Department of Chemistry, DSCE

Applied Chemistry
Chemistry of Electrical and Electronic Materials
Stream: EE (Common to EC, EE, ET & MD Programs)
I / II SEMESTER
Course Code: 1BCHEE102/202
Module - 5

DAYANANDA SAGAR COLLEGE OF ENGINEERING

Accredited by National Assessment & Accreditation Council (NAAC) with ’A’ Grade
(An Autonomous Institution affiliated to Visvesvaraya Technological University, Belagavi)
DEPARTMENT OF CHEMISTRY
SHAVIGE MALLESWARA HILLS, KUMARASWAMY LAYOUT
BENGALURU-560111

2025-26

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Electrodes and Sensing techniques

Electrode Systems

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”
Gibbs Free Energy (G): Gibbs energy is defined as maximum available energy in a system that can
be converted into useful work.
G =H -TS
The thermodynamic free energy is the amount of work that a thermodynamic system can perform. The
free energy is the internal energy of a system minus the amount of energy that cannot be used to perform
work.
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.

Reference electrode
“Reference electrode is an electrode whose potential is known and with reference to that, the electrode
potential of any electrode can be measured”. There are two types of reference electrodes. They are
primary and secondary reference electrodes. Primary Reference Electrode: It is an electrode, whose
potential is arbitrarily taken as zero at all temperatures. Eg- Standard Hydrogen Electrode (SHE)

Calomel electrode: It is a secondary reference electrode.

Figure: Calomel Electrode

Construction:
It consists of glass tube having a side tube at each end. A small amount of pure mercury is placed
at the bottom of the glass tube and covered by a calomel paste obtained by grinding together Hg,
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Hg2Cl2 and either 0.1N KCl or 1NKCl or saturated KCl. The remaining portion is filled with either
0.1N KCl or 1NKCl or saturated KCl solution. Platinum wire is dipped into the mercury layer and
is used for making electrical contact. The side tube is used for making electrical contact with a salt
bridge.
Calomel electrode can be represented as, Hg(s)/Hg2Cl2(liq)|Cl-.
Working:
Reactions: The electrode behaves either as anode or as cathode
when it behaves as anode, the electrode reaction is:
2Hg (l) + 2Cl- → Hg2Cl2(s) + 2e
When it behaves as cathode, the electrode reaction is:
Hg2Cl2(s) + 2e→2Hg (l) + 2Cl-
Net half-cell reaction is represented as: Hg2Cl2 + 2e- 2Hg + 2Cl-
Nernst equation for calomel electrode: Ecal = E0cal – 0.0591 log [Cl-] at 298 K

Hence, the electrode potential of Calomel electrode dependent on the concentration of chloride ions
Concentration of KCl 0.1N 1.0N Saturated
Potential of Calomel Electrode 0.338 V 0.281 V 0.244 V
Advantages:
 It is very simple construction.
 It can be used for long time without much attention.
 Its electrode potential will not vary with temperature.
 It is used as reference electrode.

Applications:
 pH Measurement: for calibrating pH meters and measuring pH in various aqueous solutions,
in chemical and environmental monitoring.
 Cyclic Voltammetry (CV): Acts as the reference in CV to study electrochemical behavior,
reaction mechanisms, and properties of analytes or surfaces.
 General Electrochemistry: Used in potentiometry and voltammetry to establish potential
differences and relate them to chemical changes in aqueous systems.
 Calibrating Other Electrodes: Serves as a standard benchmark to calibrate other indicator
electrodes.

ION SELECTIVE ELECTRODES

Ion selective electrode possess the ability to respond only to a specific ions, 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 an Ag-AgCl electrode, which is the internal reference electrode
and also serves for the external electrical contact.
The electrode is represented as, Glass|0.1M HCl|AgCl(s), Ag(s).
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)

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Figure: Glass Electrode.

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.
potential depends on pH of the other solution in the experimental solution.
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

In practice, pH of one of these solutions is

Working: Working: The Potential of the glass electrode is sum of 3 potentials, boundary potential (Eb),
inner reference electrode (EIRE) and asymmetric potential (Easy).
E𝐺= 𝐸𝑏 +𝐸𝐼𝑅𝐸 +𝐸𝑎𝑠𝑦
Where, EG is glass electrode potential
Eb is boundary potential ie 𝐸𝑏 = 𝐸1 −𝐸2 , E1 is the outer membrane membrane potential for the
concentration C1, and E2 is the inner membrane potential for the concentration C2.
EIRE is internal ref. electrode potential
Easy is asymmetric potential due to the curvature nature of the potential

Where, 𝐸𝑏 = 𝐸1 −𝐸2 = 2.303 log 𝐶1

𝑛𝐹 𝐶2
Where,
𝐶1=Concentration of H+ of solution to be analyzed
C2=Concentration of H+ in the internal standard electrode

𝐸𝐺= 2.303𝑅𝑇 𝑙og 1 + 𝐸𝐼𝑅𝐸 +𝐸𝑎𝑠𝑦

𝑛𝐹 𝐶2
E𝐼𝑅𝐸 𝑎𝑛𝑑 𝐸𝑎𝑠𝑦 are constants called standard reduction potential at glass electrode (𝐸0𝐺)

E𝐺 = 𝐸0𝐺 + 2.303𝑅𝑇 𝑙𝑜𝑔𝐶

𝑛𝐹
when, C1=[H+] and ∆C2=0
E𝐺 = 𝐸0𝐺 +2.303𝑅𝑇 [𝐻+]
𝑛𝐹
0
= 𝐺 − 2.303𝑅𝑇 pH
nF
E𝐺 = 𝐸0𝐺 −0.0591 pH

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Determination of pH of a solution using Glass Electrode

Cell representation: Hg|Hg2Cl2|Cl-||Solution of unknown pH|glass|0.1M HCl| Ag, AgCl

The emf of this cell is determined using potentiometer. The emf of the cell is given by.
Ecell = Ecathode - Eanode
Ecell = EG - ESCE
Ecell = EoG + 0.0591 log [H+] - ESCE (since EG = EoG + 0.0591 log [H+] and n=1)
By rearranging the above equation we obtain,
-0.0591 log [H+] = EoG- Ecell – ESCE
- log [H+] = EoG - Ecell – ESCE
0.0591
o
pH = E - Ecell – 0.244 (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) ǀ H+(1M)ǀǀ H+(1M)ǀ 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

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Applying Nernst equation for single electrode potential, we get

E cell = E Cathode – E anode
logC2  EMn log C1
0.0591 0.0591
/ M  / M 
0 0
Ecell = EMn
n n
logC2  log C1
0.0591 0.0591
Ecell =
n n
0.0591 [C 2]
Ecell = log
n C1
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 𝐶1
𝑛

0.0591 1
= log 0.05
1

= 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 𝐶1
𝑛

0.0591 100
= log
2 1

= 0.0298 x 2

= 0.0591 V

Introduction for Sensors: A sensor is a device that receives a signal (i.e. physical, chemical or biological signal) and
responds to the signal in the form of an electrical signal. The output signals correspond to some forms of electrical
signal, such as current or voltage.
Components of a sensor

Figure 1: Function of a sensor

1. Receptor- Receives/ observes and acquires information.
2. Transducer-Converts one form of energy into another form.

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3. An Actuator-Converts electrical energy into mechanical/ readable energy.

Optical Sensors:
Optical sensors are devices which detect and convert incident light rays into electrical signals.
Example: Colorimetric Sensors
Absorption-based optical sensors-Colorimetric Sensors:
Colorimetric sensors are simple type of optical sensors which use incident light of visible region (400-800nm) of
spectrum and detect and determine the concentration of colored chemical species of analyte solutions. The important
parts of colorimeter are given below.
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) =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.

Working:
When analyte solution interacts with an incident light of suitable wavelength, certain quantity of light is absorbed by
the analyte solution, and a transducer such as photo detector converts intensity of light absorbed by analyte into
electrical signal. A monochromatic light whose wavelength falls in visible region of spectrum is made to pass through
analyte solution where certain quantity of incident light is absorbed and remaining amount of light is transmitted.
Concentration of colored chemical species in analyte solution is determined by measuring absorbance or transmittance
of light of particular wave length.

Monochromator – To
select the particular wavelength filter or monochromators are used to split the light from the light source.

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 cm3 volumetric flask, add

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5 cm3 of ammonia and dilute upto the mark and mix well. Prepare a blank solution by diluting 5 cm3 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.
A series of standard solutions containing Cu (II) ions is treated with NH3 to get dilute solution of the complex of
cuprammonium complex ion
CuSO4 + 4NH3  [Cu (NH3)4]2+ SO42-
Maximum absorbance of this complex ion is 620nm.

The reason for getting a straight line is because it follows, Beers Lamberts Law.
Applications of optical sensors:
 Used to detect and measure different types of chemicals, biochemical molecules and ions.
 Estimation of Cu in effluent from PCB industry.
 Industrial and Agricultural applications

CONDUCTOMETRIC TITRATIONS:
Conductometric sensor: Estimation of weak acid
Principle: The electrical conductance depends on the concentration of solution and mobility of ions.

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).
Conductivity cells are usually made of quartz, which consist of two electrodes of platinum plates sealed into glass
tubes. The conductivity cell is connected to conductometer.

Procedure:
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.
When the acid is completely neutralized, further addition of NaOH introduces excess of fast moving OH – ions. The

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conductance of the solution begins to increase sharply. The intersection extrapolated to X-axis gives the volume of
NaOH consumed by acetic acid for neutralization.

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.

Applications of Conductmetric Sensors

1. Environmental Monitoring: Measurement of water quality by detecting dissolved salts, pollutants, and heavy
metal ions.
2. Food and Beverage Industry: Measurement of salt concentration in food processing.
3. Medical and Biomedical Applications: Detection of electrolytes in body fluids (e.g., sodium, potassium,
chloride).
4. Industrial Applications: Control of ionic strength in chemical and pharmaceutical industries.

Potentiometric titrations
Potentiometric sensors: Estimation of iron

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

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 platinum and saturated calomel electrode, respectively.

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Fig. Potentiometric titration assembly

Take 25 cm3 of the given FAS solution into a clean beaker and add 2 test tubes of dil. H2SO4. 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 K 2Cr2O7
solution. Add K2Cr2O7 solution in increments of 0.5 cm3 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 K2Cr2O7
is plotted. From the graph, volume of K2Cr2O7 at equivalence point is found out.
H+
3Fe + Cr → 3Fe3+ + Cr3+
2+ 6+

At the equivalence point, there will be sudden jump So the increase in the value of Fe 3+/Fe2+ and change in the
electrode from Pt/ Fe3+, 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 K2Cr2O7 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)
Result: Weight of FAS in given solution = ---------------g/litre

Applications of potentiometric Sensors

1. Environmental Monitoring: Water quality testing: Detection of pH, dissolved oxygen, nitrate, ammonia,
fluoride, chloride, and
2. Clinical and Biomedical Applications: Blood electrolyte analysis: Measurement of Na⁺, K⁺, Ca²⁺, Cl⁻ in
blood and serum using ion-selective electrodes (ISEs).
3. Corrosion studies: Measurement of corrosive ion activity (chloride, sulfate).
4. Food and Agriculture: pH and ion concentration tracking in brewing, dairy, and vinegar production.
Monitoring of nitrate, phosphate, and potassium levels.

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A for health monitoring using sensors

AI-based health monitoring uses sensors and machine learning to track vital signs, detect abnormalities, and predict
health risks in real time. It supports early diagnosis, personalized care, and remote monitoring, improving management
of chronic diseases despite challenges like privacy and accuracy.

1. Sensors Used in Health Monitoring (Wearable Sensors)

Heart rate & ECG – smartwatches, chest straps

Blood oxygen (SpO₂) – pulse oximeters

Motion & activity – accelerometers, gyroscopes

Skin temperature and Sleep tracking – movement, HRV(heart rate variability), respiration

Examples: Apple Watch, Fitbit, Garmin, medical-grade wearables

Implantable Sensors

 Continuous glucose monitors (CGM)

 Pacemakers with telemetry
 Smart implants for pressure or neural signals

Role of AI in Health Monitoring

AI turns raw sensor data into meaningful health insights through following steps
1. Data Processing

 Noise filtering & signal enhancement

 Sensor fusion (combining multiple sensors)
2. Machine Learning & Deep Learning

 Anomaly detection – irregular heartbeats, abnormal vitals

 Pattern recognition – disease progression trends
 Prediction models – risk of heart attack, hypoglycemia, falls
3. Real-Time Decision Support

 Alerts for patients and clinicians

 Automated recommendations
 Adaptive personalized baselines
Applications: Cardiovascular Monitoring, Diabetes Management, Elderly Care, Mental Health am
Benefits

 Continuous, non-invasive monitoring

 Early disease detection
 Personalized healthcare
 Reduced hospital visits
 Better chronic disease management

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