MODULE 5

Sensors in Analytical techniques

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.
Self-Study Components: IR and UV- visible spectroscopy.
Electrode system:
Introduction
The classification of electrodes not only depends on electrode material but the full
electrode system comprising of electrode and electrolyte as well as additional substances
that may be involved in the reaction.

Types of Electrodes
Electrodes can be classified as
Metal - metal electrode
Metal is in contact with a solution of its own ions.
Ex: Zinc rod is in contact with ZnSO4 solution (Zn/Zn2+).
Metal – metal salt ion electrode
Metal is in contact with insoluble or sparingly soluble salt as a solid phase next to the
electrode immersed in a solution containing anions of the same metal salt.
Ex: Calomel electrode consisting of mercury in contact with insoluble mercurous chloride
in contact with KCl solution is an example of this type (Hg/Hg2Cl2/KCl).
Gas electrodes
Electrode system in which one of the electrode materials is a gas bubbled over inert metal
in contact with a solution containing ions or electrodes at which gases are evolved or
consumed are called gas electrodes.
Ex: Hydrogen electrode (Pt/H2/HCl).
Amalgam electrode
Amalgam of a metal is in contact with solution containing its own metal ions. Highly
reactive metals are used in the form of amalgams since the activity of the metal can be
varied.
Ex: Znc in mercury is in contact with zinc sulfate solution [Zn2+/Zn(Hg)].
Redox electrode
Inert electrode is in contact with a solution containing metal ions of different oxidation
states.
Ex: Platium electrode is in contact with a solution containing mixture of Fe2+ and Fe3+ ions
[Pt/Fe2+ (a1), Fe3+ (a2)].
Ion selective electrodes
Electrodes which have the ability to respond to the specific ion. Ion-selective electrode (or
membrane electrode) is used for determining the activities of various ions in aqueous
solutions. The potential developed by this electrode depends only on the activity of ionic
species of interest.
Ex: Glass electrode, which is specific to H+ ions.

Ion selective electrode (ISE):

Ion selective electrodes are also called as membrane electrodes or ion sensitive
electrodes. These electrodes are fundamentally different from metal electrodes both in
design and in principle. All the ion selective electrodes make use of a kind of membrane
which has selectivity for a certain specific ions. Hence, the potential developed by the ion
selective electrode is a measure of concentration of specific ions in the solutions.
Definition: Ion selective electrodes are the electrodes that respond to certain specific ions
present in a solution containing mixture of ions and they develop potential due to the
presence of these specific ions by ignoring the presence of other ions in the solution.

Glass electrode
It is more selective towards H+ ions in the solution containing mixture of ions and
hence it is used in the measurement of concentration of H+ ions (pH) in the solution.
Besides use for pH measurement, glass electrodes are also used in various sensors
involving proton-generating or proton consuming reactions.
Construction
 Glass electrode consists of a long glass tube with glass membrane bulb at the
bottom.
 Glass membrane is made up of high electrical conductivity corning glass with
composition of 72% SiO2, 22% Na2O and 6%CaO. Its thickness varies from 0.03 – 0.1
mm.
 Ag/AgCl electrode is immersed in 0.1 M HCl solution and is used as internal
reference electrode to measure boundary potential (potential developed across the
membrane) and also for making electrical contact with other electrodes.
 Glass electrode is represented as Ag(s) / AgCl(s) / HCl(0.1M) / glass membrane
 Glass membrane involves an ion exchange reaction between sodium ions in the
interstices of the glass lattice and hydrogen ions from the solution. The ion exchange
reaction can be written as:
Working
When a glass membrane is placed between two H+ ion solution of different
concentrations, a boundary potential developed Eb or EM across the membrane. This
boundary potential depends upon concentration of H+ ions in two solutions.

Analyte solution (C1) HCl (0.1 M) = C2 Ag / AgCl Electrode

E1 E2

Membrane

1. The potential developed by Ag/AgCl electrode in contact with 0.1 M HCl solution
(Eref).
2. Potential developed by the glass membrane is Eb or EM and is given by
EM = E1 – E 2
Where, E1 and E2 are the potential which appear at the two surfaces of the glass membrane
as a consequence of ion exchange reaction between Na+ of glass and H+ in the solution.
C2 is constant = concentration of H+ ions iln the internal standard solution.
Hence, L = Constant = -0.0591 log C2 and n = 1
Therefore, EM = L + 0.0591 log C1
The potential of glass electrode is given by
Eg = EM + Eref + Easym
Therefore, Eg = L + 0.0591 log C1+ Eref + Easym
Eg = Egº + 0.0591 log C1 (where Egº = L+Eref +Easym)
Eg = Egº - 0.0591 (-log C1)
Where (-log C1) = -log [H+] = pH
Therefore, Eg = Egº - 0.0591 pH

Addition information:

Asymmetry potential (Easym): when identical solutions and reference electrodes are placed on
the two sides of the glass membrane i,e., C1 = C2, membrane potential EM should be zero.
However a small potential is developed on the membrane, i.e., E M≠0. This is due to the difference
in the radius of curvature of the glass membrane as a result of difference in strain on the two
surfaces of the membrane, a mechanical abrasion on the outer surface during use and chemical
etching of the outer surface.

Application
Determination of pH using glass electrode
In order to determine the pH of any solution, a galvanic cell is constructed by
combining glass electrode with saturated calomel electrode (SCE, reference electrode).
The EMF of the cell is measured using highly sensitive potentiometer. EMF of the cell is
measured twice; first immersing cell assembly in a solution of unknown pH and second
time immersing cell assembly in a buffer solution of known pH. Schematic representation
of the cell is given below:
EMF of the cell, Ecell(u) when immersed in solution of unknown, i.e., pH(u) is
Ecell(u) = Ecathode - Eanode
Ecell(u) = Eg - ESCE
Ecell(u) = Egº - 0.0591 pH(u) - ESCE (since, Eg = Egº - 0.0591 pH)
Ecell(u) = K - 0.0591 pH(u) (1)
(where K is constant and K = Egº - ESCE)
The value of constant K can be determined by measuring EMF of the above galvanic
cell immersed in standard buffer solution of known pH. EMF of the above cell, Ecell(b), when
immersed in a buffer solution of known pH, pH(b) is,
Ecell(b) = K - 0.0591 pH(b)
K = Ecell(b) + 0.0591 pH(b)
Substituting value of K in equation (1)
Ecell(u) = Ecell(b) + 0.0591 pH(b) - 0.0591 pH(u)
0.0591 pH(u) = Ecell(b) + 0.0591 pH(b) - Ecell(u)
Therefore,
Ecell(b) - Ecell(u)
pH(u) = pH(b) at 298 K
0.0591

Thus, pH of any given solution can be determined by measuring EMF of the above galvanic
cell immersed in buffer solution and then in solution of unknown pH.

Reference electrodes:
An electrode of known potential with respect to which potential of other electrode
can be measured is called as a reference electrode.
There are two types of reference electrodes
(i) Primary reference electrode and (ii) Secondary reference electrode.

Secondary Reference Electrode

Potential of these electrodes is first measured with respect to SHE and then, that
potential value is used as standard reference value to measure the potential of any other
electrode.
An electrode whose potential is measured with respect to SHE and then can be
used as reference electrode for measuring potentials of other electrodes is referred
to as secondary reference electrode.
There are two electrodes in this class and both are metal-insoluble salt electrodes.
1. Calomel electrode 2. Ag/AgCl elecrode

Calomel electrode
Calomel electrode is the most important electrode of all the secondary reference
electrodes. This is also called mercury-mercurous chloride electrode.
Construction:
 Calomel electrode is metal-metal salt ion electrode. It consists of mercury,
mercurous chloride and solution of KCl solution.
 It consists of a glass tube with two side tubes. One at the top is used to fill KCl
solution and the other side tube will serves as a salt bridge (may not be
compulsorily present) when coupled with the other half cell.
 Mercury of high grade purity is placed at the bottom of the glass tube over which a
layer of paste of mercurous cholride (calomel) is added.
 A solution of KCl is introduced above the paste through the side tube.
 A platinum wire dipped in the mercury later is used to measure potential of the
electrode and also for making electrical contact with other electrodes.
 The concentration of KCl solution used is either decinormal, normal or saturated.
Correspondilgly, the electrode is known as decinormal, normal or saturated calomel
electrode, respectively.

Working
The calomel electrode can be represented as Hg / Hg2Cl2 /Cl-
Calomel electrode may act as anode or cathode with respect to other electrode.
When it acts as anode, the electrode reaction is:
2Hg + 2Cl- → Hg Cl + 2e-
2 2
When it acts as cathode, the electrode reaction is:
Hg Cl + 2e- → 2Hg
2 2 + 2Cl-
The net reversible electrode reaction is,

Hg2Cl2 2e- 2Hg (l) + 2Cl-

(s)
 Electrode potential of calomel electrode is given by Nernst equation is,

0.0591 log K
ECalomel = Eo
n
0.0591 log [Cl-]2 {Where K = [Hg]2 [Cl-]2 and [Hg] = 1}
ECalomel = Eo
2

Hence, the electrode potential is decided by the concentration of chloride ions and the
electrode is reversible with chloride ions. At 298 K, the electrode potentials are as follows:
For 0.1 N KCl electrodes, the electrode potential is 0.334 V
For 1.0 N KCl electrodes, the electrode potential is 0.281 V
For Saturated KCl electrodes, the electrode potential is 0.2422 V.

Applications
 It is used as a secondary reference electrode in the measurement of single electrode
potential.
 It is the most commonly used reference electrode in all potentiometric
determination.
 Simple in construction.

Concentration cells
The electrode potential is dependent on the electrolyte concentration, with which the
electrode is in contact as given by Nernst equation. If two electrodes of the same metal are
in contact with solutions of its ions with different concentrations, they differ in their
electrode potentials. The coupling of two such electrodes also constitutes a cell and gives
rise to an EMF as the electrodes differ in their electrode potentials.
Definition: Cells which consists of two electrodes of the same substance in contact with
same solutions of different concentrations and the EMF arises due to the difference in
concentrations are known as concentration cells.

Electrolyte concentration cells

It is a galvanic cell in which electrode and electrolyte present in both half cells are
same but only the concentration of electrolyte is different.
Metal immersed in dilute solution will have lower potential and it is taken as anode,
whereas, metal immersed in concentrated solution will have higher potential and it is taken
as cathode.
A typical concentration cell in illustrated below:
In this concentration cell, two zinc electrodes are immersed in zinc sulfate solutions of
concentrations C1 and C2. The cell can be represented as:
Zn / Zn2+ (C1) // Zn2+ (C2) / Zn
Zinc immersed in dilute solution acts as anode, where oxidation occurs
Zn(s) Zn2+ (C1) + 2e-
Zinc immersed in concentrated solution acts as cathode, where reduction occurs
Zn2+ (C2) + 2e- Zn(s)
There is no net cell reaction. At one electrode zinc atoms go into the solution and at the
other electrode equal numbers of zinc atoms are deposited.
The EMF of the cell is given by,
Ecell = Ecathode - Eanode

2.303 RT logC 2.303 RT logC

Ecell = Eo 2 Eo 1
nF nF

2.303 RT logC1
Ecell = logC2
nF
2.303 RT C2
Ecell = log
nF C1
OR
0.0591 log C2
Ecell =
n C1
 It is evident from the above expression that Ecell can be positive only if C2 > C1.
 The EMF of the cell is dependent on the ratio of electrolyte concentrations at two
electrodes. Higher the ratio (C2 / C1) higher is the EMF.
 Therefore the cell can operate only as long as the concentration terms are different.
 When current is drawn from the cell, C1 increases and C2 decreases and as a result
the EMF of the cell goes on decreasing and becomes zero when the two become
equal.
Numerical problems
1. A galvanic cell is obtained by combining two zinc electrodes immersed in zinc
sulfate solutions of concentrations 0.05 and 0.25 M at 30 ºC. give the cell
representation, cell reaction and calculate the EMF of the cell.

Soln.:
Given, concentration of ZnSO4 at anode is 0.05 M (C1) and concentration of ZnSO4 at
cathode is 0.25 M (C2).
R = 8.314, F = 96500 and T = 30 ºC = 303 K
Cell represntation : Zn / Zn2+(0.05M) // Zn2+(0.25M) / Zn
Reaction at anode Zn Zn2+(0.05M) + 2e-
Reaction at cthode Zn2+(0.25M) + 2e- Zn
EMF of the cell, Ecell is given by,
2.303 RT C2
Ecell = log
nF C1
2.303 x 8.314 x 303 log 0.25
Ecell =
2 x 96500 0.05

Ecell = 0.03 x 0.6989

Ecell = 0.02 V
2. Calculate the EMF of the following concentration cell at 298 K
Ag(s) / Ag +(0.01M) // Ag +(0.5M) / Ag(s).

Soln.: Given, C1 = 0.01 M and C2 = 0.5 M

R = 8.314, F = 96500 and T = 298 K
Reaction at anode Ag Ag +(0.01M) + e-
Reaction at cthode Ag +(0.5M) + e- Ag
EMF of the cell, Ecell is given by,
2.303 RT C2
Ecell = log
nF C1
2.303 x 8.314 x 298 log 0.5
Ecell =
1 x 96500 0.01
Ecell = 0.0591 x 1.6989
Ecell = 0.10 V

3. EMF of the cell Cu / CuSO4(0.01M) // CuSO4(x M) / Cu at 300 K is 0.015 V. find the

concentration of CuSO4at cathode.
 Soln.: Given, Ecell = 0.015 V, C1 = 0.01 M and C2 = ?
R = 8.314, F = 96500 and T = 300 K
2.303 RT C2
Ecell = log
nF C1
By rewriting the above equation for C2
Ecell x n x F
C2 = C1 x Antilog
2.303 x RT

C2 = 0.01 x Antilog 0.015 x 2 x 96500

2.303 x 8.314 x 300

C2 = 0.01 x Antilog 0.5039

C2 = 0.01 x 3.19
C2 = 0.0319 M
The concentration of CuSO4at cathode is 0.0319 M

4. EMF of a cell constructed by using two mercury electrodes dipped in their own salt
solution of concentration 0.01M and 0.1 M is 0.03 V. find the valency of the mercury.

Soln.: Given, Ecell = 0.015 V, C1 = 0.01 M and C2 = ?

R = 8.314, F = 96500 and T = 29 ºC = 302 K

2.303 RT C2
Ecell = log
nF C1
By rewriting the above equation for n

2.303 RT C2
n = log
F x Ecell C1

2.303 x 8.314 x 302 log 0.1

n =
96500 x 0.03 0.01
n = 2.0 x 1.0
n = 2.0
The valency of the mercury is 2.
 Optical sensors (Colorimetry)
Colorimetry or colourimetry is a technique "used to determine the concentration of colored
compounds in solution." It involves the quantitative estimation of color. A substance to be
estimated colorimetrically, must be colored or it should be capable of forming colored
complexes (chromogens) through the addition of some reagents. Colored substances
absorb light in relation to their color intensity.
A colorimeter is light sensitive instrument that measures how much color is absorbed by
an object or substance.
Theory
When a monochromatic light passes through a colored solution, some specific wavelengths
of light are absorbed which is related color intensity. The measurement of color intensity of
a colored solution by colorimetry is governed by Beer-Lambert’s law:
It states that, “the intensity of transmitted beam of a monochromatic light decreases
exponentially as the concentration and thickness of the absorbing medium increases
arithmetically”.
OR
“The absorbance of monochromatic light is directly proportional to the concentration &
thickness of the absorbing medium”.

O. D. = A = log(I0/It) = -log T = εcl

Where, O.D. = Optical density, A = Absorbance, I0 = intensity of incident light beam,
It = intensity of transmitted beam, T = transmittance, ε = molar extinction coefficient, l = the
path length and ‘c’ = the concentration (mol/L) of the absorbing medium.
Instrumentation:

Light sources: Tungsten filament lamp.

Slit: It is adjustable which allows only a beam of light to pass through. It prevents
unwanted or stray light
Condensing lenses: Light after passing through slit falls on condenser lens which focuses
the light so that, the light moves in one direction.
Filter: Made of colored glass. Filters are used for selecting light of narrow wavelength.
Filters will be absorb light of unwanted wavelength and allow only monochromatic light to
pass through.
Cuvette (sample holder): It is made up of special glass/plastic/quartz material. It may be
square/rectangular/round shape with fixed diameter (usually 1cm) and having uniform
surface.
Detector (Photocell): Detectors are photosensitive elements which converts light energy
into electrical energy. The electrical signal generated is directly proportional to intensity of
light falling on the detector.
Output: the electrical signal generated in photocell is measured by galvanometer, which
displays percent transmission and optical density.
Working:
The white light from the source passes through the slit and falls on the lens which focuses
the light in one direction and further made to fall on the filter. Filters will allow only
monochromatic light to pass through. When the filtered light hits the sample, some of the
light is absorbed. “Darker samples will absorb more of the light while; paler samples
will absorb less of the light”. The detector measures the amount of light which is
transmitted through the sample.
Applications:
 It is widely used in chemical and biochemical estimations
 It is also used in clinical laboratories for the analysis of biomolecules.
 It is used in soil testing laboratories for the analysis of pesticides, soil nutrients and
plant nutrients.
 It is used in water and food testing laboratories.

Estimation of copper
Procedure: Using burette, add 5, 10, 15, 20 and 25 mL of copper sulphate solution into five
separate 50 mL volumetric flasks. Further, add 10 mL of ammonia solution to each flask
and make up to the mark with distilled water and mix well. Blank solution is prepared by
adding 10 mL of ammonia solution to an empty 50 mL standard flask and make up to the
mark with distilled water and mix well.
Blank solution is taken in a Nessler tube and placed inside photoelectric colorimeter. The
variable diaphragm is adjusted to get zero absorbance at 610 nm. The absorbance of
each of the standard solution and also for the test solution is measured. A graph of
absorbance (OD) against concentration is plotted and concentration of test solution is
determined.
 Electrochemical sensors (Potentiometry)
Potentiometry generally refers to all the analytical methods, based on the
measurement of electrochemistry potential of galvanic cell in the absence of current state.
Potentiometry is the field of electroanalytical chemistry in which potential is
measured. The measured potential may then be used to determine the analytical quantity
of interest, generally the concentration of some component of the analyte solution.
Theory:
Potentiometric measurements enable selective detection of ions in presence of
multitude of other substances. The principle involved in the potentiometry is when the pair
of electrodes is placed in the sample solution it shows the potential difference by the
addition of the titrant or by the change in the concentration of the ions. The measured
potential is proportional to the concentration of some component of the analyte.
According to Nernst equation potential of any electrode is measure of metal ion
concentration in the analyte soution:
0.0591
E = 𝐸0 + [𝑀𝑛+ ]
log⁡
𝑛
Where, E = Electrode potential, E0 = Standard electrode potential, n = number of electrons
involved, Mn+ = Metal ion concentration.
In potentiometry, Ecell = Eind – Eref + Ej
Eind is potential of indicator electrode
Eref is potential of reference electrode
Ej is potential at the junction of the salt bridge
Instrumentation:

In potentiometry the measuring setup always consists of two electrodes:

Reference electrode: a half cell with an accurately known electrode potential, Eref, that is
independent of the concentration of the analyte or any other ions in the solution.
The ideal reference electrode:
 must have a known potential which is constant, and completely insensitive to the
composition of the solution containing the analyte;
 must be robust and easy to assemble;
Indicator electrode: This is immersed in a solution of the analyte, develops a potential,
Eind which depends on the activity of the analyte.
The ideal indicator electrode must respond in a way which is rapid, and repeatable, to
variations in concentration of single analyte ions, or a group of ions. The indicator
electrodes are chosen on the basis of the titration to be carried out.
 titration with formation of a complex or precipitate: the electrode must consist of
the same element as the cation in the reaction;
 acid-base titration: hydrogen or “glass” electrodes must be used;
 Redox titration: the materials used must be inert to chemical reaction, eg. platinum
or gold.
Potentiometer:
A basic instrument used for comparing emf two cells. A potentiometer is a three-terminal
resistor with a sliding or rotating contact that forms an adjustable voltage divider.
Applications:
 In oxidation-reduction titration to estimate the concentration of analyte
 In acid base titration to find out concentration of pKa of analyte etc.

Estimation of iron
Procedure: Pipette out specified volume of FAS solution into a 250 mL beaker and add 25
ml of dil. H2SO4. Immerse calomel electrode and platinum electrode assembly into the
beaker. Connect this assembly to the potentiometer and measure the potential. Add
standard potassium dichromate from the burette in increments of 0.5 mL and measure the
corresponding potential after thorough mixing. Take six readings after sharp increase in
the potential.

Plot a graph of ∆E/∆V versus volume of K2Cr2O7 and determine the equivalence point.
Knowing the strength and volume of K2Cr2O7, the normality & amount of FAS in the given
solution is calculated.
 Conductometric sensors (Conductometry)
Conductance is a measure of how easily electricity flows along a certain path through an
electrical element and since electricity is so often explained in terms of opposites,
conductance is considered the opposite of resistance.
Theory:
The conductance depends directly upon the number of charge particles in the
solution. All ions individually contribute to the conductance process, but the ratio of
current carried by any species is determined by its relative concentration and its inherent
mobility. In general, conductance is due to mobility of ions. The smaller an ion, the more
mobile it is and better it conducts.
The principle of conductometric titration is based on the fact that during the
titration, one of the ions is replaced by the other and invariably these two ions differ in the
ionic conductivity with the result that conductivity of the solution varies during the course
of titration. The equivalence point may be located graphically by plotting the change in
conductance as a function of the volume of titrant added.
Instrumentation:
It consists of two platinum parallel electrodes each of unit area of cross section
placed at unit distance apart. The electrodes are dipped in the electrolyte solution taken in
the beaker.

It is then connected to conductance measuring device. The titrant is added from a burette
and the solution can be mixed properly with the stirrer. The conductance is measured after
the addition of the titrant at intervals of small volume (0.5 or 1.0 mL)
Applications:
It is used in the estimation of acids and bases present in the sample solutions. Possible
combinations and conductance responses are
1. Strong Acid with a Strong Base, e.g. HCl with NaOH
2. Mixture of a Strong Acid and a Weak Acid vs. a Strong Base or a Weak Base
3. Weak Acid with a Strong Base, e.g. acetic acid with NaOH
Estimation of weak acid
Initially the conductance is low due to the feeble ionization of acetic acid. On the addition of
base, there is decrease in conductance not only due to the replacement of H+ by Na+ but
also suppresses the dissociation of acetic acid due to common ion acetate. But very soon,
the conductance increases on adding NaOH as NaOH neutralizes the un-dissociated
CH3COOH to CH3COONa which is the strong electrolyte. This increase in conductance
continues raise up to the equivalence point. The graph near the equivalence point is curved
due the hydrolysis of salt CH3COONa. Beyond the equivalence point, conductance increases
more rapidly with the addition of NaOH due to the highly conducting OH− ions.