RNS INSTITUTE OF TECHNOLOGY

DEPARTMENT OF CHEMISTRY
Channasandra, Bengaluru - 560 098

APPLIED CHEMISTRY (BCHEE102)

Sensors in Analytical
Techniques
Module-5

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 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 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.

ELECTRODE SYSTEM
Introduction:

An important aspect of electrochemistry is the inter conversion of electrical energy and chemical energy
that takes place through oxidation-reduction (redox) reaction.

In oxidation reaction, a metal loses one or more electrons resulting in increase in oxidation number.
M Mn+ + ne-

In reduction reaction, a metal gains one or more electrons resulting in decrease in oxidation number.
Mn+ + ne- M

Electrochemical cell: The device which convers chemical energy to electrical energy or electrical
energy to chemical energy by the means of electrochemical redox reaction is called electrochemical cell.
These are of 2 types,

1. Galvanic cell: The device which convers chemical energy to electrical energy
2. Electrolytic cell: The device which convers electrical energy to chemical energy

Electrode potential (E): The potential developed between a metal rod and its own ions in a solution at
equilibrium is called electrode potential. It is denoted by E and expressed in volts.

Standard electrode potential (E0 ): The potential developed when a metal is in equilibrium with 1M
solution of its own ions at 298K is called standard electrode potential. It is represented by E0. It is also
called as standard reduction potential (SRP).

Cell Potential( Ecell): It is defined as the potential difference between the two electrodes when the cell
is being discharged. It is given by Ecell = Ecathode - Eanode.

Where Ecathode is the electrode potential of the cathode and Eanode is the electrode potential of the anode.

Types of electrodes:
1. Metal- metal ion electrode: The electrode system consisting of metal in contact with a solution
containing its own metal ion.
Example: Cu|Cu2+ . Zn|Zn2+

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2. Metal – metal insoluble salt electrode: The electrode system consisting of metal in contact with a
sparingly soluble salt of the same metal dipped in a solution containing anion if the salt.
Example: Calomel electrode (Hg|Hg2Cl2|Cl-) , Ag-AgCl electrode (Ag|AgCl|Cl-)
3. Gas electrode: The electrode system consists of gas in contact with an inert metal wire which is
dipped in an ionic solution of the gas molecule.
Example: Standard hydrogen electrode (SHE)
4. Ion selective electrode: These are the electrodes which are sensitive to particular ionic species and
will develop a potential when a membrane is in contact with an ionic solution.
Example: Glass electrode.
5. Redox electrode: Electrode in which potential arises due to the presence of oxidized and reduced
forms of the same substance in solution.
Example: Platinum electrode, Pt | Fe2+, Fe3+
6. Amalgam electrode: It is a modification of metal-metal ion electrode. Amalgam is the alloy of any
metal with mercury. In the place of metal, its solution in mercury is used.
Example: Zinc -amalgam electrode, where Zn(Hg) | Zn2+

Reference electrodes: These are the electrodes of constant potential which are used to determine
electrode potential of other electrodes. There are two types of reference electrodes.
 Primary reference electrode. Eg: Standard hydrogen electrode (SHE).
 Secondary reference electrode. Eg: Calomel electrode, Ag/AgCL electrode

Construction and working of calomel electrode:

Construction:
 Calomel electrode is a metal- metal insoluble salt electrode and is a secondary reference electrode.
 Calomel electrode consists of a glass tube. A small amount of pure mercury is placed at the bottom of
the glass tube and it is covered by a paste of Hg and calomel (mercurous chloride, Hg2Cl2).
 The remaining portion of the glass tube is filled with KCl solution of known concentration (saturated,
1N or 0.1N).
 A platinum wire is dipped into the mercury and is used to provide external electrical contact. The
porous plug at the bottom acts as a salt bridge.
 Representation: Pt|Hg|Hg2Cl2|KCl(x) Where x = sat or 1N or 0.1N.

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Working: Calomel Electrode can act as anode or cathode depending on the nature of the other electrode.
When acts as anode: 2Hg + 2Cl- Hg2Cl2 + 2e-
-
When acts as cathode: Hg2Cl2 + 2e 2Hg + 2Cl-
At equilibrium: Hg2Cl2 + 2e- 2Hg + 2Cl-
The electrode potential at 298K is given by
Ecal= E0cal – 0.0591 log [Cl-]
From the above equation it is clear that as the concentration of Cl - ion increases, the electrode potential
decreases.

Advantages:
 It is easy to construct and maintain.
 Its potential can remain constant and it can easily be reproduced.
 It can be used in the presence of oxidizing agents.

Applications:
 It is used as reference electrode in all potentiometric titrations.
 It is used as reference electrode with glass electrode in pH determination.
 It is used as a secondary reference electrode in the measurement of single electrode potential.
Note: At 298K, the electrode potentials are as follows.
KCl concentration 0.1N 1N Saturated
Ecal (V) 0.334 0.281 0.2422

Electrolyte concentration cells: The galvanic cell in which electrode and electrolyte present in both
half cells are same but only the concentration of electrolyte is different is called electrolyte
concentration cell.
Derivation:

The above concentration cell can be represented as: Zn| ZnSO4 (C1) || ZnSO4 (C2)| Zn
The electrode reactions are
At anode: Zn Zn2+ (C1) + 2e-
At cathode: Zn2+ (C2) + 2e- Zn
2+
NCR: Zn (C2) Zn2+ (C1)
Where C1 & C2 are concentrations of ZnSO4 solution at anode and cathode respectively & C2> C1
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Emf of anode is given as:
2.303RT
Eanode = E0Zn2+/Zn + logC1 …………………… (1)
nF
Emf of cathode is given as:
2.303RT
Ecathode= E0Zn2+/Zn + logC2 ……………………(2)
nF
Ecell = Ecathode – Eanode ………………………..(3)

Substitute eqn (1) & (2) in (3),

2.303RT 2.303RT
Ecell = (E0Zn2+/Zn + logC2) _
(E0Zn2+/Zn + logC1)
nF nF
2.303RT _ 2.303RT
Ecell = logC2 logC1
nF nF
2.303RT _
Ecell = [logC2 logC1]
nF
2.303RT C ………………… (4)
Ecell = log 2
nF C1

On substituting the values for R = 8.314 J/K/mol, T = 298K & F = 96500C

0.0591 C …………………(5)
Ecell = log 2
n C1

The equation (4) & (5) are known as the expression for EMF of an electrolyte concentration cell.

NUMERICAL PROBLEMS
Problem 1:A concentration cell was constructed by immersing two silver electrodes in 0.02M and
2M AgNO3 solutions. Write the cell representation, cell reactions and calculate the emf of the cell at 250C.
(i)Cell representation:
Ag|AgNO3 (0.02 M) || AgNO3 (2M)|Ag
(ii) Electrode reactions:
+
At anode: Ag Ag (0.02M) + e¯
+
At cathode: Ag (2M) + e¯ Ag
+
NCR: Ag (2M) Ag+ (0.02M)

(iii)The emf of the concentration cell:

0.0591 C
Ecell = log 2
n C1
0.0591 2
Ecell = log
1 0.02
Ecell = 0.0591 log 100
Ecell = 0.0591 × 2
Ecell = 0.1182V

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Problem 2: Represent the cell formed by the coupling of two Cu electrodes immersed in CuSO4
solutions. The concentration of cupric ions in one electrode system is 100 times more concentrated than
other. Write the cell reaction and calculate the potential at 300K.
(i)Cell representation:
Cu|CuSO4 (1M )|| CuSO4 (100M)|Cu
(ii) Electrode reactions:
2+
At anode: Cu Cu (1M) + 2e¯
2+
At cathode: Cu (100M) + 2e¯ Cu
2+ 2+
NCR: Cu (100M) Cu (1M)
(iii)The emf of the concentration cell:
2.303RT C
Ecell = log 2
nF C1
2.303  8.314  300 100
Ecell = log
2  96500 1
Ecell = 0.0297 log100
Ecell = 0.0297 × 2
Ecell = 0.0595V

Problem 3: A cell is obtained by combining two Cd electrodes immersed in cadmium sulphate solutions
of 0.1M and 0.5M at 250C. Write the cell representation, cell reactions and calculate the emf of the
concentration cell.
(i)Cell representation:
Cd|CdSO4 (0.1M )|| CdSO4 (0.5M)|Cd
(ii) Electrode reactions:
2+
At anode: Cd Cd (0.1M) + 2e¯
2+
At cathode: Cd (0.5M) + 2e¯ Cd
2+
NCR: Cd (0.5M) Cd2+ (0.1M)
(iii)The emf of the concentration cell:
0.0591 C
Ecell = log 2
n C1
0.0591 0.5
Ecell = log
2 0.1
Ecell = 0.02955× log5
Ecell = 0.02955× 0.6989
Ecell = 0.0207V

Problem 4: The emf of the cell Cu| CuSO4(0.005M) ||CuSO4(x) | Cu is 0.0295V at 250C. Find the value
of x.
0.0591 C
Ecell = log 2
n C1
0.0591
0.0295 = log
2
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 log = = 0.9983
= antilog(0.9983) = 9.9609
x= 9.9609×0.005
x = 0.0498M

Problem 5: The emf of the cell Cd|CdSO4(x)||CdSO4 (0.025M)|Cd is 0.035V at 280C. Find the value of
x.
2.303RT C
Ecell = log 2
nF C1
0.035 = log
log = = 1.172
antilog (1.172) = 14.8618
x =
x = 1.6818× 10-3M

Problem 6: The emf of the cell Ag|AgNO3 (0.001M) ║AgNO3 (xM)|Ag is 0.0659V at 250C. Write the
cell reaction and find the value of x.
Electrode reactions:
+
At anode: Ag Ag (0.001M) + e¯
+
At cathode: Ag (xM) + e¯ Ag
+
NCR: Ag (xM) Ag+ (0.001M)
0.0591 C
Ecell = log 2
n C1
0.0591 x
0.0659 = log
1 0.001
x 0.0659
log = = 1.115
0.001 0.0591
x
= antilog(1.115)= 13.03
0.001
x= 13.03 0.001
x= 0.01303M

Problem 7: The emf of the cell Cu| CuSO4(0.001 M) ||CuSO4(x M) | Cu is 0.0595V at 250C. Find the
value of x.
0.0591 C
Ecell = log 2
n C1
0.0591 x
0.0595 = log
2 0.001
x
log = 2.0135
0.001

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 x
= antilog(2.0135) = 103.16
0.001

= 103.16 0.001
x = 0.1032M

Problem 8: A spontaneous galvanic cell tin|tin ion (0.024M)||tin ion (0.064M)|tin develops an emf of
0.0126V at 250C. Calculate the valency of tin.
0.0591 C
Ecell = log 2
n C1
0.0591 0.064
0.0126 = log
n 0.024
0.0591 0.064
n= log
0.0126 0.024
n= 4.690 log 2.6666
n = 4.690 × 0.4259
n=1.99 ≈ 2 (n is the valency of tin)
Valency of tin is 2. Tin is divalent.

Ion selective electrodes: These are the electrodes which are sensitive to particular ionic species and
will develop a potential when a membrane is in contact with an ionic solution. The potential developed
at these electrodes is a function of the concentration of that ion in the solution. Example: Glass
electrode

Construction and working principle of a glass electrode

Construction:
 Glass electrode is an ion selective electrode in which a thin glass membrane is present which is
permeable to H+ ion and not to other ions in the solution.
 A glass electrode consists of a thick–walled glass tube with a very thin walled glass membrane
(bulb) at the bottom. Its thickness varies from 0.01-0.03mm.
 This glass membrane made up of special glass of low melting point and high electrical
conductivity. The approximate composition of this glass is 72%SiO2, 22%Na2O and 6%CaO.

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 This glass membrane allows only H+ ions up to a pH range from 1 to 9.
 The glass bulb is filled with 0.1M HCl in which a silver–silver chloride electrode is dipped as an
internal reference electrode which provides external electrical contact.
Representation: Ag|AgCl|HCl(0.1M) |glass membrane

Working:
When the glass electrode is dipped in the test solution, the Na+ ions of the glass membranes are
exchanged for H+ ions of the test solution.
Na+Gl- + H+ ↔ H+Gl- + Na+
Membrane Solution Membrane Solution

When a glass electrode is placed between two H+ ion solutions of different concentrations (C1 and C2),
boundary potential is developed across the membrane. The boundary potential is given by the equation

𝟎 𝟎𝟓𝟗𝟏 𝑪𝟐
𝑬𝒃 𝒍𝒐𝒈
𝒏 𝑪𝟏
0.0591 0.0591
Eb = log C2 – log C1 (n=1 for H+ ion)
n n
Eb = 0.0591 logC2 – 0.0591 logC1
Eb = L + 0.0591logC2 (Where L=- 0.0591logC1, is a constant, C1 = 0.1M)
+
Since C2 is the unknown H concentration, we can write
Eb = L + 0.0591 log[H+] (since pH = - log [H+])
Eb = L - 0.0591pH ……………………..(1)
It is found that the potential of the glass electrode (EG) has three components:
 Boundary potential (Eb)
 Asymmetric potential (Eassy)
 Potential of the internal reference Ag – AgCl electrodes (EAg/AgCl)

EG = Eb + Eassy + EAg/AgCl
…………………….(2)

Substitute equation (1) in (2), we get

EG= (L- 0.0591 pH) + Eassy + EAg/AgCl
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EG = E0G – 0.0591pH

Where E0G = L+ Eassy + EAg/AgCl . E0G is the combination of three constant terms.

Application of glass electrode

1. Determination of pH of the solution.
2. Analyze foods and cosmetics.
3. Determination of soil acidity.

Determination of pH of solution using glass electrode

The cell consists of a glass electrode as indicator electrode and a saturated calomel electrode (SCE) as
reference electrode, the cell is immersed in a solution whose pH is to be determined. The emf cell is
measured using vacuum tube voltmeter (VTVM).

The cell assembly is represented as:

Pt|Hg|Hg2Cl2 |KCl(sat)||solution of unknown pH| glass membrane|HCl (0.1M) |AgCl|Ag
The emf of the cell is given by
Ecell = Ecathode – Eanode
Ecell = EG – ESCE
E cell = (E0G – 0.0591 pH) – ESCE (Where EG =E0G – 0.0591 pH)

𝑯
𝑬𝟎𝑮 − 𝑬𝒄𝒆𝒍𝒍 − 𝑬𝑺𝑪𝑬
𝒑
𝟎 𝟎𝟓𝟗𝟏

E0G value of a glass electrode can be determined by using a solution of known pH(Buffer).

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 SENSORS AND ANALYTICAL TECHNIQUES

Introduction:

A device which provides a usable output in response to a specified measurand like light, heat, motion,
moisture, force, pressure, displacement, etc. It produces a proportional output signal (electrical,
mechanical, magnetic, etc.
Sensors : Sensors are devices which “read” a physical stimulus (heat, light, sound, weight, attraction
etc.) and then convert that reading into an electrical signal output.

 Receptor - It is interacting with analyte specifically and selectively. Observe and acquire
information.

 Transducer- Converts one form of energy into another form (normally into electric energy).

 An actuator- The signal given by transducer is amplified and converted to digital form. The
amplified signal can be displayed in various forms such as numeric value, graph, image etc. Converts
electrical signal into physical output.

There are four types of sensors.

1. Electrochemical Sensors
2. Conductometric sensor
3. Thermometric sensors
4. Optical sensors

Electrochemical sensors:

Principle: The sensors which convert the effect of electrochemical reaction between analyte and
electrode surface into a useful signal are known as electrochemical sensors. Electrochemical sensor
involves the measurement of electric current generated by electrochemical reaction.
 Electrochemical sensors consist of working (sensing) electrode, reference electrode, counter
electrode and electrolyte.
 The working (sensing) electrode has a chemically modified surface and helps in the oxidation of
analyte. The potential at the sensing electrode varies due to continuous electrochemical reaction. If
there is lack of potential on sensing electrode, it leads to poor performance of sensor.
 To improve the performance, reference electrode is placed very close to sensing electrode. It
provides stable and constant potential at sensing electrode and support the effectiveness of the
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 sensor.
 Counter electrode is connected to sensing electrode for reduction reaction.
 The electrolyte is chemically and physically stable. They help to transport ions within the sensor,
contact all electrodes effectively, solubilize the reactants and products.
 Hydrophobic membrane prevents unwanted particles reaching electrode and prevents liquid
electrolyte from leaking out.

Applications:

1. Electrochemical sensors used for the detection of blood glucose.

2. Used for pH measurements.
3. Used to detect pesticides.
4. Used in the detection of hydrocarbon pollutants.
5. Used to detect toxic gases.
6. Used in soil parameter analysis, evaluation, and in agriculture applications.

THERMOMETRIC SENSORS:

They are based on the measurement of thermal changes during the interaction between analyte and the
receptor. Thermal changes are converted to measurable change in the temperature or potential.

Ex: Flame photometer.

Flame photometer:

A flame photometer is an analytical instrument used in chemistry used in chemistry to measure the
concentration of certain metallic elements (such as sodium, potassium, lithium and calcium etc.,) in a
sample.

Principle: The process of measurement of emission radiation, when the analyte sample is introduced
into the flame is called flame photometry. Following changes takes place when a solution containing a
compound of the metal to be estimated is introduced into a flame.

1. Solvent evaporates leaving behind a solid residue.

2. Vaporization of the solid followed by its dissociation into constituent atoms which are initially in
the ground state.

3. Few gaseous atoms absorb thermal energy of the flame and get excited from the ground state.

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4. Excited atoms are unstable, and they return to ground state by emitting radiation that is proportional
to concentration of metal ions in solution and is measured using flame photometer.

M*X- MX evaporation of solvent

MX solid vaporization
MX Dissociation
M + X
Solution Mist Solid Gas Atoms

Thermal excitation of metal

atom

M Emission of characteristic radiation

M*
Atom in ground Atom in exited state

Instrumentation:

 Sample is drawn into nebulizer through capillary tube & mixed with air, to get mist.
 The mist is mixed with fuel in the mixing chamber.
 The sample mixture is sprayed over the burner. Sample gets burnt in flame and emits radiation.
 The lens converges all the radiation and fall on monochromator.
 The radiation emitted passes through a monochromator which transmits only the radiation
characteristic of the element under test. The radiation finally falls on the detector. The detector
displays the emission intensity. The output from the detector is measured on a suitable digital
recorder.

Working:

1. Wavelength is fixed in monochromator (Eg: for Na =589nm).

2. Blank solution is sprayed over the flame and emission intensity is set to zero.
3. Series of standard sample solutions of known concentration are sprayed one by one and emission
intensity is noted.

4. The sample of unknown concentration is also sprayed and emission intensity is noted.
5. The calibration graph is plotted with emission intensity against concentration.

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Applications:

1. For qualitative determination of cations like Na, K, Ca, Ba, Cu. Since these easily get excited or
higher energy level at low temperature.

2. For quantitative analysis to determine the concentration of group IA and IIA elements like,
 Concentration of calcium in hard water.
 Concentration of sodium, potassium in urine.
 Concentration of calcium and other elements in glass and ceramic materials.

Conductometric sensors
Conductometric sensors are chemical sensors, determines concentration of analyte on the basis of
measurement of changes in electrical conductivity when a specific analyte interacts between the
electrodes.

Principle:

Ohm‟s law states that the current I (amperes) flowing through a conductor is directly proportional to the
applied potential, E (volts) and inversely proportional to the resistance R (ohms) of the conductor.
I=
The reciprocal of the resistance is called the conductance.
The resistance of a material with an area of 1cm2 and length l cm is given by,
R= Where ρ = specific resistance.
The reciprocal of the specific resistance is specific conductance (κ)and it is given by
k= X l/a = cell constant and R = resistance of the solution.
Specific conductance of an electrolyte solution is the conductance of the solution present between two
parallel electrodes of 1 cm2 area of cross section and 1 cm apart.

Construction: These consists of 2 inert electrodes placed at unit distance and each having unit cross
sectional area. The electrodes are used to measure change in conductance of a solution. Conductance of
a solution is based on:

1. The concentration (number) of ions.

2. Mobility of each type of ion. Smaller the size of ion higher is mobility and higher is conductance.

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Working of conductometric sensor:

 The conductivity is result of dissociation an electrolyte, into ions.

 The migration of the ions is induced by an electric field.
 When a potential difference is applied to the electrode, there is an electrical field within electrolyte,
so the positively charged ions move towards cathode and negatively charged ions are move towards
anode.
 Thus, the current in the electrolyte is caused by the ion movement towards the electrodes where the
ions are neutralized and isolated as neutral atoms (or molecules).
 This chemical change is recognized by working electrode and transducer converts this chemical
change into electrical signal.

Application of conductometric sensor

1. Conductometric sensors is used to estimate acids, bases and their mixtures in a sample.
2. Used to determine urea.
3. It is used to check the number of ionic impurities in water samples.
4. The conductometric measuring method can be used in enzyme catalysis to determine analyte
concentration and enzyme activity and selectivity.
5. It is based on inhibition analysis as intended for the determination of organo phosphorous
pesticides.

Estimation of weak acid by conductometric sensors:

Instrumentation:
 A known volume of the weak acid is taken in the beaker and electrode is dipped. The electrode is
connected to a conductivity bridge. Initial conductance is measured.

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 NaOH is added in the increment of 0.5ml from a burette and the conductance is measured for every
0.5ml NaOH.
 The end point is determined by plotting conductance against the volume of NaOH added.

Consider the titration of acetic acid against NaOH.

CH3COOH + NaOH CH3COONa + H2O
1. The conductance will be initially low since acetic acid is a weak electrolyte.
2. When NaOH is added to the acetic acid, the sodium acetate formed is highly ionized and the
conductance increases.
3. After complete neutralization of the acetic acid, further addition of NaOH raises the conductance
sharply. This is due to increase in the concentration of the OH- ions.
4. A plot of conductance (ohm-1) against the volume of NaOH (cm3) gives a graph as shown in figure.
The point of intersection of the lines gives the equivalence point.

Observation and Calculation:

Volume of CH3COOH, VAcetic acid = 25 ml

Strength of standard NaOH solution, NNaOH (given) = ……N

Volume of NaOH required to neutralize CH3COOH, VNaOH = ..…ml

NAcetic acid VAcetic acid = NNaOH VNaOH

The strength of CH3COOH, NAcetic acid = NNaOH X VNaOH

VAcetic acid

= Y N

Weight of CH3COOH present in 1ml of CH3COOH = NAcetic acid x Eq.wt. of CH3COOH

16
 = Y x 60 g/ dm3

= ……………..... g/ dm3

Optical Sensors (Colorimeter):

Principle: This method is based on Beer-Lamberts law. When monochromatic light falls on a
homogeneous medium, a portion of incident light is absorbed by the medium and remainder is
transmitted. The extent of absorption depends on the concentration of the solution and thickness of the
medium.

Beer – Lambert‟s law: Absorbance is directly proportional to concentration and thickness of the
medium.

A = εCt

Where „A‟ = absorbance,

„C‟ = concentration of the solution

„t‟ = thickness of the medium and

„ε‟ = molar absorption coefficient

Instrumentation:

1. Light source: Tungsten lamp

2. Filter: It provides the desired wavelength range where solution gives the maximum absorbance.
3. Cuvette: Cuvette which holds the sample solution for analysis.
4. Photocell detector: It is used to convert transmitted light into electrical signal.
5. Recorder: It is used to read the electrical signal directly as absorbance.

Working:

1. Blank solution is taken in cuvette and monochromatic light of suitable wavelength is allowed to fall.
Its absorbance is adjusted to zero.
2. Different analyte solutions of known concentration are placed and its absorbance is noted.
3. The absorbance for analyte solution of unknown concentration is noted.
4. A calibration curve is obtained by plotting absorbance versus standard concentrations of analyte.
From calibration curve, the volume of analyte in unknown solution is obtained.
5.

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Applications:

1. Determination of the copper colorimetrically.

2. Used in soil testing for analysis of soil and plant nutrients.
3. Used in food testing laboratories to check concentration of chemical parameters.
4. Used in clinical laboratory for analysis of biomolecules such as glucose.

Estimation of Copper by optical sensor (colorimetry)

Instrumentation:

1. Light source: Tungsten lamp is used as light source.

2. Slit: It minimize unwanted light.
3. Lens: Give parallel beam of light.
4. Filter: 620nm wavelength because cuprammonium sulphate solution shows the maximum
absorbance.
5. Cuvette: CuSO4 solution for analysis.
6. Photocell detector: It is used to convert transmitted light into electrical signal.
7. Recorder: It is used to read the electrical signal directly as absorbance.

Procedure: A series of standard solutions of CuSO4 is prepared by adding ammonia solution and diluted to
the definite volume by using colorimetry water.

CuSO4 + 4NH3 + H2O [Cu(NH3)4 SO4 · H2O]

(Cuprammonium sulphate)

1. 2, 4, 6, 8 and 10ml of CuSO4 solution is taken in five different 25ml volumetric flasks.
2. 2.5ml of NH4OH is added to all the flasks and made up to the mark using colorimetry water.
3. Blank solution is prepared by taking 2.5ml of NH4OH and made up to the mark with colorimetry
18
 water in 25ml standard volumetric flask.
4. To the given test solution of CuSO4, 2.5ml of NH4OH is added and made up to the mark with
colorimetry water in 25ml standard volumetric flask.
5. Filter is set to 620nm and absorbance (optical density) of the blank solution is made zero.
6. Absorbance of all the prepared standard solutions and test solution is noted.

7. A graph of absorbance versus volume of CuSO4 is plotted. From the absorbance of test solution, the
volume of the given CuSO4 and the weight of copper in the CuSO4 is determined.

Observation and Calculation:

4g of CuSO4 .5H2O is dissolved in 1000ml of distilled water
Therefore, 1ml of copper sulphate solution = 4 / 1000 = 0.004 g of CuSO4
249.69 g of copper sulphate contains 63.54 g of copper.
0.004 g of copper sulphate contains = 0.004 x 63.54 = 0.001018 g of copper = 1.018mg of copper.
249.69
Therefore, 1ml of copper sulphate contains 1.018 mg of copper

The weight of copper in the test solution = Volume of CuSO4 from the graph× 1.018 mg of copper

= Y mg of copper.

Potentiometry:
Potentiometry is the estimation of substances in solution by observing sudden change in
potential of the cell at equivalence point.
Theory: The relation between electrode potential and metal ion concentration is given by the
Nernst equation.
E = E0 + 0.0591 log [Mn+]
n

Thus, the potential of an electrode (E) depends upon the concentration of the ion Mn+

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

and a device for measuring the potential. The indicator electrode responds rapidly to the
changes in the potential due to the concentration changes of the analyte. A simple
arrangement of potentiometric titration is shown in Figure.

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  A known volume of the analyte is taken in a beaker and its potential is determined
by connecting the assembly to a potentiometer.
 The titrant is added in increments of 0.5ml and the potential is measured each time.

 The end point is determined by plotting change in potentials against the volume of titrant.

Applications:
1. It is used in redox titrations to estimate the concentration of analyte in the sample
solution. Example: Estimation of FAS potentiometrically using standard K2Cr2O7 solution.
2. It is used in precipitation titrations, which involves insoluble salt metals. Example:
Titration of silver ion with a halide ion. Silver electrode is used as indicator electrode.

Application: Estimation of iron using potentiometer

Principle:

The potentiometric titration is the titration to find-out the equivalence point (endpoint) of the
redox reaction by measuring the change in the potential of an indicator electrode. The
potential at the indicator electrode arises from, ions in one of the oxidation states to more stable
oxidation state, which is according to Nernst equation

E = Eo + 0.0591 log [ Oxidizedform ]

n [ Reduced form ]
Where,
Eo is the standard reduction potential of the system.
E is measured when the concentration ratio of [Ox] /[ Red ] changes during the course of
titration.
As the reaction proceeds, the ratio and hence the potential changes more rapidly in the
vicinity of the electrode. The equivalence point is obtained by sudden change in the emf of
the cell. The reaction that takes place between FAS and K2Cr2O7 in acidic medium is

K2Cr2O7 + 7H2SO4 + 6FeSO4 → K2SO4 + Cr2(SO4)3 + 3Fe2(SO4)3 + 7H2O

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Procedure and working:
Burette : Standard K2Cr2O7 solution.

Accessories: Digital potentiometer attached with calomel and platinum

electrodes. Beaker : Given ferrous ammonium sulphate (FAS) solution + 1 t.t. of
dil.H2SO4 + magnetic bead for stirring.
Place the electrodes inside the beaker containing FAS solution and note down the
potential. Add K2Cr2O7 solution from the burette in increments of 0.5ml, with constant
stirring and measure the potential after each addition. After a sudden jump of potential,
record 8-10 more readings.
 Initially, the potential of Pt electrode is dependent on the concentration of Fe2+ ions
in the denominator. As the amount of K2Cr2O7 is added to the solution, gradually,
Fe2+ ions gets oxidized to Fe3+ increasing its concentration. As a result, the potential
of the electrode increases depending on their ratio of respective ions.
E = E° + 0.0591 log [Fe3+]
1 [Fe2+]
 When there is no Fe2+ions in the solution, there is abrupt increase of potential with
addition of potassium dichromate. This indicates the equivalence point of the
titration. The sudden jump in the potential value at the Pt electrode is also due to
developed potential as a result of the redox reaction Cr6+ 3+
in the solution.
E = E° + 0.0591 log[Cr6+]
6 [Cr3+]
 After the end point there is gradual increase in potential since concentration of Cr6+
ion increases. Determine the equivalence point of titration by pl ot ti ng ∆E/ ∆V
versus vol um e of K2Cr2O7.
 QUESTION BANK
1. Define single electrode. Explain different types of electrodes with an example.
2. What are the types of reference electrode. Explain the construction and working of calomel
electrode. Mention its applications.
3. What are electrolyte concentration cells? Derive an expression for emf of an electrolyte
concentration cell.
4. The EMF of the cell Ag|AgNO3 (C1M)||AgNO3(2M)|Ag is 0.8V at 270C. Find the value of
C1 .
5. Define the following terms (i) Reference electrode (ii)Concentration cell (iii) Standard
electrode potential (iv) EMF of the cell.
6. Define ion selective electrode. Explain the construction and working principle of glass
electrode.
7. Explain how glass electrode can be used in determination of pH of unknown solution?
8. Discuss the theory, construction and applications of conductometric analysis.
9. Explain the instrumentation of conductometric sensor. Illustrate the graph of Weak acid Vs
Strong base.
10. Explain the working principle and applications of electrochemical sensor.
11. Explain the working principle and applications of thermometric sensor.
12. Illustrate the working principle and applications of optical sensor.
13. Give the principle and instrumentation of colorimetric sensors for estimation of copper.
14. Describe the theory, instrumentation and applications of potentiometric sensor.
15. Explain the estimation of Fe using potentiometric titration.

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