APPLIED CHEMISTRY

STUDY MATERIAL

FOR THE STUDENTS OF B.E.

(AUTONOMOUS - 2024)
For EC, VLSI, ETE, EIE and EEE Branches

Dr. N. Suresha. [Link]., Ph. D., [Link]., [Link].

He obtained [Link]. degree with the specialisation in Physical

Chemistry from the University of Mysore in 1997, [Link]. degree from
Mysore University in 1998, [Link]. degree from Karaikudi
University in 2009 and Ph.D. degree in the area of “Catalysed
Oxidation Kinetics of Drug Molecules; A Mechanistic Investigation”
from Visweswaraya Technological University in 2022. He has more
than 21 years of teaching experience. He has been working in
Bangalore Institute of Technology, B`lore from 2007 and at Present
working as HOD of Chemistry.
 Applied Chemistry study material (EC-stream)– Module -2: Dr. N Suresha, [Link]., Ph.D., [Link]., [Link].

Module-II
Electrodes and Sensors in Analytical Techniques
Syllabus
[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, working and applications of Concentration cell. Numerical
problems.

Sensors in Analytical techniques: Sensors: Introduction, Types of sensors. Working principle and
instrumentation of Optical Sensor (Colorimetric sensor) and its application in the estimation of Copper.
Working principle and instrumentation of Potentiometric sensors and its application in the estimation of
Iron. Principle and instrumentation of Conductometric sensors and its application in the estimation of weak
acid].

Electrode system

Electrochemistry is the branch of chemistry mainly deals with the study of inter conversion of
electrical and chemical energies that takes place through redox reaction.

Oxidation reaction: A reaction in which species loses one or more electrons and there is increase
in its oxidation number.

Ex: Fe2+ → Fe3+ + e-

Reduction reaction: A reaction in which species gain one or more electrons and there is decrease
in its oxidation number.

Ex: Fe3+ + e-→Fe2+

Electrode: A metal or non-metal having the tendency of losing or gaining electrons is called an
electrode.

Ex: Cu, Zn, Mg electrodes etc.

An electrochemical cell is made of two electrodes, anode and cathode. Each electrode is called a
single electrode or half-cell.

Anode: The electrode at which oxidation takes place is called anode and it assigned negative sign
(in galvanic cell).

Cathode: The electrode at which reduction takes place is called cathode and it is assigned positive
sign (in galvanic cell).

Generally, two types of electrode systems are there, viz. i. Two electrode system and ii. Three
electrode system.
 Applied Chemistry study material (EC-stream)– Module -2: Dr. N Suresha, [Link]., Ph.D., [Link]., [Link].

Two electrode system is composed of working electrode (WE) and counter/reference electrode
(CE/RE) to measure the potential across the complete cell.
Three electrode system is composed of working electrode (WE), counter electrode (CE) and
reference electrode (RE) to measure the potential and current precisely.

Working electrode is the one where the oxidation/reduction reaction of interest takes place and its
potential is sensitive to analyte concentration. Reference electrode serves to complete the electric
circuit and provides reference potential against which the working electrode`s potential is measured.
Counter electrode plays the opposite role to the working electrode, it will not participate with the
electrochemical reaction except to balance the current observed at the working electrode.

Single Electrode Potential (E): The potential developed when metal is in equilibrium with its own
ions in the solution when it is connected with other half-cell.

Standard Electrode potential (Eo):

Standard electrode potential is the potential developed when metal is in equilibrium with its own
ions in the solution of unit concentration at STP.

EMF of a cell (Ecell): “Potential difference between the two electrodes which causes a current to
flow from an electrode having high reduction potential to the electrode having lower reduction
potential is called as EMF”.

i.e. Ecell=Ecathode -- Eanode

Electrochemical cell: A device which converts chemical energy into electrical energy and vica-
versa is called an electrochemical cell. There are two types of electrochemical cells.

i. Galvanic cell: An electrochemical cell which converts chemical energy into electrical
energy.
ii. Electrolytic cell: An electrochemical cell in which chemical changes can be brought by the
application of electrical energy.

Daniel cell: It can be constructed by placing zinc rod in 1M ZnSO4 solution and copper rod in 1M
CuSO4 solution. The electrodes are externally connected through a sensitive voltmeter and
internally connected through a salt bridge as shown in the diagram.
 Applied Chemistry study material (EC-stream)– Module -2: Dr. N Suresha, [Link]., Ph.D., [Link]., [Link].

Working: Zinc undergoes oxidation and release electrons. The electrons generated at anode
compartment move through the external circuit and involve in the reduction of Cu 2+ ions in cathode
compartment.

Cell reaction:
Anode: Zn → Zn2+ +2e- -- oxidation
Cathode: Cu2+ + 2e- → Cu -- reduction
Zn + Cu2+↔ Zn2+ + Cu

Electricity is generated in opposite direction to the flow of electrons. Therefore cell potential can be
defined as the potential difference which causes a current to flow from the electrode at high
reduction potential to the electrode at low reduction potential.
Eocell = Eocathode --Eoanode
= EoCu2+/Cu – EoZn2+/Zn
= 0.34 – (-0.76)
= 1.1 v

[Salt bridge: It is a u-tube containing jelly with KCl solution. It prevents the mixing of electrolytes
in both the compartments and allows only the passage of ions. It also maintains electrical neutrality
in both the compartments.]

Types of single electrodes: The important types of electrodes are--

1. Metal ion-metal electrode: where metal is in contact with its own ions in the solution.
Ex: Cu2+/Cu, Ag+/Ag, Zn2+/Zn,..
2. Metal insoluble salt electrode: where metal is in contact with anion of the insoluble salt.
Ex: Calomel electrode, Ag/AgCl electrode
3. Gas electrode: where gas is in contact with inert metal dipped in ionic solution of gas
molecule.
Ex: SHE
4. Redox electrode; where inert metal is in contact with the solution containing ions of two
different oxidation states.
Ex: Pt/Fe2+. Fe3+
5. Amalgam electrode: where metal dissolved in mercury is in contact with its salt solution.
Ex: Na+(c1) Hg/Na+(c2)
 Applied Chemistry study material (EC-stream)– Module -2: Dr. N Suresha, [Link]., Ph.D., [Link]., [Link].

6. Ion-selective electrode: where membrane is in contact with ionic solution.

Ex: Glass electrode, Solid state membrane electrode, Liquid membrane electrode.

Reference Electrode:

The electrode, whose potential is known and is used to determine the potential of other electrodes is
called reference electrode.

Primary reference electrode: The electrode, whose potential is arbitrarily fixed as ZERO at all
temperature and pressure is called Primary reference electrode.

Ex: Standard hydrogen electrode (SHE)

Limitations of SHE: 1. It is difficult to construct.

i. It is difficult to maintain H2 gas continuously at 1 atm pressure.

ii. The electrode becomes poisonous in presence of impurities.

Secondary reference electrode: The electrode, whose potential is known with respect to SHE is
called secondary reference electrode.
Ex: 1. Calomel electrode 2. Ag-AgCl electrode
Calomel electrode:
Construction: It consists of glass tube in which pure mercury is placed at the bottom and it is
covered with the paste of mercury, mercurous chloride and KCl. Remaining volume is filled with
KCl solution of known concentration. For electrical contact, insert platinum wire so that it touches
mercury at the bottom. There is a porous disc at the bottom of glass tube which acts as salt bridge.

Calomel electrode can be represented as, KCl / Hg2Cl2 / Hg(l).Pt

The calomel electrode can acts as anode or cathode depending on the nature of the other electrode
in the cell.
When it acts as cathode, the electrode reaction is,

½ Hg2Cl2 + e- Hg + Cl-
 Applied Chemistry study material (EC-stream)– Module -2: Dr. N Suresha, [Link]., Ph.D., [Link]., [Link].

When it acts as anode, the electrode reaction is,

Hg + Cl- ½ Hg2Cl2 + e-
2.303 RT
Electrode potential is given by, ECE = E°CE − log[Cl− ]
nF

The electrode potential of calomel electrode is depending upon the concentration of KCl. For
saturated KCl solution, the potential is +0.2414 V, for 1M and 0.1MKCl the values are 0.281V and
+0.334V respectively.

Advantages:
1. It is very simple to construct.
1. Potential does not vary with temperature.
2. Potential is reproducible and constant for long period of time.

Applications:
1. It is used as secondary reference electrode to measure the potential of other electrodes.
2. It is used as reference electrode in all potentiometers.
3. Used in determining whether the potential distribution in ship hulls and pipelines protected by
cathodic protection.
4. As a portable reference electrode for measuring the different depths of submerged oil
pipelines etc.

Ion selective electrode:

‘Ion selective electrode is one which selectively sensitive to a particular type of ions and develops
potential proportional to the concentration of those ions in the solution’.

These electrodes are used to measure concentration of particular cations or anions in the solution
and are sensitive up to 10-9 M concentration.

Glass electrode: A glass electrode is more selective to H+ ions and potential depends upon the
concentration of H+ in the medium.

Principle: When a glass bulb containing internal solution of known concentration (c1) is dipped in a
solution of unknown concentration (c2), due to the concentration gradient, potential develops across
the membrane, is called boundary potential Eb. It is given by

RT c 2
Eb = ln ⸪ n=1 for H2
F c1

Eb =  RT ln c1  RT ln c2
F F
Eb= A + 0.0591 log c2 ⸪ R, T, F and c1
are constants
Since c2= H+
-log c2 = -log[H+]
 Applied Chemistry study material (EC-stream)– Module -2: Dr. N Suresha, [Link]., Ph.D., [Link]., [Link].

⸫ Eb= A - 0.0591pH

Construction: It has long glass tube and a thin glass bulb at one
end. It has low melting point and high ionic conductivity. It can
sense the [H+] up to the pH = 9. The composition used in the
preparation of glass bulb is SiO2=72%, CaO = 22% and Na2O =
6%. It consists of silver electrode as internal reference electrode
immersed in 0.1M HCl.

It can be representation as, Ag/AgCl/0.1 M HCl/Glass

Working: When glass electrode is dipped in a solution of unknown

concentration, there is exchange of N+ ions with H+ ions as;
Na+Glass + H+Soln. ↔ Na+Soln. + H+Glass

Due to this exchange, glass electrode potential (EG) is developed. It is given by

EG = Eb + EAg/AgCl
Even when c1 = c2, Eb ≠ 0, a small potential is shown in the meter, it is called asymmetry potential.
This should also be taken into account.
⸫ EG = Eb + EAg/AgCl + Easym
= A - 0.0591pH + EAg/AgCl + Easym

⸫ EG = B - 0.0591pH where B = A + EAg/AgCl + Easym

[The potential value varies from time to time & also one electrode to other, its value can be
determined by using known concentration (buffer) solution.]

Application of glass electrode for the determination of pH of solution: To determine the pH of a

given solution, a galvanic cell should be constructed by connecting glass electrode with calomel
electrode as shown below.

The cell assembly is represented as,

Hg/ Hg2Cl2/KCl//Solution of unknown pH/glass/0.1M HCl /AgCl/Ag

Dip the electrodes in the solution whose pH has to be determined, and measure Ecell(T).
Then,Ecell(T) = Ecathode – Eanode
 Applied Chemistry study material (EC-stream)– Module -2: Dr. N Suresha, [Link]., Ph.D., [Link]., [Link].

ECell(T) = Ecathode − EAnode

Ecell(T) = EG − ESCE
Substitute EG value to the above equation

Ecell(T) = B − 0.0591pH(T) − ESCE ⸪ EG = B – 0.0951pH

ESCE is constant at saturated KCl solution, above equation can be written as

Ecell(T) = K − 0.0591pH(T) …….(1)
Where, K = B − ESCE
Now, determine Ecell(b) for buffer solution (solution of known pH) and rewrite eqn. (1) for it.
i.e. Ecell(b) = K − 0.0591pH(b) ……… (2)
Subtract eqn. (2) from eqn. (1), it gives
Ecell(T) = Ecell(b) + 0.0591pH(b) − 0.0591pH(T)

Ecell(b) −Ecell(T)
∴ pH(T) = pH(b) + at 298K
0.0591

Then, pH(T) can be determined by knowing pH(b), Ecell(T) and Ecell(b).

Advantages of glass electrode:

1. This electrode can be used to determine PH in the range 0-9.
2. It can be used even in the case of strong oxidizing agents.
3. It is simple to operate, hence extensively used in various laboratories.

Concentration cell:
Concentration cell is a type of galvanic cell, in which both anode and cathode are made of same
metal placed in same salt solutions of different concentration. It can be constructed as follows.

n+ n+
Generally concentration cells are represented as: M⁄M(C 1)
//M(C 2)
⁄M. Where, C2 > C1 ,

Metal immersed in dilute solution acts as anode at which oxidation reaction occurs.

M → MC1n+ + e-
 Applied Chemistry study material (EC-stream)– Module -2: Dr. N Suresha, [Link]., Ph.D., [Link]., [Link].

Whereas metal immersed in more concentrated solution acts as cathode at which reduction reaction
occurs.
MC2n+ + e- → M

Net cell reaction is MC2n+ ↔ MC1n+

The net cell reaction is merely the change in concentration of metal ions, as a result of which
current flows. This will take place till the concentration in both the half cells becomes equal.

Emf of concentration cell:

We know that electrode potential depends upon the concentration of the electrolyte

⸫ Econcentration cell = Ecathode − EAnode

o
0.0591 o
0.0591
[Link] = Ecathode + log[C2 ] − Eanode − log[C1 ]
n n

o o
0.0591
[Link] = (Ecathode − Eanode )+ {log[C2 ] − log[C1 ]}
n
o o
Ecathode − Eanode = 0, because both the electrodes are made of same metal

0.0591 [C ]
[Link] = log [C2 ] at 298K
n 1

From the above equation, following conclusions can be drawn.

1. When C1 = C2, [Link] = 0 i.e. no electricity will be generated.
2. When C2 > C1, log C2/C1 is positive & electrode potential is positive, the reaction is spontaneous.
3. Higher the ratio C2/C1, higher is the cell potential.

Example: Copper concentration cell

It consists of two copper electrodes immersed in CuSO4 solutions of different concentrations. The
electrodes are externally connected through voltmeter and internally by a salt bridge.
 Applied Chemistry study material (EC-stream)– Module -2: Dr. N Suresha, [Link]., Ph.D., [Link]., [Link].

The cell is represented as,

Cu⁄Cu2+ 2+
(C1 ) //Cu(C2 ) ⁄Cu
By convention left hand electrode is the anode and right hand electrode is cathode.
2+
At anode: Cu 𝐶𝑢(𝐶 1)
+ 2𝑒 −
2+
At cathode: 𝐶𝑢(𝐶2)
+ 2𝑒 − Cu

2+ 2+
Net cell reaction: 𝐶𝑢(𝐶2)
𝐶𝑢(𝐶1)

The net cell reaction is merely the change in concentration, as a result of which current flows.

Numerical Problems:

1. Calculate the emf of Copper concentration cell at 250 C, where the copper ions ratio in the cell is
10.
[Cu2+ ]cathode C2
Given:
[Cu2+ ]anode
= = 10
C1

0.0591 [C ]
w.k.t [Link] = log [C2]; at 298 K
n 1

0.0591
[Link] = log(10)
2

[Link] = 0.0296 V.

2. A concentration cell was constructed by immersing two silver electrodes in 0.05M and 1M.
AgNO3 solution. Write the cell representation, cell reactions and calculate the EMF of the cell.

Cell representation:Ag⁄Ag + +
(0.05M) //Ag (1M) ⁄Ag

0.0591 [C2 ]
[Link] = log
n [C1 ]

At anode: Ag Ag +
(0.05M) + e
−

At cathode: Ag +
(1M) + e
−
Ag

Net cell reaction: Ag +

(1M) Ag +
(0.05M)

0.0591 1
[Link] = log ( )
1 0.05

[Link] = 0.0768V
 Applied Chemistry study material (EC-stream)– Module -2: Dr. N Suresha, [Link]., Ph.D., [Link]., [Link].

3. The spontaneous galvanic cell Sn⁄Snn+ n+

(0.024M) //Sn(0.064M) ⁄Sn develops an emf of 0.0126 V at
25oC, Calculate the valency of Tin.
0.0591 C2
[Link] = log ( )
n C1

0.0591 C2
n= log ( )
[Link] C1

0.0591 0.064
n= log ( )
0.0126 0.024

n = 2 (valency)

Sensors:
Sensors are devices used to detect the presence of chemical species and monitor physical
parameters like temperature, humidity, etc. There are different types of sensors like gas sensors,
chemical sensors and biological sensors, developed for various applications.

Working principle: Sensor selectively interacts with the analyte and generates analytical signal.
Transducer converts the analytical signal into electrical signal. Detector detects the electrical signal
and reading is recorded on the recorder.

Properties: Sensors are -

 selectively sensitive to particular type of chemical species (analyte).

 have ability to interact with the exceptionally small concentrations of analyte and send
signal.
 increased sensitivity and fast response.
 available in compact instrumentation size.
 have ability to expand previous and existing analytical detection range.
 cost effective and eco-friendly.

Applications: sensors are used-

 in military and defence applications for the detection of explosives or toxic gases.
 to detect various polluting chemicals in the atmosphere.
 in biomedical applications for early detection of disease, toxins.
 to monitor physical parameters such as temperature, humidity, etc.
 to monitor glucose in blood.
 to study neurotransmitters in brain for understanding neurophysiology.
 Applied Chemistry study material (EC-stream)– Module -2: Dr. N Suresha, [Link]., Ph.D., [Link]., [Link].

 in food industry to determine the quality and freshness of food samples.

 in agriculture to detect soil humidity, pesticide/insecticide residues and nutrient
requirements.

Analytical techniques:
Analytical techniques are the methods used for the qualitative and quantitative analysis of chemical
species present in the sample. Volumetry and gravimetry are classical methods used for the
quantitative determinations. Now a day, there are several analytical techniques like Colorimetry,
Potentiometry, Conductometry, etc., used for the analysis of chemical species.

Advantages of analytical techniques:

 Time saving – Analysis time has been reduced from several hours or days to even minutes.
 Accuracy - Improvement in accuracy of results by eliminating errors introduced due to
personal bias.
 Sensitivity - Highly sensitive to analyte present in the sample.
 Less amount of sample – Micro amounts of sample is enough for analysis.

1. Colorimetric Sensor:
Colorimetric sensors are electronic components designed to detect and convert incident light rays
into electrical signals.

Colorimetry is used for the determination of concentration of a substance present in its solution.
This method is used for colored solutions or solutions which produce color on treating with suitable
reagent.

Theory: When a monochromatic light of intensity (I0) is passed through a transparent medium, a
part of it is absorbed (Ia) by the species and electrons get excited from lower energy level to higher
energy level, some part is reflected (Ir) and remaining is transmitted (It). So intensity of incident
light is equal to the sum of Ia, Ir and It.
i.e. I0= Ia + Ir+ It
For a glass-air interface Ir is negligible and therefore, I0 = Ia + It
It/Io = T is called transmittance, log 1/T = log I0/It is called the absorbance or optical density. The
relationship between absorbance (A), concentration, (c) (expressed in mol/dm3) and path length, (t)
(expressed in cm) is given by Beer-Lambert’s law. Beer`s law states that amount of radiation
absorbed by solution is directly proportional to the concentration (c) of species in the solution.
Lambert`s law states that amount of radiation absorbed by solution is directly proportional to path
length (t) of the solution. i.e.
I
A  log 0   .c.t
It
Where ‘ɛ’ is the molar extinction coefficient and is a constant for a given substance at a given
wavelength. If ‘t’, the path length is kept constant, then, A  C. Hence the plot of absorbance
against concentration gives a straight line (calibration curve).
 Applied Chemistry study material (EC-stream)– Module -2: Dr. N Suresha, [Link]., Ph.D., [Link]., [Link].

Instrumentation:

Source: tungsten filament or sodium vapor lamp is used as a source of light.

Filter: a device used to obtain monochromatic light of required wavelength.
Sample tube: cuvette to hold the sample usually made of glass or quartz cell.
Photocell: converts the emitted light into electrical signal.
Detector: detects the light radiation absorbed by solution.
Recorder: records the numerical value.

Application: For the estimation of Copper:

When a solution of cupric ions is treated with ammonia, deep blue colored complex is formed. The
color intensity is depends on concentration of copper ions.

Cu2+ + 4NH3 → Cu(NH3)42+ (Deep blue)

Procedure:
1. Prepare a stock solution of CuSO4 by dissolving 1g in 250 ml of water.
2. Transfer 2.5, 5.0, 7.5 and 10.0 cm3 of the solution into separate, labelled 50 ml standard
flasks.
3. Add 5 ml of 1:1 ammonia solution to each of above solutions and also to the test solution,
make up to the mark with ion exchange water and mix well.
4. Prepare a blank solution by dissolving 5 ml ammonia in 50 ml std. flask and use this
solution to set the colorimeter to ZERO at 620 nm.
5. Measure absorbance to all the solutions at 620 nm.
6. Draw a calibration curve by plotting absorbance versus concentration of copper (mg/ml).
7. Using the calibration curve, determine the volume of copper sulphate in the test solution and
calculate the amount of copper (mg/ml) in the test solution.

[Link] Vol.
CuSO4 Absorbance
of
NH3
Blank 5 0
2.
5 0.06
5
5.0 5 0.12
7.
5 0.17
5
10 5 0.22
TS 5 0.2
 Applied Chemistry study material (EC-stream)– Module -2: Dr. N Suresha, [Link]., Ph.D., [Link]., [Link].

Calculation:

249.6 g of CuSO45H2O contains 63.55 g of Cu2+

63.55
⸫ 1 g of CuSO45H2O contains = = 0.2545 g of Cu2+
249.6
2+
250 ml contains = 0.2545 g of Cu
⸫ 1 ml contains = 1.018 mg of Cu2+
Volume of CuSO4intestsolution = ml
Concentration of Cu in test solution= Volume of T S x 0.02mg/ml.

Result: Concentration of Cu2+intestsolution = mg/ml

2. Potentiometric sensors:
Potentiometric sensor is a device used to determine the concentration of analyte by measuring the
change in potential of reacting system. It is based on Nernst equation, which gives the relationship
between metal ion concentration (Mn+) and electrode potential (E).

Theory: Redox titrations can be carried out potentiometrically using platinum-calomel electrode
combination. For the reaction,

Reduced form → Oxidized form + n electrons

the potential is given by the Nernst equation,

0.0591 [oxidizedform]
E  E0  log
n [reducedform]
Where, 𝐸𝑜is the standard potential of the system. The potential of the system is thus depends on the
ratio of the concentration of the oxidized to that of the reduced species. As the reaction proceeds,
the potential changes more rapidly at the vicinity of the end point of the titration. This may be
followed potentiometrically and a plot of change in potential against volume of titrant (titration
curve) is characterized by a sudden change of potential at the equivalence point also called
endpoint.

Instrumentation: A potentiometer consists of a reference electrode and an indicator electrode

(sensor) and a device to measure the change in potential during the reaction. Calomel electrode is
commonly used as reference electrode and platinum electrode as indicator electrode. The indicator
electrode responds rapidly to the changes in the potential with respect to the concentration of
analyte, which is converted to electrical signal and displayed as numerical value on potentiometer.
 Applied Chemistry study material (EC-stream)– Module -2: Dr. N Suresha, [Link]., Ph.D., [Link]., [Link].

Application: Estimation of FAS using K2Cr2O7 solution.

Procedure:
i. Pipette out 25.0 cm3 of FAS solution into a beaker. Add two test tube of dil. H2SO4.
ii. Immerse the reference-indicator electrodes assembly in the solution and connect them to
the potentiometer.
iii. Note down the emf of the cell before the addition of titrant from the burette.
iv. Now add 0.5 ml of K2Cr2O7 from the semi micro burette. Allow the solution to mix well
and measure the potential. Continue the procedure till a sudden rise in emf of the cell is
observed. Take about 5-6 more readings and tabulate the reading as mentioned be low.
v. Determine the end point by plotting ∆E/∆V versus volume of K2Cr2O7 as shown in the
figure.
vi. From end point, find the normality of FAS and calculate amount of FAS/dm3.

Vol. ofK2Cr2O7 Emf ∆E /∆V

E (mv) (mv/ml)
(V) ml

0
0.5
1.0
1.5
2.0
,
,

Calculation:
N K 2Cr2O7 xVK 2Cr2O7 0.5 xVe
Normality of FAS  
VFAS 25
Weight of FAS per liter = Normality x Equivalent weight of FAS (392)
Result: Weight of FAS per liter = ………… g/dm3.
 Applied Chemistry study material (EC-stream)– Module -2: Dr. N Suresha, [Link]., Ph.D., [Link]., [Link].

3. Conductometric sensor:
It is used to determine the end point of acid-base titration by observing the change in specific
conductance of solution.

Theory: The principle underlying conductometric titration is the replacement of ions of particular
conductivity by ions of different conductivity during titration. It is based on Ohm`s law, which
states that the current (I) flowing through a conductor is directly proportional to the applied
potential (E) and inversely proportional to the resistance (R).
i.e. I = E/R or E = I R
The reciprocal of resistance is called conductance.
1 a
i.e. C = 1/R = x Ω-1 or mho or Siemens
 l

l l
⸫ R =    , where ρ is specific resistance, is called cell constant
a a
The reciprocal of specific resistance is called specific conductance ‘  ’
1l l
i.e.  =   or C  
Ra a
Specific conductance is defined as the conductance of the solution which is placed between two
electrodes of 1cm apart and having unit area of cross section.
The conductance of a solution is depends on temperature, number of the ions and their mobility.

Instrumentation:

It consists of two platinum electrodes each of unit area of cross section placed unit distance apart.
The electrodes are dipped in the electrolyte solution taken in a beaker and connected to a
conductance measuring device.

Applications: Conductometric titrations are used to

1. Estimate mixture of weak acid and strong base
2. Estimate the concentration of colored or turbid solutions which cannot be titrated using
indicators.
3. Estimate weak acids or bases where no suitable indicators are available.
4. Estimate very dilute solutions.
 Applied Chemistry study material (EC-stream)– Module -2: Dr. N Suresha, [Link]., Ph.D., [Link]., [Link].

Ex. Estimation of weak acid (CH3COOH) versus strong base (NaOH).

CH3COOH + NaOH → CH3COONa + H2O

Initially conductance is very low because acetic acid is a weak electrolyte. When NaOH is added to the
acid, the salt formed is highly ionized and hence conductance increases. On complete neutralization
of the acid, further addition of base leads to an increases in the number of OH- ions. Hence the
conductance increases sharply.
A plot of conductance against the volume of base added is shown in the figure. The point of
intersection of two curves gives the neutralization point.

Procedure:
i. Pipette out 50 ml of acetic acid into a beaker.
ii. Immerse the conductometric sensor in the solution and connect them to the conductometer.
iii. Note down the conductivity of the solution before the addition of NaOH from the burette.
iv. Now add 0.5 ml of NaOH from the semi micro burette. Allow the solution to mix well and
measure the conductance. Continue the procedure till the acid is completely neutralized.
Take about 5-6 more readings after neutralization and tabulate the reading as mentioned
below.
v. Determine the neutralization point by plotting conductance versus volume of NaOH as
shown in the figure.
vi. From end point, find the normality of CH3COOH and calculate amount of CH3COOH/dm3.

Vol. of NaOH conductance

(V) ml

0
0.5
1.0
1.5
2.0
,
,

Calculation:
N NaOH xVNaOH 0.5 xVe
Normality of CH3COOH   = ‘a’
VCH3COOH 50
Weight of CH3COOH per liter = Normality x Equivalent weight of CH3COOH (60)
= ‘a’ x 60

Result: Weight of CH3COOH per liter = ………… g/dm3.

 Applied Chemistry study material (EC-stream)– Module -2: Dr. N Suresha, [Link]., Ph.D., [Link]., [Link].

Question Bank:
1. What are reference electrodes? Discuss the construction, working and applications of
Calomel electrode.
2. Describe the construction and working of glass electrode.
3. Elucidate the application of glass electrode for the determination of pH of solution.
4. What are concertation cells? Derive an equation for cell potential of concentration
cell.
5. What is electrochemical sensor? Explain the working principle and applications of
electrochemical sensor.
6. Discuss the principle and instrumentation of colorimetric sensor.
7. Elucidate the application of colorimetric sensor for the estimation of copper.
8. Describe the principle and instrumentation of potentiometric sensor.
9. Discuss the principle and instrumentation of conductometric sensor.
10. Discuss the application of potentiometric sensor for the estimation of iron.
11. Describe the application of conductometric sensor for the estimation of weak acid.