Dept of Chemistry 18CHE12/22

SAI VIDYA INSTITUTE OF TECHNOLOGY

MODULE 5

INSTRUMENTAL METHODS OF ANALYSIS AND NANOMATERIALS

Instrumental methods of analysis and Nanomaterials
Instrumental methods of analysis: Theory, Instrumentation and applications of Colorimetry,
Flame Photometry, Atomic Absorption Spectroscopy, Potentiometry, Conductometry (Strong
acid with a strong base, weak acid with a strong base, mixture of strong acid and a weak acid
with a strong base)
Nanomaterials: Introduction, size dependent properties (Surface area, Electrical, Optical,
Catalytic and Thermal properties). Synthesis of nanomaterials: Top down and bottom up
approaches, Synthesis by Sol-gel, precipitation and chemical vapour deposition, Nanoscale
materials: Fullerenes, Carbon nanotubes and graphenes – properties and applications.
(RBT Levels: L1 & L2)
Course outcome: Different techniques of instrumental methods of analysis. Fundamental
principles of nanomaterials.

COLORIMETRIC TITRATION:

Introduction: this method is useful to determine the concentration of unknown solution. The
concentration of the unknown solution is determined by measuring the absorbance of the light
w.r.t known concentration. The instrument name is Photoelectric Colorimeter
Theory: Theory of the colorimeter is explained by Beer – Lambertz Law.
Law of absorption: When light falls upon homogenous medium, a portion of the light is
reflected, a portion is absorbed, and reminder is transmitted.
Io = It + Ia + Ir
Where Io = intensity of the incident light
Ir = intensity of the reflected light
Ia = intensity of the absorbed light
It = intensity of the transmitted light
When glass is used Ir = 0 negligible
Io = Ia + It
A = log (Io / It)
Lambert’s Law: The intensity of the monochromatic light decreases exponentially as the
thickness of the medium increases arithmetically.

K is proportion constant.

on integrating & Substitute I = Io when t = 0& I=It at t

dI - K dl
I

In l

Prof. RAVEENDRA.R.S/Prof. SATHYANARAYANI. S/Prof. BHAGYA.N.P Page 1

Dept of Chemistry 18CHE12/22
SAI VIDYA INSTITUTE OF TECHNOLOGY

It = I0 e-Kl
Beer’s law: the intensity of the monochromatic light decreases exponentially as the concentration
of the medium increases arithmetically.

K .dc

on integrating between the I=I0 at c=o and I=It at c.

In = K .C. or It = I0 .e-Kc

Beer-lambert’s law
Absorbance is directly proportional to concentration and thickness.
A = € ct , € = molar absorption co-efficient.
A = log =Ktc

Relationship between absorbance & transmittance

Reciprocal of transmittance, I0 / It is called absorbance.
A= log I0 / It =log I/T = -log T
Reciprocal of absorbance, It / I0 is called transmittance.
A= log It / I0 =log I/A = -log A
I.e. transmittance of the colored solution is equal to the ration of the intensity of the transmitted
radiation to that of intensity of the incident radiation I0.
Procedure: Pipette out 2, 4, 6, 8, 10ml of standard copper
sulphate solution into 25ml standard flask. Add 2.5ml of
ammonia solution into each of them and make up to the
mark with distilled water and shake well. Set the filter to
620nm. Adjust the initial reading to zero by using blank
solution in the sample tube. Measure the absorbance for
each standard flask solution and plot graph of absorbance
v/s concentration of copper sulphate.

Prof. RAVEENDRA.R.S/Prof. SATHYANARAYANI. S/Prof. BHAGYA.N.P Page 2

Dept of Chemistry 18CHE12/22
SAI VIDYA INSTITUTE OF TECHNOLOGY
Instrumentation:
Source: tungsten bulb is used as a light source.
Filter: It is a device for isolating monochromatic light.
Sample: sample is hold in glass cell.
Photocell: Converts the emitted light into electrical signal.
Applications:
• In quantitative analysis: large number of metal ions, anions and cations compounds can be
determined by in this method
• Photometric Titration i.e. equivalence point can also be determined
• Determination of the composition of colored complex
Advantages:
• Can be determine the concentration of the colored solution
• It is very simple method
• Colorimeter gives most accurate value
• Used for lower concentration
FLAME PHOTOMETRY

Introduction: Elements impart characteristic color with Bunsen flame. The flame photometry is
based on the measurement of intensity of the light emitted when a metal is introduced into a
flame. The intensity of the emitted light tells about the concentration of the element present.
Principle: When liquid sample containing metallic salt solution is introduced into aflame, the
flowing process is involved in that.
• Solution containing the metal is aspirated into flame
• Solvent evaporates leaving behind a solid residue
• Salt is vaporized or converted into a gaseous state
• In the gaseous state salt is dissociates into constitute atoms
• Gaseous atoms get excited from ground state to excited state.
• The exited atoms are unstable quickly emit photons & return to the lower energy level
• The intensity of the emitted radiation is measured using flame photometry
These steps are schematically represented as follows

M+X- (aq) flame M+X-evaporation MX(s) vaporization (g) dissociation(g)+X(g)

excitation

emission flame M*(g)

hγ
Relationship between ground state & excited state atoms is given by Boltzmann equation
N1/N0 = ( g1/go) e-∆E/RT

N1= atoms in excited state, N0= atoms in ground state

g1/go = ratio of statistical weights for ground & excited states.
∆E = excitation energy K= Boltzmann constant, T= temperature.
Procedure: Flame photometric estimation of sodium

Prof. RAVEENDRA.R.S/Prof. SATHYANARAYANI. S/Prof. BHAGYA.N.P Page 3

Dept of Chemistry 18CHE12/22
SAI VIDYA INSTITUTE OF TECHNOLOGY
Prepare 1ppm NaCl solution by weighing 2.52g of sodium chloride and dissolved one liter of
distilled water. Transfer 2, 4, 8, 10ml of standard NaCl solution into different standard flask. Set
the instrument to zero by using distilled water and hundred by using pure NaCl solution.
Measure the emission intensities for other standard solutions. Draw a calibration curve by
plotting the emission intensity (y axis) and concentration of NaCl in ppm (x axis). From the
curve find out concentration of NaCl and calculate the amount of Na.

Instrumentation:

Applications:
It is used in the quantitative determination of metals in solution, especially alkali & alkaline earth
in the given sample.

POTENTIOMETRIC TITRATION

Aim: Determination of the weight of ferrous ammonium sulphate and ferrous iron in the given
solution by potentiometric titration method.

Principle: In this titration the amount of substance in the solution is determined by measuring
the emf between two electrodes that are dipped into the solution. When the metal M is immersed
in the solution containing its own ions Mn+ ions, the electrode potential is given by Nernst
equation,
E=Eo+ 0.0591log [Mn+]
N
emf of the solution can be measured by combining reference electrode with indicator electrode.
The electrode which responds to the change in the concentration of the ion in the solution is
called indicator electrode& reference electrode is one whose potential is constant.
The titration of Mohr’s Salt solution with K2Cr2O7 in the presence of H2SO4 is a redox titration.
Before the titration is started, the solution contains only ferrous ions in the solution. When a
small volume of the dichromate solution is added, equivalent small quantity of Fe2+ ions are
converted into Fe3+ ions. In the process, the Cr6+ ion in dichromate is reduced to Cr3+ ion.
3Fe2++cr6+ 3Fe2++Cr3+

Prof. RAVEENDRA.R.S/Prof. SATHYANARAYANI. S/Prof. BHAGYA.N.P Page 4

Dept of Chemistry 18CHE12/22
SAI VIDYA INSTITUTE OF TECHNOLOGY
In the presence of both Fe2+ and Fe3+ ions in the solution developing an electrode potential which
is picked up by a Pt wire [P+/Fe3+;F2+], whose electrode potential is given by
E=Eo+ 0.0591 log [Fe3+]
N [Fe2+]
The electrode potential of the indicator electrode depends upon the ratio of the concentrations of
oxidized and reduced species in the solution. As the titration proceeds, the concentration of Fe3+
goes on increasing and that of Fe2+ goes on decreasing. As a result, the ratio in the above
expression for electrode potential goes on increasing and the increase in the value of the ratio
becomes very large near the end point. This results in the large increases in the electrode
potential and in turn, in the measured emf of the cell.
At the equivalence point, all the Fe2+ ions are converted into Fe3+ ions, the Pt/Fe3+, Fe2+ electrode
ceases to exist. But addition of a slight excess of dichromate solution introduces Cr6+ ions into
the solution, which along with the Cr3+ ions in the solution (formed during the oxidation of Fe2+)
form a new oxidation reduction electrode, Pt/Cr6+, Cr3+.
After the equivalence point potential of the redox reaction is determined by the equation
E=Eo+ 0.0591 log [Cr2O72-]
N [Cr3+]
Procedure: Pipette out 25cm3 of FAS solution into a 50cm3 beaker. Add one test tube full of dil
H2SO4. Immerse Pt. & calomel electrodes into the solution, & connect the electrodes to a
Potentiometer.
Fill the burette with K2Cr2O7solution .Add K2Cr2O7 solution from the burette with increment of
0.5cm3, stir well and measure the potential after each addition. Continue the titration till the
potential indicates a rapid jump with a drop of titrant.
Plot the graph of ∆E/ ∆V v/s vol. of K2Cr2O7

∆E
∆v

Volume of K2Cr2O7

Instrumentation

Prof. RAVEENDRA.R.S/Prof. SATHYANARAYANI. S/Prof. BHAGYA.N.P Page 5

Dept of Chemistry 18CHE12/22
SAI VIDYA INSTITUTE OF TECHNOLOGY
A potentiometer consists of an indicator electrode (e.g.: Platinum), A standard reference
electrode (E.g.: Calomel electrode), & potentiometer to read the values directly as change in
potential.
Applications:
1. Coloured solution can also be titrated.
2. Acid-base titration can also be done in this method.
3. In this method Oxidation-reduction titrations can also be carried out.
4. Precipitation reactions can also be carried out potentiometrically.

CONDUCTOMETRIC TITRATION

Conductance is ease with which current flows through the solution. It is reciprocal of resistance.
C=1/R = Ω-1 or mho or siemen
Theory:
The Conductance of the solution is explained by considering ohm’s law.
According to ohm’s law the current flowing through the conductor is directly proportional to
voltage and inversely proportional to the resistance.
I= or E = I R
The resistance of the any conductor is directly proportional to the length of inversely
proportional to the area of cross section of the conductor
Therefore R = S (l/a) where S is specific resistance
Therefore C = 1/R = 1/S (a/l), K (a/l), K = specific conductance
It is defined as the conductance of the solution which is place between two electrodes of area
1cm2 and 1cm apart
The conductance of the solution is depends on mobility of the ion and number of the ion
Types of conductance: There are three type’s namely specific conductance, equivalence
conductance, and molar conductance.
Specific conductance (K) is conductance of the solution which are placed between two
electrodes of area 1cm2 and at 1cm apart
K = 1/R (l/a) K = Siemen m-1
Equivalence conductance (λ) is the conductance of the solution when 1g equivalent weight of
solution is placed between two electrodes of area 1cm2 at 1cm apart.
Molar conductance (µ) is the conductance of the solution when 1g molecular weight of solute is
placed between two electrodes of area 1cm2 at 1cm apart
Conductometric titration
Strong acid v/s strong base
HCl v/s NaOH
If the strong acid like HCl is titrated against a strong base such
As NaOH, the conductance first decreases due to replacement
of fast moving H+ ions by slow moving Na+ ions
HCl + NaOH NaCl + H2O
After the neutralization point, conductivity rapidly rises with further addition of NaOH because
of continuous addition of fast moving OH- ions. A plot of conductance against the volume of

Prof. RAVEENDRA.R.S/Prof. SATHYANARAYANI. S/Prof. BHAGYA.N.P Page 6

Dept of Chemistry 18CHE12/22
SAI VIDYA INSTITUTE OF TECHNOLOGY
base added is shown in the figure. The point of intersection of two curves gives the neutralization
point.
Strong acid v/s weak base
HCl v/s NH4OH
Conductivity of the solution decreases due to the replacement
Of fast moving H+ ions by NH4+ ions but after equivalence point,
conductivity almost remains constant, since NH4OH is weak
electrolyte and ionizes to small extent giving very small
conductivity.
HCl + NH4OH NH4Cl + H2O
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.
Weak acid v/s Strong base
Consider the titration of acetic acid against NaOH.
The conductance of the acid will be initially low since acetic
acid is a weak electrolyte. When NaOH is added to the acid,
the salt formed is highly ionized and the conductance increases.
On complete neutralization of the acid, further addition of base
leads to an increases in the number of mobile OH- ions. Hence
the conductance increases sharply.
CH3COOH+ NaOH CH3COONa + H2O
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.
Weak acid v/s weak base
Consider the titration of acetic acid against NH4OH. The conductance
of acid will be initially low since acetic acid is a weak electrolyte.
When NH4OH is added to acid salt is formed and the conductance
of the solution increases. On complete neutralization of acid
conductance does not change rapidly since NH4OH is a weak base.
CH3COOH+ NH4OH CH3COONH4 + H2O
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.
Mixture of strong acid and weak acid v/s strong base
HCl, CH3COOH v/s NaOH
the strong acid like HCl is titrated against a strong base such
as NaOH, the conductance first decreases due to
replacement of fast moving H+ ions by slow
moving Na+ ions
HCl + NaOH NaCl + H2O
The weak acid do not get neutralized initially
because of the well known common ion effect.
In the presence of excess of H+ ions, the ionization
of the weak acid is suppressed and hence, weak acid
like CH3COOH ionizes gradually after the first end point and the available H+ ions are
neutralized giving the second end point.

Prof. RAVEENDRA.R.S/Prof. SATHYANARAYANI. S/Prof. BHAGYA.N.P Page 7

Dept of Chemistry 18CHE12/22
SAI VIDYA INSTITUTE OF TECHNOLOGY
Because of common ion effect dissolution of acetic acid is suppressed. Hence it does not provide
H+ ions which required for neutralization.
After the neutralization point of HCl, CH3COOH, conductivity rapidly rises with further addition
of NaOH because of continuous addition of fast moving OH- ions. 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.
Advantages:
• Mixture of acid can be titrated
• Indicators are not used
• Very weak acids can be titrated
• Can be used with colored solution

NANO MATERIALS

Nano Materials: Introduction, properties (size dependent). Synthesis-bottom up approach (sol-

gel, precipitation, gas condensation & chemical vapour condensation processes). Nano scale
materials- carbon nano tubes, nano wires, fullerenes, dendrimers, nano rods, & nano composites.

COURSE OUTCOME: Over viewing of synthesis, properties and applications of

nanomaterials Program.

INTRODUCTION: Nanotechnology is a multidisciplinary science and technology and

encompasses physical, chemical, biological, engineering and electronic processes. It is the study
deals with various structures of matter having dimensions of the order of billionth of a meter.
These materials or particles are called as nano particle. Nano technology is the making of usage
and technique, in order to solve a problem to perform specific functions. The particles which are
smaller than about 100nm give rise to enhance properties of nano structures built from them.
Matter arranged by exercising control over length of one to hundred nanometers and the
formulating structures exhibit characteristics that are specific to their size and dimensions, the
resulting materials are called nano materials.

SIZE DEPENDENT PROPERTIES

a) Surface area: Nanomaterials have a significant proportion of atoms existing at the surface.
Properties like catalytic activity, gas adsorption and chemical reactivity depend on the surface
area. Therefore nanomaterials can show specific related properties that are not observed in bulk
materials.

b) Electrical properties: the electronic bands in bulk materials are continuous due to
overlapping of orbitals of billion of atoms. But in the nanomaterials, very few atoms or
molecules are present so the electric band becomes separate and the separation between different
electric stated varies with the size of the nanomaterials. Hence, some metals which are good
conductors in bulk semiconductors and insulator as their size is decreased to nano level.
Prof. RAVEENDRA.R.S/Prof. SATHYANARAYANI. S/Prof. BHAGYA.N.P Page 8
Dept of Chemistry 18CHE12/22
SAI VIDYA INSTITUTE OF TECHNOLOGY

c) Optical properties: Nanomaterials have particular optical properties as a result of the way
light intersects with their fine nanostructures. The discrete electronic states of nanomaterials
allow absorption and emission of light at specific wavelength. Hence, nanomaterials exhibit
unique color different from bulk materials.

SYNTHESIS OF NANOMATERIALS
There are two methods of preparing nanomaterials. One is top-down approach & the other is
bottom-up approach.

• In top-down approach, the material is reduced from bulk size to nano scale.
Examples for top-down approach are ball milling method & nanolithography.
• In bottom-up approach, matter in atomic or molecular level gets assembled to form tiny
clusters which grow to reach nano-size.
Examples for bottom-up approach are arc discharge method, chemical vapor deposition, physical
vapor deposition & sol gel method.

SOL – GEL PROCESSES

Sol gel processes principle is conversion of precursor solution into gel via hydrolysis and
condensation reactions.
Sol gel processes allow to synthesis of nano materials of high purity.
This process involves five steps
1. Preparation of sol: sol is prepared by suspended particles in water during suspension
hydrolysis reaction takes place.

2. Conversion of sol into gel: sol is converted into gel by condensation reaction forming
network between oxides. When networking takes place, the viscosity of the solution increases.

3. Aging of gel: during which poly condensation reaction continue until the gel is
transformed into solid mass.

Prof. RAVEENDRA.R.S/Prof. SATHYANARAYANI. S/Prof. BHAGYA.N.P Page 9

Dept of Chemistry 18CHE12/22
SAI VIDYA INSTITUTE OF TECHNOLOGY
4. Removal of solvent: Further the solid mass is isolated from the solvent by thermal
evaporation. The product formed is xerogel.
5. Heat treatment: solid mass (xerogel) obtained is dried at nearly to 800C to get fine nano
particle powder.

Advantages:

Nano materials of high purity with good homogeneity can be obtained.

Samples can be prepared at low temperature.

Easy to control the synthesis parameters like shape and size of resulting material

PRECIPITATION METHOD
Principle: The principle involved in the precipitation of precursor materials at constant pH via
condensation.
Processes: In this method inorganic metal salt such as chloride, sulphate, nitrate ions etc.., are
used as precursor. Precursor materials is dissolved in water and undergo hydrolysis where metal
ions exist in metal hydrates form. On adding base like NaOH/NH4OH, pH of the solution
changes and reaches super saturation level leading to condensation of precursor to form metal
hydroxide precipitate. The precipitate is washed with water, filtered and finally calcinated at
higher temperature to convert metal hydroxide into metal oxide by dehydrogenation takes place.

Advantages: The process is relatively economical.

The wide range of single and multi components to oxide nano powders can be
synthesized.

CHEMICAL VAPOUR CONDENSATION

Prof. RAVEENDRA.R.S/Prof. SATHYANARAYANI. S/Prof. BHAGYA.N.P Page 10

Dept of Chemistry 18CHE12/22
SAI VIDYA INSTITUTE OF TECHNOLOGY

Principle: the process involved is conversion of precursor (metal organic compound) into vapors
in reduced pressure atmosphere.
Processes: the precursor (starting material) is vaporized in a bubble and mixed with inert gas
like helium to carry vapors into heating furnace. Condensation reaction takes place in heating
furnace at a particular temperature. The product formed after the condensation process is in the
form of clusters. The clusters are then condensed into nano particles in a cold finger which are
removed by scraping.
Advantages:

Simple technique and does not require high vacuum

It is possible to deposit nano materials with almost any shape and size.
The byproducts are removed to gas phase. Therefore the product obtained is pure.

NANO SCALE MATERIAL

Nano scale materials are defined as a set of substances where atleast one dimension is less than
approximately 100nm. A nanometer is one millionth of a millimeter. Nano materials are of
interest because of this scale unique optical, magnetic, electrical and other properties emerge.
These emergent properties have the potential for great impacts in electronics, medicine and other
fields.

FULLERENES: Fullerenes are class of molecules made of

only carbon atoms having closed cage like structure. Many number
of fullerene molecules with different carbon atoms like C60, C70,
C74, C76 etc.., have been prepared but C60 is more stable. The C60
molecule had spherical shape resembling a soccer ball (foot ball). It
is also commonly called as Bucky ball. The C60 molecule consist of
12 pentagons and 20 hexagons and each pentagon is surrounded by
five hexagons and each hexagon is surrounded by three hexagons

Prof. RAVEENDRA.R.S/Prof. SATHYANARAYANI. S/Prof. BHAGYA.N.P Page 11

Dept of Chemistry 18CHE12/22
SAI VIDYA INSTITUTE OF TECHNOLOGY
and three pentagons placed next to each other alternately fold in the form of ball. Each carbon
atom on the cage surface is bonded to three carbon neighbors therefore is sp2 hybridized. The
chemical formula for fullerene is C20+2n.
In fullerenes, 12 pentagonal rings are necessary and sufficient to form the cage closure. It
is quite stable, breaking the balls requires temperature of about 1000C. Fullerene has high tensile
strength and high packing density.
Applications:

It is used in electrographic imaging, solar cells, non linear optical thin films etc..,

Used to make carbon films, diodes, double layer capacitor and storage devices.

Used for the conversion of diamond

Used as gas sensors, temperature sensors, particle sensors and detection of organic
vapors.

CARBON NANO TUBES: Carbon nanotubes are allotropes of carbon with a cylindrical
nanostructure having diameter of 1nm and longer than a micrometer. It is one dimensional
material like nano wires. CNT is made up of graphite sheet. When the graphite sheet is rolled up
hexagonally, it forms a tube like structure is called as CNT.
Types of CNT:
1. Single walled nanotubes (SWCNT): These are formed by rolling up of single graphite layer.
Diameter is 1.4nm and length upto few micrometers.

2. Multi walled nanotubes (MWCNT): These are formed by rolling up of two or more graphite
layers. Diameter is from 30 to 50nm and length upto few micrometers.
Properties:

CNTs have High Electrical Conductivity, Tensile Strength, Thermal Conductivity
And flexibility and elasticity.
Applications: It can be used in

Conductive plastics ,Structural composite materials, Flat-panel displays, Gas storage
Micro- and nano-electronics, Radar-absorbing coating, Batteries with improved lifetime,
Biosensors for harmful gases

*********************

Prof. RAVEENDRA.R.S/Prof. SATHYANARAYANI. S/Prof. BHAGYA.N.P Page 12