Unit 3: Nanotechnology and Instrumentation

There are two methods for the synthesis of nanomaterials:

1) Solution combustion method
2) Hydrothermal method
1) Solution combustion method

Figure: Solution combustion process and the synthesized nanomaterial formed inside the
muffle furnace (not required for exam and just for understanding)

Q. What is solution combustion synthesis? Mention the advantages of this method.

Explain synthesis of nano ZnO particles using solution combustion method.
Solution combustion process is a self-propagating high temperature synthesis in which
exothermic reaction takes place accompanied by the evolution of gases.
 Oxidizer (O) metal Fuel (F)
nitrate

Distilled water

O/F=1

Aqueous redox mixture in preheated

muffle furnace (~400 C)

Combustion
(Flame-temperature 900-1200 C)

Nanocrystalline powder of
metal oxide

Flow – Chart for synthesis of nano particles by solution combustion method

Procedure
It is another wet-chemical method like sol-gel and hydrothermal, which has been proved to be an
excellent technique for preparing several grams micro/nanocrystalline materials due to its short
processing time, low processing temperature. This technique is based on exothermic redox
reactions that undergo self-sustaining combustion. Mixtures of oxidizer (usually metal nitrates)
and a fuel (organic compound containing carbon and hydrogen; e.g. urea, citric acid or glycine as
fuel) undergo spontaneous combustion under heating and the chemical energy from the
exothermic reaction heats the precursor mixture to high temperatures. Such a high temperature
leads to formation and crystallization of nano materials).

Advantages of solution combustion method:

Among wet chemical routes, the low temperature solution combustion process is an attractive
one and finds several advantages like-
 The synthesis temperature (300 OC) employed is lower than those currently used in
conventional route.
 Simple and energetically attractive process.
  Ability to dope desired amounts of impurity ions with better homogeneity.
 The powders are voluminous, foamy, sinteractive and in nanoscale having large surface
area.
 Short reaction time (few seconds to 5 minutes)
 Chemical homogeneity
Example: Synthesis of ZnO nano particles by solution combustion method: Refer lab
manual

2) Hydrothermal method for the synthesis of nanomaterial’s

Figure : Different parts of Hydrothermal autoclave synthesis reactor (not required for exam
and just for understanding)
Figure 2: Chemical reaction through Hydrothermal synthesis method (not required for exam
and just for understanding)

Principle
In the hydrothermal synthesis, reactants are taken in water and heated at high temperatures
(above 100 oC) and pressures (above 1 atm) in a closed vessel. A sealable Teflon-lined container
is called a bomb (or) autoclave which is used to keep the reactants and water inside. Since it is
operating at a very high temperature and high pressure, hence it is also called as the
hydrothermal bomb.
Procedure
The crystal growth is performed in an apparatus from consisting of a steel pressure vessel called
autoclave in which precursors is supplied along with water. After sealing, the autoclave is used
to keep at high temperatures inside an oven. High temperature and pressure provides unique
conditions for the solution to attain super saturation. Growth of nucleus is initiated from super
saturated solution. Further, aging of the reaction mixture produces particles of well-defined
morphology (a particular form, shape or structure). The product obtained is filtered, washed with
water, air dried and finally, subjected to calcination (heating to high temperatures in the presence
of air or oxygen).
The Hydrothermal autoclave synthesis reactor used to carry hydrothermal reaction at high
pressure and high temperature.
Hydrothermal synthesis has been used to synthesize a variety of nanomaterials like nano-zeolite,
nano metal oxides (Ex: TiO2, MnO2, etc).
Example:
Preparation of Bismuth ferrite (BiFeO3) by hydrothermal method
Equimolar mixtures of bismuth nitrate (Bi(NO3)3.5H2O) and iron nitrate (Fe(NO3)3.9H2O) are
dissolved in distilled water. Add 8M sodium hydroxide (NaOH) and stir for 30 min and poured
into an autoclave. The hydrothermal treatment is conducted at 180oC for 12 h. The produced
powder is collected at the bottom of the autoclave after cooling to room temperature. The
product is washed several times by repeated cycles of centrifugation in distilled water and
ethanol. The obtained powder is heated at 80oC for 1 hour.
Applications of Hydrothermal Bomb (not required for exam and just for understanding)
1) Chemical Synthesis of Nano materials
2) Cultured crystal growth
3) Catalyst synthesis
4) Crystallization process
5) Hydrothermal oxidation
6) Petrochemicals
7) Sterilizing processes in the medical care industry
8) Microbiology
9) Medical Science
10) Dentistry
11) Polymerization reaction

Q - Mention the various techniques used in characterization of nano powder sample

The various characterization techniques used are – (i) Powder X-ray diffraction (ii) Scanning
electron microscopy (SEM) (iii) Transmission electron microscopy (TEM)

Figure: Characterization techniques for Nano materials

Applications of Nano materials

Figure: Applications of Nano materials

Application (field) Examples

Medicine Diagnostics, Drug delivery, Tissue engineering, Cryonics

Information and Memory storage, Novel semiconductor devices, Electronic devices,

communication Displays, Quantum computers
Heavy Industry Aerospace, Catalysis, Catalysis, Construction Vehicle manufacturers

Consumer goods Foods, Household, Optics, Textiles, Cosmetics, Sports

Environment Water treatment: The removal of color, heavy metal, fluoride, etc
Nano materials have better photo catalytic activity than their bulk
counterparts due to very high surface area. Nano photo catalysts like
ZnO, TiO2 and CuO are used to degrade organic dyes and other
impurities from waste industrial waste water.
Instrumental methods of analysis

Figure: Representation of methods of analysis through instrumentation (not required for exam
and just for understanding)

Introduction to analytical methods and instrumental method of analysis

 Analytical chemistry is a branch of chemistry that deals with chemical analysis. It also
deals with the qualitative and quantitative characterization of a material or materials.
Analytical chemistry is the study of the separation, identification, and quantification of
the chemical components of natural and artificial materials. Analytical chemistry deals with
the “qualitative and quantitative characterization of materials.

 Qualitative analysis is used to determine the identity of chemical species in the samples,
whereas quantitative analysis is used to determine the amount or concentration of
species present in samples. Two steps of chemical analysis in the characterization of matter or
identification (qualitative analysis) which gives one or more components of the sample and
estimation (quantitative) which gives exact quantity of constituents of a substance.
 Instrumental methods are mostly physical methods which use a simple or advanced
instrument to measure physical quantities of the analyte by relating the concentration
with light absorption, fluorescence, conductivity or potential. The physical methods have
enabled the analyst to broaden the scope of analysis, since in many cases accurate
measurements can be made without destruction of the sample. The instrumental methods
have great advantage that it can investigate the structure of complex organic molecules,
reaction kinetics, and even the biochemistry of living cells.
 An instrumental method of analysis is a physical property of a substance that are
measured to determine its chemical composition. An instrument used for chemical
analysis converts the property of the substance under investigation into a form that can be
readily measured. The measured quantity is related to the quantity or quality of sample.
 Example: Colorimeter measures the amount of radiation absorbed by a colored solution
by converting the light radiation into electrical signal. Further the amount of light
radiation absorbed is a function of concentration of the solution and the wavelength at
which the absorption takes place, in the characteristic of the substance present.

Types of Instrumental methods of analysis

 Electrical methods ( Electroanalytical )

 Optical methods ( Spectroanalytical )

1) Electrical methods ( Electroanalytical )

Electrical method of analysis involves the measurement of current, voltage or resistance
in relation to the concentration of a certain species in solution. For example
potentiometry, involves the measurement of the potential of an electrode in equilibrium
with an ion to be determined.
Example: Potentiometry, conductometry
2) Optical methods are based on, how the sample acts towards the electromagnetic
radiation.

Colorimetry
Simple technique used to determine the concentration of compounds in a solution. This method
is used for solution which are themselves coloured or which gives color with a suitable reagent.
The intensity color of the solution is directly proportional to the concentration of the solution.
Theory
This method is based on Beer-Lambert’s law. According to this law, when a monochromatic
light is passed through a solution, part of light is absorbed by the solution. The extent of
absorption depends on the concentration of the solution and on the path length of the light
through the solution.
A= € Ct
A= absorbance, C= concentration of the solution, t = path length, €= molar absorption which is a
constant at given wavelength.
Instrumentation
 Photoelectric colorimeter consists of following parts
1. Tungsten lamps as light source
2. A filter which provides the desired wavelength range
3. A sample cell
4. A photocell detector

Light from tungsten lamp, after passing through the filter is allowed to fall on the solution taken
in the sample cell. First, a blank solution is taken in the sample cell and placed in the path of
light beam. Its absorbance is measured and it is adjusted to zero. Then the analyte solution is
placed in the path of light and its absorbance is measured.

Example: Colorimetry is used in the estimation of copper in sample solutions

Principle
Solution containing Cu2+ ions is treated with NH3 solution. Cu+2 ions react with NH3 to form a
deep blue coloured cuprammonium complex ion.

2+
Cu2+ 4NH3 Cu(NH3)4
Deep blue coloured
cuprammonium complex ion

Procedure
Prepare 100 ml of 0.1 M solution of CuSO4. Transfer 2, 4, 6, 8 and 10 cm3 of prepared CuSO4
solution into different volumetric flasks from the burette. Add 2.5 cm3 of ammonia solution to all
the flasks and make upto to mark using distilled water. Stopper the flasks and shake well to get
uniform concentration.
Prepare a blank solution by taking 2.5 cm3 of NH3 in volumetric flask, make upto the mark by
using distilled water and shake well. Measure absorbance of all the solutions against blank at 620
nm using a photoelectric colorimeter.
To the given unknown solution, also add 2.5 cm3 of NH3 and make up to the mark with distilled
water.
Then a calibration curve is obtained by plotting absorbance against concentration. From the
calibration curve, the concentration of the Cu+2 in the solution can be determined.

Applications of colorimetry
1. Colorimetry is the most common analytical technique used in chemical and biochemical
estimations in various laboratories including clinical laboratories.
2. It’s the most widely used in clinical laboratories for the analysis of bio-molecules such as
glucose, urea, creatinine, etc.
3. It is used in water and food testing laboratories to check the concentration of critical
chemical parameters periodically.
Figure: Colorimetry (just for understanding and not required for the exam)

Potentiometry
The procedure of using measurement of e.m.f to determine the concentration of ionic species in
solution is referred to as potentiometry. The relation between electrode potential and metal ion
concentration is given by the Nernst equation:

0.0591 n+
E = Eo log M
n
It can be seen from the equation that the potential of an electrode E depends upon the
concentration of the ion Mn+ to which it is reversible.

Instrumentation
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 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 1 ml and the potential is
measured each time. Close to the equivalence point, there is a sharp increase in the potential. The
end point is determined by plotting change in potential against the volume of titrant.

Applications of potentiometry

1. It finds applications in oxidation-reduction titrations to estimate the concentration of

analyte in the sample solution.
2. In redox titrations, the indicator electrode is an inert metal such as platinum and reference
electrode (Saturated calomel electrode). The potential of the electrode depends on the
concentration of the substance being oxidized or reduced.
0.0591 Oxidized
E = Eo + log10
n Reduced

pH-sensor (Glass electrode)

Applications of pH

pH measurement is used in a wide variety of applications:

1) Food and beverages: It is important to monitor pH levels in the production of any
food or beverage product.
2) The pH level of soft drinks ranges from 2.1 to 7.4 depending on what kind of
ingredients and additives are added.
3) Agriculture
4) Wastewater treatment
5) Industrial processes
6) Environmental monitoring
7) Research and development
8) pH is a measure of the acidity or alkalinity of a solution
9) Aquariums and fish tanks

Prepared and compiled by

Dr. Sampath Chinnam, M.Sc., Ph.D., Post-Doc (South Africa)
Assistant Professor
Department of Chemistry
M.S. Ramaiah Institute of Technology
MSR Nagar
Bengaluru, Karnataka 560054
India