: the length of time over which the sensor will operate. The maximum storage time (shelf life)
must be distinguished from the maximum operating life. It should be determined whether a sensor is
suitable for continuous operation or for repeated on-off cycles

ELECTROCHEMICAL TRANSDUCERS:

Electrochemical sensors operate by reacting with the analyte of interest and producing an electrical signal
proportional to its concentration. The electrical signal may be change in current or voltage or impedance.

The types of transducers:

• Potentiometry, the measurement of a cell potential at zero current.

• Voltammetry (amperometry), in which an oxidizing (or reducing) potential is applied between the
cell electrodes and the cell current is measured.

• Conductometry, where the conductance (reciprocal of resistance) of the cell is measured by an

alternating current bridge method.
POTENTIOMETRIC SENSORS – WORKING PRINCIPLE:

Potentiometric transducers involve the measurement of the emf of an electrochemical cell at

equilibrium. The electromotive force (E or EMF) is defined as the maximum difference in potential
between the two electrodes of the cell, obtained when the cell current is zero.

The electrochemical cells designed for analytical applications consist of two electrodes :

1. Working electrode or Indicator electrode: Responds selectively to the analyte ions in a solution - also
called as an ION-SELECTIVE ELECTRODE (ISE).

AND

2. Reference Electrode : Generally Ag/AgCl/KCl 0r Calomel electrode is used.

The measured Ecell = Ecathode – E anode. One of the electrodes is the reference electrode which shows
a constant potential and the other working electrode shows a potential proportional to the activity of
analyte ions, as given by the nernst equation .

Therefore the measured cell EMF will be proportional to the activity, a of the analyte ions.

The number of active ions is called the activity of the solution and

a=Cxf

where a is the activity of the species concerned, C is concentration and f is the activity coefficient of the
ionic species. In dilute solutions, the ionic activity and the concentration are practically identical but in
solutions containing many ions, activity and concentration may differ. In order to fix the analyte solution
so that the activity and concentration of the analyte ion are equal, a constant concentration of an inert
electrolyte is added to the analyte solution. The inert electrolyte is called Ionic Strength Adjustment
Buffer (I.S.A.B.). The most commonly used ISABs are KCI, NaN03, NaOH and acetate buffer solutions.
ION SELECTIVE ELECTRODE COMPONENTS:

The potential developed in the ion-selective electrode will be a sum of the membrane potential, internal
reference electrode potential and the asymmetry potential that depends on the nature of the membrane.

E ISE = Emembrane + E inernal ref + E Ass

The membrane potential is developed as a result of either an ion exchange process or an ion transport
process occurring at the interface between the membrane and inner solution and the interface between
the membrane and outer analyte solution.

The membrane potential is given by

The difference between EISE and that provided by the Eexternal reference electrode leads to the potentiometric
readout, i.e., EMF of the electrochemical cell .

The cell is represented as

Since the reference electrode shows a constant potential, the EMF of the cell will be proportional to the
analyte ion activity.
TYPES OF ION SELECTIVE ELECTRODES (ISE):

ISE– GLASS MEMBRANE TYPE

Ion-selective membranes typically consist of (1) glass, (2) crystalline solids, (3) liquid or (4) polymeric
materials. The chemical composition of the membrane is designed to achieve an optimal permselectivity
towards the ion of interest.

Glass membrane electrode – used for A typical pH combination electrode consists of a

measuring H+, Na+, K+ , Li+, Ag+ glass bulb containing a standard HCl solution
(0.1N) with an internal reference electrode.
• The composition of the glass membrane
decides its selectivity towards a A second reference electrode is incorporated in
particular ion. a concentric glass tube around the main
electrode tube containing saturated KCl.
• The electrode used for determining pH,
called the universal pH electrode is Contact between this electrode and the test
made of special glass of relatively low solution is through a small glass frit. The two
melting point and high electrical reference electrodes are normally of the
conductivity. The usual composition of Ag/AgCl type.
the glass employed for detecting
hydrogen ions is 22% Na20, 6% CaO and
72% Si02.

• The thin glass membrane is highly

selective to hydrogen ions over a very
wide range of concentrations, with the
composition of the glass being critical
for this performance. If it is changed,
this may make the glass membrane
selective to other ions.

The basic ion – exchange reaction occurring in

the membrane is as follows:

SiO-Na+ + H+ ⇋ SiO-H+ + Na+

The cell is represented as,

 Practically, the emf of the cell formed by combining the glass and reference electrodes is measured, from
which the pH of the solution is computed using the following expression.

ISE–SOLID STATE MEMBRANE TYPE

The solid-state membrane can be a

• solid crystal, e.g., LaF3 in the fluoride ion • The fluoride electrode is regularly used
selective electrode, in water-treatment plants for measuring
the fluoride levels in drinking water.
• or a pressed pellet of powdered
material, such as AgS in sulfide
electrodes.

Flooride ion selective electrode: In the Fluoride

ion selective electrode containing a solid LaF3
crystal, which ionises as

LaF3(s)⇋LaF2+(s)+F−(aq)

• The formation of LaF2+ creates a charge

at the surface. The equilibrium will be
shifted to the right for the solution with
a smaller F- concentration, and the
potential will become more positive
relative to the other side of the
membrane.

• It is this potential difference across the

LaF3 crystal membrane that is measured
and related to F- concentration.

ISE–LIQUID MEMBRANE TYPE

An ion-exchanger or ionophore (neutral macrocyclic ion carrier) is dissolved in a viscous organic liquid membrane. This
membrane is sandwiched between two porous partitions. Ionophores cannot diffuse out of the membrane and but can
“trap” the analyte ion at the interface between the solution and membrane.

Liquid membrane based calcium ion selective electrode:

The liquid membrane electrode used for calcium determination is prepared by dissolving a cation-exchanger, which is an
aliphatic diester of phosphoric acid, (RO)2PO2-, where each R group is an aliphatic hydrocarbon chain containing between
8 and 16 carbons. The membrane is held in a porous compartment between the analyte solution and internal reference
calcium chloride solution. The membrane works by exchange of ions.
 • The phosphate group in the ion exchanger can be
protonated, but has a strong affinity for Ca2+.

• The ion-exchanger uptakes Ca2+ from the

solutions into the membrane.

Ca2++ 2(RO)2PO2−H+ ⇋ [(RO)2PO2]2Ca + H+

Due to difference in the concentrations of cacium ions on

either side of the membrane a potential is developed.

ISE–POLYMER MEMBRANE TYPE

The membrane is made of a hydrophobic material such as plasticized poly(vinyl chloride) (PVC).
A liquid ion-exchange material or ionophore is absorbed into this membrane.
The important feature of the neutral carrier molecule is its cavity, which has dimensions approximately that of a molecule
or ion.

VALINOMYCIN

The electron-rich center of valinomycin efficiently extracts

K+ ions due to the similarity between the diameter of K+ and
the inner diameter of the valinomycin molecule. The K+ ions
are transported across the membrane from higher
Example : Potassium ion selective electrode: concentration to lower concentration via the valinomycin
molecules. This leads to the development of a membrane
• Valinomycin (liquid ion exchanger) is absorbed on
potential.
to a PVC membrane.
The outer lipophilic part of the valinomycin
molecule makes it compatible with the polymeric
membrane and remains strongly attached to it.

In order to replenish and maintain the concentration of valinomycin in the membrane, a reservoir of valinomycin
dissolved in an organic solvent is provided in an outer tube.
ISE – PERFORMANCE ANALYSIS:

The performance of an ISE is ascertained by determining its characteristics like sensitivity, selectivity, detection limits
etc.

1. DETERMINATION SENSITIVITY - NERNSTIAN RESPONSE:

The potential of ion selective electrode depends on the logarithm of the ionic activity of analyte, according to the
Nernst equation.

In the expression 2.3RT/nF is termed the Slope Factor.

For example, the slope at 298K (25°C) has a value of 59.16 mV, when measuring Potassium ions, (i.e. n = +1).

The ISE is expected to show NERNSTIAN RESPONSE or an Ideal Slope Factor i.e., for each tenfold change in a
monovalent ion concentration, the ISE potential will show a change of 59.16 mV. The measurement of slope factor
gives an indication of the performance of the electrode system. This is done by construction of a calibration curve.

Calibration Curve.

• Standard solutions of different concentrations of

the analyte ion are prepared.

• The recommended Ionic Strength Adjustment

Buffer (ISAB), is added to each standard solution
.
• EMF of the ISE/reference electrochemical cell in
each of the standard solution is measured and a
plot of EMF Vs logarithm of anlyte ion
concentration is constructed, which is the
calibration curve.

Nernstian response - The ion-selective electrode is

expected to show a Nernstian response over a given
range of activity (or concentration) in which a plot of
the EMF of cell vs the logarithm of the ionic activity
of a given species (aA) is linear with a slope of
2.3RT/nF.

Note: This calibration curve can also be used to determine analyte concentration in unknown solutions. This is done
by measuring the EMF of the cell in the unknown solution, to which the ISAB is added. The concentration of ions
corresponding to the measured EMF can be read from the graph
 2. DETERMINATION OF DETECTION LIMITS:

Detection limits are also determined from calibration graphs. Detection limit is the concentrations of the ion
below and above which the ISE does not give reliable results. A calibration curve ordinarily has the shape shown
in figure given below.

The practical limit of detection may be taken as the activity (or concentration) of A at the point of
intersection of the extrapolated linear segments of the calibration curve.

3. DETERMINATION OF SELECTIVITY:

• Ion-selective electrodes are selective but not specific. The ion to be determined is referred as the primary
ion (determinant) and other ions to which the electrode responds are known as interfering ions (interferent).

• The preference of an electrode for the primary ion over the interfering ion is called the selectivity of the
electrode.

• To take into account, the response of the electrode to an interfering ion, an additional term is incorporated
in the nernst equation. This new equation is called the Nikolskii-Eisenman equation.

Where CA and CB are the concentrations of the analyte and the interfering ion with charge z and kA,B is the selectivity
coefficient.

• Selectivity coefficient, KA,B is a numerical value indicating how well the electrode can discriminate
the analyte ion against the interfering ion. Good selectivity is obtained when the selectivity
coefficient is sufficiently low in order to render the k A,B term negligible when compared with CA.

• The smaller the kAB values, the less impact the interfering ion will have on the measured potential.
When kAB values are less than 1, the ISE is more responsive to the analyte ion, A and when kAN values are
greater than 1, the ISE is more responsive to the interfering ion. For example, a kAB value of 0.01 means that
the electrode is 100 times more responsive to ion A over B. For example,
AMPEROMETRIC TRANSDUCERS
A fixed potential is applied to an electrolytic cell containing the analyte, to carry out a redox reaction and the
current is measured. The current is proportional to the analyte concentration
Sensitivity:
 Sensitivity of amperometric sensors is greater than potentiometric sensors.
 The sensitivity of a potentiometric sensor is limited by the Nernstian response of the system under
test. (i.e. 59/n mV for a 10-fold change in analyte concentration). For example, a redox reaction
involving a two electron transfer will only result in a 29 m V change for a 10-fold change in the
analyte concentration at 25°C.
 But with amperometric devices, the current resulting from such an oxidation and for such a
concentration change will be about twenty times that for a single electron transfer reaction.

AMPEROMETRIC CELLS:
Electrochemical cells used in amperometric transducers generally are three electrode configurations as shown
below.
The cell consists of : • A Polarisable working electrode
• A non- polarisable reference electrode and
• A counter electrode with area much larger
than the working electrode.
• The voltage is applied to the cell by means
of an electronic instrument called a
potentiostat.
• This instrument allows the electrolytic
current to flow between the working and
counter electrodes, whilst no current flow
through the reference electrode. Therefore,
the equilibrium at the reference electrode is
not disturbed.
• The large area of the counter electrode ensures a very low current density and hence only small
deviations from the equilibrium state.

• The current measured will be only due to the reaction of the analyte at the working electrode.
• Platinum and glassy carbon are typical counter electrode materials.
• Generally the reaction at these electrodes is oxygen or hydrogen evolution, depending on the
electrode polarity.
WORKING PRINCIPLE OF AMPEROMETRIC SENSORS:
A potential is applied to the working electrode wherein the analyte undergoes oxidation or reduction at the
electrode (depending on whether an anodic or cathodic potential is applied).
Suppose the WE is cathodically polarised, the analyte undergoes reduction at the electrode as

Where Ox and Red are the oxidised and reduced forms of the analyte.

According to Faraday’s law, reduction of 1 mole of analyte, Ox (and formation of 1 mole Red) involves the
exchange of nF coulombs of electricity (F is the Faraday constant). The cathodic current i is proportional to the
rate of the electrochemical reaction, Ve and is given as:

Where A is the area of the electrode and Ve is the rate of the electrochemical reaction.
As the reaction proceeds, the Ox concentration at the electrode surface decreases and soon a concentration
gradient is set up near the electrode surface upto a certain distance from the electrode (called the diffusion layer),
as shown in the figure.

• The concentration of the analyte increases

from Coi at the electrode surface to Cob(bulk
concentration of analyte) at the end of the
diffusion layer as shown in the figure.
• When the analyte solution is constantly
stirred, the concentration gradients become
localised within a very thin layer of length
δo near the electrode surface. Concentration profile of analyte in the diffusion layer
For the reaction to proceed further, the analyte must be transported from the bulk to the electrode surface
across the diffusion layer. The rate of the reaction will depend on the rate of analyte mass transport. This
transport can occur by
 Diffusion - displacement of molecules or ions from a region of a higher concentration to
a region of a lower concentration.
 migration of ions due to the electric field
 Convection - movement of the whole solution, carrying the charged particles with it .
Reproducible convection conditions can be achieved by stirring the solution.
For obtaining current proportional to analyte concentration, the electrochemical reaction is carried
out under diffusion mass transport control, by eliminating migration.
• Migration is suppressed by the addition of excess of an indifferent electrolyte (base electrolyte)
to the sample solution. The supporting electrolyte ions will be the major current carrying ions,
thus reducing the transport number of the analyte ions. A simple salt (such as KNO3, NaClO4 or
KCl) can act as supporting electrolyte.
• In addition, the supporting electrolyte imparts good electrical conductivity to the solution and
lessens the ohmic potential drop.
When migration is prevented,
The rate of electrochemical reaction = rate of diffusion of the analyte from bulk to electrode surface.
Limiting current and concentration of electrolyte:
The potential to be applied for amperometric measurements is determined from a voltammogram. When
voltage applied to the cell is varied and current is measured, the following current-voltage curve is
obtained, called the voltammogram.

The current levels off after a sharp rise and becomes independent of the applied voltage; this is called a
limiting current. The limiting current is proportional to the concentration of the analyte as
where i is the measured current in amperes,
n equals the number of electrons in the electrochemical reaction (reduction in this case)
F is Faraday’s constant (96,487 coulombs/mol )
A is the electrochemical surface area of the working electrode (in cm2)
D is the diffusion coeffcient (in cm2/s) of the electroactive species (Ox in this case)
δ is the diffusion layer thickness (in centimeters), ( by maintaining constant stirring
conditions in the solution i.e., convection, the diffusion layer thickness remains small
and constant).
C is the concentration of the analyte species in mol/cm3.
The D/ δ term is often denoted as mo, the mass transfer coeffcient of the Ox species to the
surface of the working electrode.

E1/2 Value from votammogram:

In the voltamogram, the potential of the working electrode that corresponds to a current that is exactly
one-half the limiting current is termed the E½ value. This value is not dependent on analyte concentration
but is determined by the thermodynamics (E°) of the given redox reaction. Hence, the E½ values is
characteristic of an electroactive species and helps in identifying electroactive species and also to
distinguish one electroactive species from another in the same sample, if the E½ values for various
species differ significantly (e.g., >120 mV)..

Amperometric measurements are performed under stable stirring conditions, at fixed potentials
(greater than E1/2 values) and the limiting current measured will be proportional to the
concentration of the analyte.
-----------------------------------------------------xxxxx-------------------------------------------------------------------
-
NOTE:
1. Diffusion membranes are included in designing the sensors:
• Amperometric sensor design mostly includes membranes with selective permeability.
• This is because the limiting diffusion current depends on the thickness of the diffusion layer,
which, in turn, is determined by the convection conditions (e.g., stirring rate and stirring
procedure).
• Reliable results are obtained in amperometric determinations when performed only under stable
and reproducible convection conditions. This is difficult to be brought into the sensor design. If
the sensor is operating without convection conditions, the diffusion current shows large
fluctuations owing to spontaneous convection in the solution that affects randomly the thickness
of the diffusion layer.
• By incorporating a membrane, permeable to the analyte such that about a 10 μm solution layer
is sandwiched between them, the current fluctuation is eliminated.
The membrane
 causes the current to be almost independent of the convection in the test solution.
BIOSENSORS

A biosensor is an analytical device which is used to determine the presence and concentration of a
specific substance in a biological analyte.

Bioreceptor may be an antibody, enzyme, nucleic acid (DNA) or cell. Transducer may include optical
(absorption, fluorescence, interference), Electrochemical (potentiometric, amperometric, conductometric),
Mass based, Temperature based, Electric and magnetic based transducers.

AMPEROMETRIC GLUCOSE BIOSENSOR: WORKING MECHANISM:

Glucometers allow diabetic patients to monitor their blood glucose levels with a minimal amount of blood
sample. Most of the glucose biosensors are based on amperometric transducers. They utilize disposable
electrochemical cells called test strips. These strips consist of a three electrode system as shown below.

(i) working electrode(WE) at which the

active species undergoes the reaction. It is a Pt
strip coated with a thin film of a conducting
polymer like polyaniline, containing an enzyme,
glucose oxidase(GOx) and a mediator species
immobilised in it.

(ii) reference electrode(RE) made of

Ag/AgCl. The potential of WE electrode is
controlled relative to the RE.

(ii) counter electrode(CE) (made of Pt or

carbon).
A potential is applied across the working and the reference electrode, and the current passing between the
working and the counter electrode is measured. The schematic diagram of amperometric cell is shown below.

The current measured is equivalent to the quantity of glucose in the blood sample and it is computed in terms
of amount of glucose in mg/dL and displayed in the screen.

Electron Transfer processes at the working Electrode :

When blood is placed on the test strip, glucose is oxidized to gluconolactone by enzyme coated on a working
electrode. The reaction steps involved in the electron transfer at the working electrode are:
Step 1: Oxidation of Glucose by Enzyme
The enzyme GOx, oxidises glucose molecules in the blood to gluconate and the cofactor of the GOx i.e.,
flavin adenine dinucleotiede (FAD gets reduced to FADH2.)

Glucose + GOx (FAD) → Gluconate + GOx (FADH2)

Step 2: Reoxidation of the enzyme by a Mediator

The GOx(FADH2) is reoxidised to GOx(FAD) by a mediator molecule which is capable of existing in both
oxidized and reduced forms and reacts quickly to donate or receive electrons. E.g., ferrocene derivatives,
quinone derivatives.

GOx(FADH2) + mediator → GOx(FAD) + reduced mediator

The mediator in turn delivers the electrons to the working electrode for electrochemical measurement. Thus
the whole process involves electron transfer reactions starting from glucose to the working electrode:

Glucose → Gox → mediator → working electrode.

Role of mediators in facilitating electron transfer is shown in the schematic representation.

LATEST TECHNOLOGIES:
Latest technology aims at eliminating the use of mediator species and incorporates features that facilitate
direct electron transfer between the electrode and active center of enzyme, in the test strips.
The major hindrance for direct electron transfer is the intrinsic barrier in the enzyme to electron flow
because the active site of GOx enzyme is buried deep inside a cavity of ~13A◦ in the globular structure of
GOx. Direct electron transfer can be achieved by using charge transter complexes (conducting organic salts)
like tetracyanoquinodimethane (TCNQ) and tetrathiafulvane (TTF). Single walled carbon nanotubes
(SWCNTs) immobilized vertically on the electrode surface also provides suitable orientation for enzyme
immobilization and establishing connection between electrode surface and the deeply buried active site of the
enzyme.
CONDUCTOMETRIC TRANDUCERS: Detection and determination of concentration of
analytes by conductometric transducers are based on measuring the changes in conductivity
occurring in a solution or in chemoresistive materials such as conducting polymers or metal
oxides embedded within the sensing element.

Conductivity occurring in a solution is due to migration of ions i.e., electrolytic

conductance.

Factors influencing electrolytic conductance:

i. Concentration of ions:– it depends upon whether the electrolyte is strong (Completely

ionized- HCl, NaCl, H2SO4) or weak (partially ionized – CH3COOH, NH4OH, HCOOH).

ii. Mobility of ions: Distance travelled by an ion under a unit potential gradient (1V/cm). H+ and
OH- ions have high nobilities compared to any other ions. This is because H+ and OH- ions
migrate from one water molecule to another through the rearrangement of H-bonds (hopping
mechanism). For other ions, smaller ions are more solvated because of their greater charge
densities and so are less mobile compared to larger ions.

iii. Temperature : As temperature increases, conductance increases.

iv. Solvent: If the viscosity of solvent is high, lesser is the conductance. If the dielectric constant
of the solvent is higher, higher will be conductance of the electrolyte.

Measurement of Conductance:

The conductance of a solution is measured in using a conductance bridge which works based on
wheatstone principle. A Wheatstone bridge is an electrical circuit used to measure an unknown
electrical resistance by balancing two legs of a bridge circuit (R1 and R2 are constant), one leg of
which includes the unknown component (R4) and R3 is a variable resistance is adjusted.

R1/R2 = R3/R4
The conductivity cell contains of two parallel platinized platinum foils of one cm2 area separated
one cm apart. These foils are fused in a glass cylinder and connected to contacts the wire as
shown in the figure. Alternate current of higher frequency (1KHz) is used in conductometric
titration to avoid polarization of the electrodes. If DC is applied the ions in the solution migrate
and may get discharged at the electrodes (electrolysis may occr).

Specific conductance or conductivity of the solution (Scm-1)

= the measure conductance (S or Ω-1) x cell constant (cm-1)

Applications of conductance measurement:

1. It can be used for acid base, redox, precipitation, or complexometric titrations and for the
titrations between weak acids and weak bases.
2. Used when colored or turbid solutions are to be titrated, in which end point cannot be seen by
the naked eye.
Estimation of Mixture of acid strength using base

HCl +CH3COOH Vs NaOH

The conduction of electricity through a solution is due to the movement of ions present in that
solution. When known volume of the base (say NaOH) is added into the acid mixture containing
both strong and weak acids (say HCl & CH3COOH). The strong acid is neutralized first and then
followed by the neutralization of weak acid because the weak acid and its dissociation is further
suppressed due to the presence of H+ (common ion effect) from the strong acid, therefore weak
exists practically in the unionized form in the solution and does not react with the base till all the
H+ from strong acid are consumed. The fast moving hydrogen ions present in strong are
progressively replaced by slow moving sodium ions. As a result, conduction of the solution
decreases till the complete neutralization of strong acid occurs. The reaction between strong and
base is represented as, H +Cl- + Na+OH- → Na+ Cl- + H2O and this reaction account for the first
neutralization point. After the complete neutralization of strong acid, the neutralization of weak
acid, commences. CH3COO- H + + Na+ OH- → CH3COO- Na+ + H2O and this reaction account
for the second neutralization point. Now the conduction of solution slowly increases with the
addition of strong base, due to the formation of readily ionisable salt of weak acid (CH3COONa).
When all weak acid is neutralized, further addition of strong base causes steep increase in
conductance due to the availability of fast-moving hydroxide ions.
 From the first intersection point of the
straight lines, the titre value of sodium
hydroxide required to neutralize the strong
HCl is obtained. The difference between the
second and first intersection points(V2-V1)
gives the titre value of sodium hydroxide
required to neutralize the acetic acid. From
the volumes of NaOH, the strength and of
strong and weak acids are calculated.

First decrease in conductance is due to

CO2 sensor using chemiresistive material:

Chemiresistive materials are those which show changes in electrical resistance in the presence of
a target chemical.

The sensing principle for polyaniline CO2 sensor, which consists of a thin uniform polymer film
lying on the top of a pair of coplanar electrodes supported by an insulating substrate.

Dissolved CO2 in aqueous solution exists as a weak carbonic acid or as bicarbonate and
carbonate in basic solutions.

CO2 + H2O ↔ H2CO3 (H+ + HCO3-)

CO2 + H2O ↔ H+ + CO32- Protonic acid doping of the insulated polyaniline and form the
conductive counter part.

The increase in CO2 concentration results in the changes of the pH of the internal electrolyte with
proton production, the conductivity increases as of the doping of polyaniline by the protons.
The increase of conductivity reduce the resistance of polymer layer and thereby the
concentration of CO2 can be measured. Adsorption is the key and the first step in all the sensing
techniques. The adsorbability of H2O and CO2 onto polymer film influences the sensing
properties and the working range of sensing materials.
 DETERMINATION OF FERRIC IRON BY PHOTOCOLORIMETRIC METHOD
COLORIMETRY PRINCIPLE:
Quantitative chemical analysis by colorimetric method is based on the analysis of light
absorption by a coloured analyte species or by a coloured compound of the analyte species
that is generated by the addition of a reagent.

The absorption of light by the analyte is directly proportional its concentration in the sample.
The relationship between absorbance (A) and the concentration is given by Beer-lamber’s law.
𝐼𝑜
𝑙𝑜𝑔 = 𝐴 = e 𝐶𝑥
𝐼
Where, 𝐼𝑜 = Intensity of incident light, I = intensity of transmitted light, e molar absorption co-
efficienty, x = thickness of the cell and C = concentration of the solution. From the equation it
is seen that, the absorbance (A) is directly proportional to molar concentration and thickness of
the cell.

PHOTOCOLORIMETER:
Colorimetric analysis is carried out using a colorimeter, which measures the absorbance of
light of specific wavelength that passes through the coloured sample taken in the cuvette. A
simplified diagram of the photocolorimeter is shown in the figure given below.

When a sample is placed in the

colorimeter, light of selected wavelength
enters the cuvette and any light that is not
absorbed is transmitted to a photocell
detector. The detector generates an
electric signal. The instrument displays the
absorbance values that depend on how
much light is absorbed by the analyte in the
sample.
 Estimation of Ferric iron by Colorimetry:
Iron exist in two oxidation states namely Fe2+ and Fe3+. Iron in the +3 oxidation state (ferric
ion) reacts with thiocynate to form intensely colored (blood red) complex, using which the
amount of Fe3+ ion can be quantitatively determined using photocolorimetric principle.

𝐹𝑒3+ + 6𝐾𝐶𝑁𝑆 [𝐹𝑒(𝐶𝑁𝑆)6]3 ─ + 6𝐾 +

3-
The red color is due to the formation of [Fe(CNS)6] complex. Color is the human eye’s
perception of reflected radiation from an object in the visible region of the electromagnetic
spectrum (400–700 nm). The intensity of the colour depends quantitatively on the amount of
Fe3+ ions present in the sample. This red colour intensifies as the Fe3+ ion concentration
increases.
Fe3+ reacts with water by a hydrolysis reaction and gets precipitated as Iron (III) hydroxide,
decreasing the amount of iron available in solution to complex with thiocyanate
𝐹𝑒3+ + 3 𝐻2𝑂 𝐹𝑒 (𝑂𝐻)3 + 3𝐻+
In order to suppress the hydrolysis reaction, the experiment is conducted in acid medium.

Construction Calibration Curve:

The colorimetric procedure involves making up a series of known Fe3+ ion solutions and
treating them with potassium thiocyanate. At the same time, the unknown solution (whose
iron concentrations are to be determined) is also treated with the KSCN. After the
development of colour in these solutions, the colour of the unknown solution is compared
with the known standard solutions using a photo calorimeter.

The absorbance values of each sample is read using a colorimeter and a graph of
concentration of each known iron solution is plotted against its absorbance. The graph gives
a straight line, called a calibration curve.

The calibration curve enables one to determine the iron content of the unknown solution
by measuring the absorbance of the unknown solution and reading the corresponding
concentration of iron in ppm on the calibration curve.