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Module 5 - ECE D1

The document outlines the principles and applications of various electrode systems and sensors in electrochemistry, including ion-selective electrodes, glass electrodes, and reference electrodes like the calomel electrode. It details the construction, working, and limitations of these electrodes, as well as the principles behind conductometric and optical sensors used for measuring pH and detecting analytes. Additionally, it discusses the functioning of concentration cells and the significance of electrochemical sensors in various applications such as blood glucose detection and environmental monitoring.

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0% found this document useful (0 votes)
28 views16 pages

Module 5 - ECE D1

The document outlines the principles and applications of various electrode systems and sensors in electrochemistry, including ion-selective electrodes, glass electrodes, and reference electrodes like the calomel electrode. It details the construction, working, and limitations of these electrodes, as well as the principles behind conductometric and optical sensors used for measuring pH and detecting analytes. Additionally, it discusses the functioning of concentration cells and the significance of electrochemical sensors in various applications such as blood glucose detection and environmental monitoring.

Uploaded by

sagarhegde1818
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

Dr Puneetha J, Assistant Professor, Chemistry Department, JSSATEB

JSS ACADEMY OF TECHNICAL EDUCATION, BENGALURU


JSS Campus, Uttarahalli-Kengeri Main Road, Bengaluru-560060.
Department of Chemistry
Electrical & Electronics Engineering and Allied branches (BCHEE202/202)
Academic Year: 2022-23

Module 5
Electrode System: Introduction, types of electrodes. Ion selective electrode –
definition,construction, working and applications of glass electrode. Determination of pH
using glasselectrode. Reference electrode- Introduction, calomel electrode– construction,
working and applications of calomelelectrode. Concentration cell– Definition,
construction and Numerical problems.
Sensors: Introduction,working principle and applications of Conductometric sensors,
Electrochemicalsensors, Thermometric sensors, and Optical sensors.
Analytical Techniques: Introduction, principle and instrumentation of Colorimetric
sensors; its application in the estimation of copper, principleandinstrumentationof
Potentiometric sensors; principle and instrumentation of its application in the estimation
of iron, Conductometric sensors; its application in the estimation of weak acid.

Electrode System

Introduction:
Electrochemistry is the branch of chemistry which deals with the transformation of electrical
energy to chemical energy and vice versa. In brief it deals with the chemical applications of
electricity. Electric current is a flow of electrons generated by a battery, when the circuit is
completed. Electrolysis is one process where electrical energy causes chemical changes. It is
carried out in an apparatus called electrolytic cell. The cell contains electrolyte and electrodes.
The electrode connected to the positive pole of the current source is called anode. The electrode
connected to the negative pole of the current source is called cathode. When an electric current
is passed through the electrolytic solution, cations move towards cathode (-ve electrode and
anions move towards anode (+ve electrode)
Ex: Electrolysis of water yields H2 and O2
In other process, certain chemical reactions takes place in a vessel and produce electric energy.
The device is called electrochemical cell. Eg. Galvanic cell, batteries and fuel cells. Broadly we
can classify the cells as Electrolytic cells and Galvanic cells.
Electrolytic cell: A device which converts electrical energy to chemical energy
Galvanic cells: A device which converts chemical energy to electrical energy

The Types of electrodes are:


1) Metal-Metal ion electrode
2) Metal-Metal salt ion electrode
3) Gas -ion electrode
4) Redox electrode
5) Ion Selective electrode

1) Metal-Metal ion electrode: An electrode of this type consists of a metal rod dipped
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Dr Puneetha J, Assistant Professor, Chemistry Department, JSSATEB

into a solution of its own salt.

E.g.: Zn rod dipped in a solution of ZnSO4 (Zn/ZnSO4)


2) Metal -Metal salt ion 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.

E.g.: Calomel electrode (Hg/Hg2Cl2/Cl-)

3) Gas-ion electrode: It consists of an inert metal dipped in a solution containing ions to


which the gas is reversible

E.g.: Hydrogen electrode

4) Redox electrode: It consists of an inert metal dipped in a solution containing ions in


two oxidation states of the substance.

E.g: Quinhydrone electrode (Pt/Q/H2Q), (Pt/Fe3+, Fe2+)

5) Ion Selective electrode: “Ion-selective electrode is one which selectively responds to


specific ions in a mixture and the potential developed at the electrode is a function of the
concentration of those ions in the solution”.

E.g: Ag/AgCl(s), HCl (0.1M)/ Glass+


Ion-selective electrode:
“Ion-selective electrode is one which selectively responds to specific ions in a mixture and the
potential developed at the electrode is a function of the concentration of those ions in the
solution”.
Uses:- To determine the concentration of a number of cations and anions such as H+, Li+, Na+,
K+, Pb2+, Cu2+, Mg2+, CN-, NO3-, F- etc.

There are Four types of membranes,


They are
1) Glass membranes
2) Heterogeneous membranes
3) Solid State membranes
4) Liquid membranes

Glass electrode:
Principle: -
A glass electrode is a type of ion- selective electrode and consists of a thin- walled glass bulb
(22%Na2O, 6%CaO, and 72%SiO2) attached to a glass tube. A very low melting point and
high electrical conductivity glass are used for the construction of this bulb. The glass tube
contains a dilute solution of constant pH of HCl (0.1N) solution. A silver–silver chloride
electrode or platinum wire is immersed as reference electrode in the HCl solution. The working
of glass electrode is based upon the observation that when a glass surface is in contact with a
solution, there exists a potential difference between the glass surface and the solution, the
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Dr Puneetha J, Assistant Professor, Chemistry Department, JSSATEB

magnitude of which depends upon the H+ ion concentration of the solution and the nature of
glass. The glass electrode may be represented as

Ag, AgCl (s) /0.1 N HCl / glass /H+ = unknown

A thin-walled glass bulb containing an acid is immersed in another solution a potential is


developed across the glass membrane. The potential difference, Eb at the interface is referred to
as boundary potential is the difference in potential (E1-E2) developed across the layer of the
glass membrane b/w the two liquids.
The potential of glass electrode EG is given by
EG=EM + ERef + Easymm …………(1)
Where, EM = E1-E2
EM = Potential developed across the membrane
E1 are the potential developed when outer membrane in contact with analyte solution

E2 are the potential developed when inner membrane in contact with standard solution

EM= [Eo+0.0591 log [C1]] - [Eo+0.0591 log [C2]] ……..2


Where C1 & C2 are the concentration outer & inner acid solutions.
EG 0.0591.log[ C1] - 0.0591.log[ C2] ……3
Since the H+ concentration inside the glass bulb is a constant. The first term on RHS of the
above equation becomes constant.
Constant= - 0.0591.log[ C2]
EG = Constant + 0.0591log[C1] + ERef + Easymm
EG =EOG + 0.0591log[C1]
Constant = EOG = Constant + ERef + Easymm
Since, C2= [H+], Where pH = -log [H+]

EG =EOG - 0.0591 pH
Advantages
1. This electrode can be used to determine pH in the range 0-9, with a special type of glass
even up to 12 can be calculated.
2. It can be used even in the case of strong oxidizing agents.
3. The equilibrium is reached quickly.
4. It is simple to operate, hence extensively used in various laboratories.

Limitations
1. The glass membrane though it is very thin, it offers high resistance. Therefore ordinary
potentiometers cannot be used; hence it is necessary to use electronic potentiometers.
2. This electrode cannot be used to determine the pH above 12.
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Dr Puneetha J, Assistant Professor, Chemistry Department, JSSATEB

Determination of pH using 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. In practice, pH of one of these solutions is kept constant
and therefore the electrode potential depends on pH of the other solution ie. Experimental
solution.

Procedure: glass electrode is immersed in the solution; the pH is to be determined. 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|Ag+|AgCl The emf


of the above cell, Ecell is measured using an electronic voltmeter with a pH meter. The emf
of the cell is given by
Ecell = Ecathode - Eanode ............. (1)
Ecell = Eglass - ESCE .................... (2)
Since ESCE is knowing EMF of the cell, Substitute the value of EG to equation (2)

Ecell = Eg - 0.2422

Ecell = EOg - 0.0591 pH - 0.2422

pH = EOg - 0.2422 - Ecell


0.0591

Reference electrodes: “Reference electrodes are the electrode with reference to those, the
electrode potential of any electrode can be measured”.
The Primary reference electrode used for cell potential measurement is the SHE, whose potential
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Dr Puneetha J, Assistant Professor, Chemistry Department, JSSATEB

is Zero. The secondary reference electrodes are Calomel and Silver-Silver chloride electrode.

Calomel electrode:
Calomel electrode is a metal-metal salt ion electrode. It consists of mercury, mercurous Chloride
and a solution of KCl. Mercury is placed at the bottom of a glass tube.
A paste of mercury and mercurous chloride is placed above the mercury. The space above the
paste is filled with a KCl solution of known concentration. A platinum wire is kept immersed
into the mercury to obtain an electrical contact. Calomel electrode can be represented as,
Hg| Hg2Cl2|Cl-.
The calomel electrode can act as anode or cathode depending on the nature of the other
electrode of the cell.
The net cell reversible electrode reaction is,

Hg2Cl2(s) + 2e-  2Hg(l) + 2Cl-

The Nernst equation is given by,


𝐸 = E 𝑜 − 0.0591 log [𝐶𝑙 − ] at 298 K
The electrode potential of calomel electrode is depending upon the concentration of KCl used,
0.1N KCL→ 0.334V, 1N KCL→0.281V, Sat.KCL→0.2422V.

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Dr Puneetha J, Assistant Professor, Chemistry Department, JSSATEB

Advantages:-
1. Simple to Construct.
2. Cell potential does not vary with temperature.
3. The cell potential is reproducible and constant over a long period.

Concentation Cell
“Concentration cell is an electrochemical cell in which the electrode material and the
solution in both the electrodes are composed of the same substances but only the
concentrations of the two solutions (electrolyte) are different”.
A typical example of Copper concentration cell is shown below.

It consists of two Copper electrodes are immersed in two different concentration of CuSO4
solutions. These two electrodes are externally connected by metallic wire and internally by
a salt bridge. The cell can be represented as,

By convention left-hand electrode is the anode and right-hand electrode is a cathode.


At Anode

At Cathode

Net reaction

The net cell reaction is merely the change in concentration as a result of current flow.
Emf of concentration cell:
We know that electrode potential depends on the concentration of the electrolyte. By
convention, the potential of the cell is
Ecell=Ecathode - Eanode

0.0591 log [𝑀2 ] 0.0591 log [𝑀1 ]


𝐸𝑐𝑒𝑙𝑙 = −
𝑛 𝑛
0.0591 [𝑀2 ]
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔
𝑛 [𝑀1 ]

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Dr Puneetha J, Assistant Professor, Chemistry Department, JSSATEB

1. When M2=M1 EMF of the cell is Zero

2. When M2/M1>1 i.e M2>M1, log M2/M1 is positive & electrode potential is positive.
3. Higher the ratio of M2/M1, higher is the value of cell potential.

Sensors
Sensors are basically devices which “read” a physical stimulus, and then convert that reading into
an electrical signal output.
Physical Stimulus: heat, light, sound, weight, attraction

• Sensor - observe and acquire information


• Transducer- Converts one form of energy into another form
• An actuator- Converts electrical energy into mechanical energy
Measurement process for the instrumentation model
Sensor input - the physical value or measurand (X) is observed by the sensor device
Sensor output - The sensor generates a signal variable (S) output which is normally electrical
Signal conditioning - The signal is transmitted and conditioned if needed
(amplified, converted, filtered, etc.)
Display of measurement – the measurement is then displayed by the output device.

Electrochemical sensors,
Sensors which convert the effect of electrochemical reaction between analyte and electrode
surface into a useful signal are known as electrochemical sensors.
In Electrochemical sensors the electrode is used as transducer element. They are divided into
several types:
• Potentiometric (measure voltage)
• Amperometric (measure current)
• Conductometric (measure conductivity)

Working Principle
Electrochemical sensor consists of a transducer element covered by a recognition element.
The recognition element interacts with target analyte and signal is generated.
Electrochemical transducers transform the chemical changes into electrical signals
The electric signals are related to the concentration of analyte.
Electrochemical sensing always requires a closed circuit. Current must flow to make a measurement.
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Dr Puneetha J, Assistant Professor, Chemistry Department, JSSATEB

Since we need a closed loop there should be at least two electrodes. These sensors are often called
an electrochemical cell.

Applications
1. Electrochemical sensors used for the detection of blood glucose
2. Electrochemical sensors are used for pH measurements
3. Used to detect pesticides
4. Used in the detection of hydrocarbon pollutants
5. Optical sensors are used to measure the concentration of coloured analyte.

Conductometric Sensors:
Conductometric sensors are two electrode devices, measures the electrical conductivity in sample
solution between two electrodes.
Principle:
The basic principle of conductometric detection involves a reaction that can change the
concentration of ionic species. This reaction leads to changes in electrical conductivity or
current flow. In this method, two inert metal electrodes are used. The ions or electrons produces
during an electrochemical reaction may change the conductivity or resistivity of the solution.

Working:
The conductivity is result of dissociation an electrolyte, into ions. The migration of the ions is
induced by an electrical field. When a potential difference is applied to the electrode, there is an
electrical field within the electrolyte, so the positively charged ions move towards cathode and
negatively charged ions are move towards anode. (Figure). 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 transducers converts this chemical change into electrical signal.
Applications:
• The conductometric measuring method can be used in enzyme catalysis to determine
analyte concentration and enzyme activity and selectivity.
• Screen-printed conductometric sensor with inter digital gold electrodes on glass substrate
coated with molecularly imprinted polyurethane layers was fabricated to detect polycyclic
aromatic hydrocarbons (PAHs) in water.
• A conductometric sensor consisting of a silicon substance with a pair of gold inter
digitized and serpentine electrodes is used to determine urea.
• The conductometric biosensor based on inhibition analysis, was intended for the
determination of organo phosphorous pesticides.
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Dr Puneetha J, Assistant Professor, Chemistry Department, JSSATEB

Optical sensors
Optical sensors are electronic components designed to detect and convert incident light rays into
electrical signals.
Example: Colourimetric Sensors
Principle: When a sample solution is interacted with a light of suitable wavelength, certain
quantity of light is absorbed by the analyte solution and it is observed by a sensor and transducer
converts intensity of absorbed light into electrical signal. The change in intensity at certain
wavelength within visible (400–800mm) range can be determined using special instrumentation.

A photon (ultraviolet, visible, or near-infrared light) is converted in the photocathode into a low-
energetic electron, emitted into the vacuum. This electron is accelerated towards and focused
onto the first dynode, releasing secondary electrons. This multiplication is repeated in subsequent
dynodes, resulting in a measurable electric charge at the anode.
Application:
Absorption-based optical sensors (Colourimetry)
Absorption-based optical sensors can be colorimetric or spectroscopic in nature.
Colorimetric sensors are an important part of optical sensors that depends on the colour of the
analyte with in the visible range (400-800nm)
Its basic components include a light source, a wavelength selector, a photodetector and a read-
out device. A block diagram of a typical instrumentation system employed colurimetry is shown
in Fig.

A monochromatic light is made to pass through analyte solution where certain quantity of light
is absorbed and it is a function of concentration of analyte. The change in the intensity of light is
detected by photodetector (sensing). The light source generates an intense and stable radiation
signal needed to probe an optical property of the molecular recognition element in the sensor.
The amount of absorbance is governed by Beer- lamberts law.

Analytical Techniques:
Potentiometry
Theory
Determination of concentration of ionic solution by measuring the emf (electromotive
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Dr Puneetha J, Assistant Professor, Chemistry Department, JSSATEB

force) is referred to as potentiometry.

Potentiometric methods include two types of measurement


Direct measurement of an electrode potential from which the concentration of an active ion
may be found.
Changes in the emf of an electrolytic cell brought about by an addition of a titrant. The
potential of an electrode is given by Nernst eqn,

E = E0 + 0.0591 log [ M n+]


n

E0 Standard electrode potential, Electro potential depends on the concentration of the


ion. (E0 – It is the electrode potential of a metal in contact with its ions in 1 molar)
Instrumentation:-

The Potentiometer consists of a reference electrode, an indicator electrode and potential


measuring device. The indicator electrode response rapidly to the changes in the concentration
of analysis i.e the solution understudy. This is made up of platinum, indium, gold and other
noble gases. The potential of the indicator electrode is measured using an electrode known as
reference electrode. It is made up of mercury, mercury oxide or silver-silver chloride. A
known volume of analyte is taken and its potential is determined. The titrant is added in
increment of 1ml and the emf is measured each time at equivalence point, the emf tends to
increase rapidly.
At this point readings are more taken frequently at the intervals of 0.5cm3 to find the
equivalence point plot a graph of ΔE/ΔV Vs volume of the titrant added.
Applications
a) Oxidation Reduction reactions;Estimation of amount Fe in FAS solution
FAS vs. K2Cr2O7
Redox reaction can be followed by an inert indicator electrode (i.e Pt).
The Electrode potential is proportional to log of the concentration ratio of the
oxidation states of reactant
Oxidized form + n electrons → Reduced form
Electrode potential at 25 oC is given by
0 (Oxidized
E = E +0.0591 log
10 form)
(Reduced
n form)
These titration involves the transfer of electrons from the substance being oxidized
to the substance being reduced

10
Dr Puneetha J, Assistant Professor, Chemistry Department, JSSATEB

In this titration the potential of the two systems are important i.e the one oxidized and
one reduced, the change of potential end point is maximum generally the oxidizing
agent is placed in burette.

Eg: Iron (II) with K2Cr2 O7

Fe2+ Fe3+ + 3e-


K2Cr2O7 + 14H+ 6e 2 Cr3+ + 7 H2O

For finding endpoint plot a graph of change in emf again the volume of titrant . A more
sensitive and satisfactory method of finding the endpoint to plot a graph of ΔE/ΔV against
V.

Application:
1. It is easy to interpret titration curves
2. It is inexpensive, reliable and readily available
3. It can be used for colored solutions.

Conductometry:
Conductometry is an electrochemical method of analysis based on measuring the resistance
of an electrolytic solution.

Definition of conductance: Reciprocal of resistance is called conductance i.e. C=1/R


It is expressed in ohm-1 or Mho.
Theory: Ohm’s law states that the current (I) in amperes flowing in a conductometer is
directly proportional to the applied emf. E (vol) and inversely proportional to the resistance,
R (ohm) of the conductor.
𝑰
𝑬=𝑹

The reciprocal of resistance is called the conductance.


The theory involved in conductometric titration is that conductance of an electrolytic
solution depends upon the nature, number, and mobility of the ions in solution. Larger the
concentration of fast mobile ions higher will be the conductance and Vice versa.

Types of Conductance
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Dr Puneetha J, Assistant Professor, Chemistry Department, JSSATEB

Specific Conductance:-
Ability of an Electrolyte to conduct electricity in meters is called Specific Conductance. The
Specific Conductance is measured according to the length and the area covered by an Electrolyte
or the Conductor. It is also inversely proportional to Specific Resistance ‘ρ’. It is given as
Siemens/meter or G/m. it is denoted by ‘k’.

Equivalent conductance:
Conductance of a volume of a solution consisting of one equivalent weight of dissolved substance
when it is placed between two parallel electrodes. The electrodes are placed with a 1 cm distance
between them. It is large enough to contain the solution between them. It can be described as the
net conductance of every ion that is produced from 1 gram equivalent of a particular substance.

Molar conductance : is the conductance of all the ions furnished by one mole of an electrolyte
present in a definite volume of the solution. The term molar conductivity refers to the property
of having a molar conductance.

Factors affecting conductance


1. Temperature : The temperature at which the electrolyte dissolves in the solutions has a
significant impact. The greater temperature is thought to be better for this process because it
improves the electrolyte's solubility, which boosts ion concentration and electrolytic
conduction.
2. The size of the ion: The conductance of an ion is inversely proportional to its size, implying
that the larger the ion, the lower the conductance.
3. The type of solvent: Higher conductance is present when the nature of the solvent has a
higher polarity.
4. The viscosity of the solvent: Electrolytic conduction and viscosity have been found to have
an inversely proportional relationship. When the viscosity of the solvent is high, the
conductance suffers as a result of the lower conductance.

Instrumentation:
Conductometer consists of two platinum electrodes and a conductance
measuring device. The two electrodes have unit area of cross section and are placed unit
distance apart. The assembly responds rapidly to the changes in the concentration of the
analyte.

Applications:
Titration of a weak acid and strong base

An example of a weak acid and strong base are CH3COOH and NaOH respectively. As
the acid is a weak acid it will dissociate partially into H+ and CH3COO− ions and hence
number of ions will be few in the solution and hence the solution will show low conductance
12
Dr Puneetha J, Assistant Professor, Chemistry Department, JSSATEB

value. Now as we add few drops of base from burette, acid-base reaction will take place.

Titration curve: Weak acid vs strong base


As the base is strong one also, it will also dissociate into Na+ and OH- ion completely.
During the acid-base reaction, the OH− ion will consume H+ to form water. So, we can
say by addition of few drops of base at first conductance will decrease slightly. Now as we
move further with addition of more drops of base, all H+ will be consumed and hence the
dissociation of the weak acid will increase which will be reflected by gradual increase in
conductance value.

Beyond the equivalent point when all the H+ ion is consumed, additional addition of NaOH
will simply add more Na+ and OH− in solution and hence conductance will increase again
sharply. If will plot a conductance vs drops of base, we will get a graph like this. Now in first
half the increase of conductance is due to more dissociation of actic acid and in second half of
the graph the increase of graph is due to addition of OH−.

CH3COOH + NaOH  CH3COONa + H2O

Titration of a weak acid and weak base

An example of a weak acid and strong base are CH 3COOH and NH4OH respectively. As
the acid is a weak acid it will dissociate partially into H+ and CH3COO− ions and hence
number of ions will be few in the solution and hence the solution will show low
conductance value.
Now, as we add few drops of base from burette, acid-base reaction will take place. During
the acid-base reaction, the OH− ion will consume H+ to form water. So, we can say by
addition of few drops of base at first conductance will decrease slightly. Now as we move
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Dr Puneetha J, Assistant Professor, Chemistry Department, JSSATEB

further wilh addition of more drops of base, all H+ will be consumed and hence the
dissociation of the weak acid will increase which will be reflected by gradual increase in
conductance value.
After reaching equivalent point when all the H+ ion is consumed, additional addition of NH4OH
will have no effect. This is due to the fact that NH4OH will not dissociated further as it is
weak base and due to common ion effect. So, the conductance value will be unchanged or we
will get a parallel line to X-axis.

CH3COOH + (NH4OH) CH3COONH4 +4 H2O


Advantages:

1. No need of Indicator
2. Mixtures of acids can be titrated
3. Accurate in dilute and Coloured Solutions
4. Very weak acids which can’t be titrated potentiometrically but it can be titrated
conductometrically

Colorimetry

Theory:- Chemical analysis through measurement of absorption of light of a particular


wavelength is known as Colourimetry.
Beer – Lambert’s Law:

When a monochromatic (light having only one colour) radiation of intensity ‘I’ is
passed through a solution of a sample under investigation taken in a cell of thickness ‘t’ a
portion of radiation is absorbed (Ia), a portion is reflected (Ir) and the remainder is
I=I +I +I
transmitted (It) then,
a r T
In the case of transparent medium the intensity due to reflection is negligible,
Therefore, I = Ia + It

Lambert’s Law:
It states that “when monochromatic light passes through a transparent medium, the rate
of decrease in intensity with the thickness of the medium is proportional to the intensity
of the light mathematically it can be expressed as
-dI = KI
dt
Here ‘K’ is proportionality constant

Writing the above eqn


-dI = K. dt
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Dr Puneetha J, Assistant Professor, Chemistry Department, JSSATEB

I
Integrating this eqn & substituting I =I0 when t=0
ln I0 = Kt It = I0 e-kt
It
This eqn shows the exponential decrease in intensity of transmitted light with the increase
in thickness of the medium

Beer’s law:
This law is stated as ‘The intensity of the transmitted light decreases exponentially
as the concentration of the medium increases arithmetically, mathematically this may be
expressed as

It = I0 −
Where C – Molar Concentration (mol/dm3) of the beer’s law & Lambert’s law eqn for Beer
Lambert’s

sample solution combining eqn for law can be written as It = I0 −


It = I0 / 10 ct
Where called molar absorption coefficient is is a constant for a given substance at
a given wavelength,
It is expressed in dm3 mol-1 cm-1. The above eqn can be written as
Log I0 = ct
It

If I0 is called transmittance then Log I0 is called absorbance (A),


It It
- Molar absorption co-efficient is constant for a given substance at a given
wavelength, C- concentration of the medium and path length or thickness (t) of the
medium and is referred as Beer – lambert’s law
A = ct = Log I0 = Log 1 = - log T
It T
Path length of the cell is kept constant, and then absorbance ‘A’ is proportional to
the concentration.
Instrumentation
The essential parts of colorimeter are
1. Light Source-Mercury lamp.
2. Filter- To filter undesired radiations, it allows radiations of a definite wave length
range to pass through it and reach the sample
3. Cuvette- To take sample
4. Photocell- To receive the transmitted light and convert to electrical signal.
5. Recorder – to record the absorbance in nm.

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Dr Puneetha J, Assistant Professor, Chemistry Department, JSSATEB

Application:-
Colorimetric

determination of copper

When cupric ions are treated with ammonia, it gives deep blue coloured cupra ammonium
compound. The absorbance is measured at 620 nm(λmax). Since the complex shows the
absorbance maximum at this straight line will be obtained. From this unknown solution
concentration can be obtain by measuring the absorbance of unknown solution.

Procedure:-
Take known amount of standard solution 2, 4, 6, 8 and 10 cm3 in deferent 25 cm3 standard
flasks, add 2.5 ml of ammonia into each of these flask and make up to the mark with distilled
water. Stopper the flask and mix the solutions well. After measure the absorbance of all
solutions against blank at 620 nm using a photo electric colorimeter. Note down the optical
density of all solutions and tabulate the readings. Draw a calibration curve by plotting
absorbance against concentration of copper or volume of copper of solution taken. Using
fine calibration curve find out the unknown volume of copper sulphate solution given and
calculate the amount of copper present in it (Blank solution -2.5 ml ammonia and water in
standard flask)

A
Absorba
nce

Concentration of Copper

16

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