MODULE -5

Sensors and Electrode System in Analytical Techniques

Electrochemistry: It is a branch of chemistry which deals with the study of
transformation of chemical energy into electrical energy and vice versa”

Electrochemical cells: An electrochemical cell is a device which converts chemical

energy into electrical energy or electrical energy into chemical energy”

EMF of a cell Or Cell Potential : “Emf is the potential difference between the
two electrodes of a galvanic cell, which causes the flow of current from one
electrode to other. It is also called as cell potential or cell voltage. It is
expressed in volts.

Mathematically, Ecell = Ecathode – Eanode

Ecell = Eright electrode – Eleft electrode

Single electrode potential or half cell potential [E]:

The potential that is developed due to the tendency of an element (metal or non-metal) to lose
or gain electrons, when it is in contact with the solution containing its own ions is known as
single electrode potential.

Standard electrode potential [Eo]:

The potential that is develop when an element is in equilibrium with the solution containing
its own ions of unit concentration (1 M) at 298 K is known as standard electrode potential.
Types electrodes:

In Electrochemical work various type of electrodes are employed depending upon the
purpose for which they are used. Some of them are

1.Metal-Metal ion electrode: An electrode of this type consists of a metal dipped in a

solution containing its ions. Ex- Zn/Zn2+, Cu/Cu2+ etc.

The electrode reaction is, in general

2. Metal-Metal insoluble salt electrode: These electrodes consist of a metal in contact with a
sparingly soluble salt of the same metal dipped in a solution containing anion of the salt.

Example-Calomel (Hg|Hg2Cl2|Cl- ), Silver- Silver salt electrode (Ag| AgCl |Cl-).

3. Gas electrode: Gas electrode consists of a gas bubbling about an inert metal wire,
immersed in solution containing ions to which the gas is reversible. The metal provides
electrical contact and facilitates the establishment of equilibrium between the gas and its ions.

Example-Hydrogen electrode (Pt|H2|H+), Chlorine electrode (Pt|Cl2|Cl-).

4. Oxidation-Reduction electrode: An oxidation-reduction electrode is a one in which the

electrode potential arises from the presence of oxidized and reduced forms of the same
substance in solution. The potential arises from the tendency of one form changes into the
other more stable form. The potential developed is picked up by an inert electrode like
platinum.

Example-Pt|Fe2+, Fe3+, Pt|Ce3+, Ce4+

5. Amalgam electrode: It is an electrode which consists of a metal-amalgam dipped in a

solution containing its own metal ions. It is similar to Metal-Metal ion electrode.

Example-Pb-Hg|Pb2+, Zn-Hg|Zn2+

6. Ion selective electrode: it is an electrode, which consists of a membrane and in contact

with a solution, with which it can exchange ions.

Example- Glass electrode.

ION SELECTIVE ELECTRODES

Ion selective electrode possesses the ability to respond only to a specific ion, there by
developing a potential w.r.t that species in a mixture and ignoring the other ions totally.
For example: Glass electrode
Construction: The glass electrode consists of a glass bulb made up of special type of glass
which has low melting point and relatively high electrical conductivity. The glass bulb is
filled with a solution of constant pH (0.1MHCl) and insert with a Ag-AgCl electrode, which
is the Internal reference electrode and also serves for the external electrical contact. The
electrode is represented as, Ag|Agcl|0.1M HCl|Glass
The potential of glass electrode when dipped in a solution containing H+ ions, is given by
EG= E0G+ 0.0591 log [H+] (Since n = 1)
Principle: When a thin glass membrane is placed between two solutions of different pH
values, a potential difference arises across the membrane. The potential difference varies as
the pH of these solutions varies. In practice, pH of one of these solutions is kept constant and
therefore the electrode potential depends on pH of the other solution in the experimental
solution.

Working: The membrane undergoes an ion exchange reaction, the Na+ ions in the glass
membrane are exchanged for H+ ions.

H+ + Na+Gl- Na+ + H +Gl-

Solution membrane Solution membrane

DETERMINATION OF pH USING GLASS ELECTRODE

To determine the pH of the given solution the glass electrode is dipped into the solution. It is
combined with a reference electrode such as a calomel electrode through a salt bridge.

The cell assembly is represented as,

Hg|Hg2Cl2|Cl-||Solution of unknown pH|glass|0.1M HCl|AgCl|Ag

The emf of this cell is determined using potentiometer. The emf of the cell is given by.

Ecell = Ecathode - Eanode

Ecell = Eglass - ESCE

Ecell = Eo+0.0591 log [H+] - ESCE (since EG = EGo + 0.0591 log [H+] and n=1)

By rearranging the above equation we obtain,

-0.0591 log [H+] = Eo - Ecell – ESCE

- log [H+] = Eo - Ecell – ESCE

0.0591

pH = Eo - Ecell – 0.224 (Since, - log [H+] = pH)

0.0591

Concentration cells

The cells in which the EMF produced is due to the difference in the concentrations of the
electrodes or electrolytes.

There are two types of concentration cells.

i) Electrode concentration cells: A cell is formed by combination of same electrodes of

different concentrations dipped in same electrolyte solutions is called electrode concentration
cell.

For example: Pt, H2 (1atm) / H+(1M) / H2 (2 atm),Pt

ii) Electrolyte concentration cells: A cell is formed by combination of same electrodes
dipped in same electrolyte solutions of different concentration is called electrolyte
concentration cell.

For example: Cu(s) / Cu2+ (C1) // Cu2+ (C2) / Cu(s) Where C2 > C1

EMF of a concentration cell: Consider a concentration cell

M / Mn+ (C1) // Mn+ (C2) / M Where C2 > C1

Anode Cathode

E cell = E Cathode – E anode

Applying Nernst equation for single electrode potential, we get

0 . 0591 0 .0591
E0Mn+ ¿ M + log [ C2 ] −E 0Mn+ ¿ M − log [ C 1 ]
Ecell = n n

0 .0591 0 . 0591
log [ C2 ]− log [ C 1 ]
Ecell = n n

0 .0591 [C 2 ]
log
Ecell = n [C 1 ]
Numerical Problems:

1. A concentration cell was constructed by immersing two silver electrodes in 0.05M

and 1M AgNO3 solution. Write the cell representation and calculate E cell at 298K.

Ans: Ag/AgNO3 (0.05M) // AgNO3 (1M) / Ag

 0.0591 C2
Ecell = log
n C1

0.0591 1
= log
1 0.05

= 0.0768 V

2. Represent the cell formed by coupling two Cu-electrodes immersed in CuSO4

solutions concentrations of Cu2+ ions in one electrode system and 100 times more
concentrated than other. Calculate the Ecell at 298 K.

Ans: Cu/ Cu2+ (1M) // Cu2+ (100M) / Cu

0.0591 C2
Ecell = log
n C1

0.0591 100
= log
2 1

= 0.0298 x 2

= 0.0591 V
Sensor:
Definition: A sensor is a device that detects and responds to changes in its environment by
converting the physical change into an electrical signal.

A typical sensor consists of three main parts: the sensing element, the transduction element,
and the signal processing unit.
Sensing Element: The sensing element is the part of the sensor that interacts directly with
the environment. In a mobile phone's touch sensor, for instance, the sensing element might be
a capacitive or resistive surface that detects changes in electrical properties when touched.
A transducer converts a non-electrical signal into an electrical signal and vice versa.
Signal Processing Unit: This unit interprets the electrical signal from the transduction
element, making it usable for the system it's integrated into.
Electrochemical Sensors:
Electrochemical sensors produce an electrical signal based on the electrochemical
reaction of the substance which is proportional to the concentration of that substance.

Electrochemical sensors are devices that convert chemical information into an electrical
signal. They are commonly used for detecting and measuring concentrations of specific
substances in a mixture, such as gases in air quality monitoring.

The basic principle of electrochemical sensors involves three main steps:

1. Diffusion: The substance diffuses through a membrane and reaches the electrode
surface.
2. Reaction: An electrochemical reaction occurs at the electrode, which is specific to the
substance being detected.
3. Signal generation: The reaction produces an electrical current.

Construction and Working of Electrochemical Sensors:

Key Components:

1. Electrodes: The primary components where the electrochemical reactions occur.

2. Electrolyte: A medium that allows ions to move between electrodes.
3. Membrane: Separates the sample from the electrode and selectively allows specific
substances to pass through.

Working :

Electrochemical sensors are made up of an electrochemical cell with of three electrodes in

contact with an electrolyte. The electrodes are the transducer elements that recognize the
analyte of interest.
1. The working electrode (WE) is the place where the reaction happens that can be
controlled or to investigate.
2. A counter electrode (CE) is completes the electrical circuit and allows current to
flow. It's also known as an auxiliary electrode.
3. The main function of the CE is to respond to the counteraction of the reaction at
the WE. As the WE undergoes a reduction reaction, the CE enacts
an oxidation reaction, and the current starts to flow.
4. The reference electrode’s (RE) role is to act as a reference in measuring the working
electrode potential, without passing any current. The reference electrode should have
a constant potential at low current density.
5. The current that is produced from the reaction in the form of signal used to calculate
concentrations from the sample

Types of Sensors

Different types of sensors can be classified on the basis of various factors including the
physical quantity they measure (like temperature, pressure, light), the operating principle they
employ (such as resistive, capacitive, inductive, or optical), the type of output signal they
generate (analog or digital), the nature of their interaction with the environment (contact or
non-contact), their field of application (medical, automotive, environmental, etc.), and the
specific technology they utilize (semiconductor, MEMS, fiber optics, etc.).Classification of
sensors based on the physical property they measure are
Mechanical Sensors: Mechanical sensors detect changes in physical properties, such as
pressure, force, or displacement. Examples of mechanical sensors include strain gauges,
accelerometers, and pressure sensors. These sensors often use a mechanical element, such as
a diaphragm or a spring, to convert the physical change into an electrical signal.

Optical Sensors: Optical sensors rely on the interaction between light and matter to detect
changes in their environment. Common examples of optical sensors are photodiodes, fiber
optic sensors.

Electrical Sensors: Electrical sensors detect changes in electrical properties, such as

capacitance, inductance, or resistance. Capacitive sensors, for example, measure changes in
capacitance caused by the proximity of an object, while inductive sensors detect changes in
inductance due to the presence of a metallic object.

Thermal Sensors: Thermal sensors measure temperature or changes in temperature.

Common types of thermal sensors include thermocouples, which generate a voltage
proportional to the temperature difference between two dissimilar metals, and resistance
temperature detectors (RTDs), which measure changes in resistance as a function of
temperature.
Electrochemical Sensor Applications
Electrochemical sensors are used in a variety of applications, and they continue to play an
important role in many industries. Some of the most common applications include:

1. Environmental monitoring of air quality

The major contributors of air pollution being nitrogen oxides, sulfur oxides, hydrogen sulfide,
and some volatile organic substances. Electrochemical gas sensors are now becoming an
essential tool in monitoring and controlling contaminations affecting atmospheric quality.
They offer a cheaper widespread air monitoring alternative to the traditional and more
expensive air quality monitors based on infra-red spectroscopy and gas chromatography.

2. Detection of explosive gases and toxic vapours

There is an increased focus on explosion prevention within hazardous locations in
manufacturing and chemical industries due to the presence of toxic and combustible gases.
This has seen an increase in the use of electrochemical gas sensors, which provide improved
sensitivity and selectivity for a broad range of toxic gases.

3. Oxygen monitoring in the medical sector

Electrochemical oxygen sensors are used in many brands and models of medical respirators
and ventilators used in respiratory therapy, life support systems and emergency medicine..
It’s small size, ease of implementation, and simple operation makes the electrochemical
sensor an ideal detection and monitoring device in the healthcare sector.

4. Food quality control

Carbon dioxide and ethanol are used in the food and beverage industry, and therefore, there is
a need for continuous gas detection by sensors to prevent people ingesting poisonous or
harmful gases. Other applications where gas detection is required is in steam processes, inert
gases for packaging, CO2 for carbonation, toxic gases for sterilization and ammonia used in
refrigeration.

Analytical Techniques: Introduction

Analytical chemistry is a science in which materials are separated, identified and quantified.
The techniques used in this branch of chemistry are defined as the chemical or physical
principles employed to study a substance which is to be analyzed (the analyte). The
techniques for carrying out these aims may be combined or each may be done separately. The
identification of the matter under study is performed using qualitative analysis, while
quantitative analysis is used to determine how much (relative concentration or total amount)
of the substance is present in the analyte.
Colorimetric sensors

Colorimetric analysis involves measurement of quantity of light absorbed by a colored

solution.

Principle

Quantitative analysis by colorimetry is based on Beer-Lambert’s law.

When a beam of monochromatic radiation is passed through a solution of an absorbing

substance. The intensity of incident radiation decreases exponentially with increase in
thickness and concentration of the solution.

log (I0/It) = εCl

(or)

A= εCL
Io= intensity of the incident light
It = intensity of transmitted light
A= absorbance
ε = molar absorption co-efficient
l = length of light path
C = concentration

The term, log (I0/It) is called the absorbance or optical density of the light absorbing medium.
Since ε is a constant and thickness l is kept constant,

Light Source – The most common source of light used in colorimeter is a tungsten filament.
Monochromator – To select the particular wavelength filter or monochromators are used to
split the light from the light source.

Bl
ock diagram of photoelectric colorimeter

Sample holder – Test tube or Cuvettes are used to hold the color solutions they are made up
of Glass at the visible wavelength.

Photo Detector System – when light falls on the detector system, an electric current is
generated, this reflects the Galvanometer reading.

Measuring device (recorder) – The current from the detector is fed to the measuring
device, the Galvanometer, shows the meter reading that is directly proportional to the
intensity of light.

Transfer the given copper sulphate solution (stock solution) to a burette and draw out
5, 10, 15, 20 and 25 cm3 of the solution into 50 cm3 volumetric flasks. Add 5 cm3 of ammonia
solution to each of them and dilute up to the mark with ion exchange water. Stopper the flasks
and mix. To the test solution given in a 50 cm 3 volumetric flask, add 5 cm3 of ammonia and
dilute upto the mark and mix well. Prepare a blank solution by diluting 5 cm 3 of ammonia
solution in a 50 cm3 volumetric flask up to the mark with ion exchange water and mix well.
Measure the absorbance of the solutions against blank at 620 nm using photoelectric
colorimeter. Draw a calibration curve by plotting optical density (OD) against volume of
copper sulphate (cm3). Using the calibration curve, find out the concentration of copper in the
test solution and calculate the amount of copper in 50 cm3 of the given test solution.
 CuSO4 + 4NH3  [Cu(NH3)4]2+ SO42-
Maximum absorbance of this complex is (λmax) 620 nm.
[Note: The reason for getting a straight line can be concluded as follows
Absorbance (A) = εCl
The cell, the path length is fixed so the absorbance is directly proportional to concentration
The absorbance is measured using the same cell, same wavelength and same filter. From the
calibration curve the concentration of the unknown CuSO4 solution can be easily evaluated.
A series of standard solutions containing Cu(II) ions is treated with NH 3 to get dilute solution
of the complex of cuprammonium complex ion]

Calculation
The volume of copper solution (unknown) from the graph = Y__ ml.
The amount of copper present in the 1.0 ml of copper sulphate solution = ___W_ g.
The amount of copper present in the given unknown solution = Y X W = ______ g.

CONDUCTOMETRIC TITRATIONS:
Principle

The electrical conductance depends on the concentration of solution and mobility of ions.
Theory:
Analysis based on measurements of conductivity of solution is called conductometric
analysis. The migration of ions is responsible for the conduction of electricity in solutions.
Conductance is defined as the reciprocal of resistance.
C=1/R Where R is resistance
The unit of conductance is ohm-1 or Ω-1. The SI unit is Siemen(S).
The reciprocal of specific resistance is called specific conductance (ρ).
The unit of specific conductance is ohm-1 cm-1 and SI unit is Sm-1.
Conductivity cells are usually made of highly insoluble glass, such as pyrex or quartz. The
two electrodes are consisting of platinum plates (coated with platinum black in order to
reduce polarization) sealed into glass tubes with pass through an ebonite cover. The
conductivity cell connected to conductometer.

Conductometric application in the estimation of weak acid.

The acetic acid is taken in the beaker and immersed conductivity cell into it and
NaOH in the burette. The conductance of the acid will be low because of its poor
dissociation. On adding, the NaOH, highly ionized sodium acetate is formed and hence the
conductance begins to increase till complete neutralization of acetic acid. When the acid is
completely neutralized further addition of NaOH introduces excess of fast moving OH – ions.
The conductance of the solution begins to increase sharply. The intersecting point joined to
X-axis which gives the volume of NaOH consumed by acetic aicd.

NaOH(aq) + CH3COOH(aq) → CH3COONa(aq) + H2O(aq)

Calculation

V1N1 (CH3COOH) =V2N2 (NaOH)

Strength of acetic acid N1 =V2N2/ V1 = a N

Weight of acetic acid = Strength of acetic acid X equivalent weight of acetic acid (60)

= a X 60 = b g/litre.

Result: The weight of acetic acid present in the given solution is = b g/litre.

Potentiometric titrations

Principal

The potential of an electrode depends on the concentration of the solution.

Theory:
Potentiometric titrations involve in measurement of electrode potentials with addition of
titrant.
The electrode potential is given by Nernst equation

E=E0 + (2.303RT/nF) log[Mn+]

The potentiometric titration requires the selection of the appropriate indicator electrode and
reference electrode is usually a saturated calomel electrode.
Indicator electrode means whose electrode potential depends upon concentration of solution
which is to be determined.
Reference electrode means whose electrode potential independent of concentration of
solution.
Take 25 cm3 of the given FAS solution into a clean beaker and add 2 test tubes of dil. H 2SO4.
Immerse platinum electrode and saturated calomel electrode assembly, connect to a
potentiometer and note down the potential value in milli volts (mV). Fill a micro burette with
the given standard K2Cr2O7 solution. Add K2Cr2O7 solution in increments of 0.5 cm 3 to FAS
solution in the beaker. Stir the solution thoroughly and measure the emf after each addition.
When the reaction reaches the equivalence point, there is a maximum increase in the emf
value. After the equivalence point, there will be slight increase in emf on continued addition
of K2Cr2O7. Graph of E/ V against volume of K 2Cr2O7 is plotted. From the graph, volume of
K2Cr2O7 at equivalence point is found out.

3Fe2+ + Cr6+ → 3Fe3+ + Cr3+

During the titration 3Fe3+ goes on increasing and 3Fe2+ goes on decreasing as K 2Cr2O7 is
added continuously, gradually changing the potential, but at the equivalence point, there will
be sudden jump in potential after end point electrode potential which is going to change
gradually. So the increase in the value of Fe 3+/Fe2+ and change in the electrode from Pt/ Fe 3+,
Fe2+ (0.77V) to Pt/Cr6+, Cr3+ (1.33V), there is a huge change in potential at the end point.

E= E° +0.0591 log [ Fe2+]/[Fe3+]

The ∆E/∆V plotted against the volume of K 2Cr2O7 added, the end point where the slope of
curve is maximum.
Calculation
Normality of K2Cr2O7 = N (will be given) ----- (b)
Normality of FAS = Normality of K2Cr2O7 × Volume of K2Cr2O7 (from graph)/Volume of FAS
N= b×a/ 25 = ------N (z)
Weight of FAS /dm3 = Normality of FAS × Equivalent weight of FAS (392.24)
= z × 392 g = ----------g/litre (w)
Weight of iron in the given FAS solution = W X 55.8/392
Result: Weight of iron in the given FAS solution = ---------------g/litre