LECTURE NOTES

ON

APPLIED CHEMISTRY

I B.Tech II Sem

Common to

(ECE, CSE, CSIT&IT)

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B.Tech I Year II Semester Course Structure

L T P C
APPLIED CHEMISTRY 3 1 0 4
(ECE, CSE, IT Only)
Internal Marks: 40

Course Code: P18BST05 External Marks: 60

Course Prerequisite: Basic Chemistry at Intermediate or equivalent level.

Course Objectives
In this course. Student will learn the concepts and applications of chemistry in engineering.
● It aims at strengthening the students with the fundamental concepts of chemistry. Plastics
are nowadays used in household appliances; also they are used as composites (FRP) in
aerospace industries.
● It enables the students to know analysis of Advanced materials and used in diverse fields.
● It makes the students to effectively use of electro chemistry, battery technology, and
corrosion science in engineering applications
● It enables the students to Spectroscopic techniques and applications.
● Course Outcomes: After completion of course student will be able to
● CO1: The advantages and limitations of plastic materials and their use in design
would be understood.
● CO2: Analyze the different types of electrodes and batteries for technological
applications.
● CO3: To understand the 3D structure of the organic molecules.
● CO4: Analyze the structure of the chemical compounds.
● CO5: The students would aware of materials like nanomaterials, liquid crystals, green
chemistry.

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UNIT I: HIGH POLYMERS AND PLASTICS (12 Lectures)
Polymerization: Introduction, classification, types of polymerization, Stereo regular polymers,
Methods of polymerization (emulsion and suspension), Physical and mechanical properties.
Plastics as engineering materials: Advantages and limitations, Thermoplastics and
Thermosetting plastics, Compounding and fabrication (4/5 techniques), Preparation, properties
and applications of polyethene, PVC, Bakelite and Teflon
Elastomers: Natural rubber, compounding and vulcanization, Synthetic rubbers : Buna S, Buna
N, Thiokol- preparation ,properties and applications, applications of elastomers. Composite
materials & Fiber reinforced plastics, conducting polymers.

UNIT II: ELECTROCHEMISTRY AND CORROSION (12 Lectures)

Introduction, Single electrode potential, EMF, Galvanic cell, Nernst equation and applications.
Reference Electrodes-SHE, calomel electrode. Electro chemical series and uses of this series,
Concentration cells
Batteries: Introduction, Types: Dry Cell, Ni-Cd Cells, Pb-acid storage cells, Li ion cells.
Corrosion: Causes Theories of Corrosion (chemical and Electro chemical), types- galvanic,
differential aeration, stress corrosion, corrosion control methods– material selection and designing
aspects, Cathode protection – sacrificial anodic protection and impressed current cathode.
Galvanizing, Tinning, Electroplating of Copper and electro less plating of nickel.

UNIT III: STEREOCHEMISTRY (12 Lectures)

Representations of 3 dimensional structures, structural isomers and stereoisomers, configurations
and symmetry and chirality, enantiomers, diastereomers, optical activity, absolute configurations
and conformational analysis. Isomerism in transitional metal compounds.

UNIT-IV: SPECTROSCOPIC TECHNIQUES AND ORGANIC SYNTHESIS OF DRUG

MOLECULE (12 Lectures)
Principles of spectroscopy and selection rules. Electronic spectroscopy. Vibrational and rotational
spectroscopy. Basic concepts of Nuclear magnetic resonance spectroscopy, chemical shift.
Introduction to Magnetic resonance imaging.
Synthesis of commonly used drug molecules- Ibuoprofen, Aspirin, Paracetmol.

UNIT -V: CHEMISTRY OF ADVANCED MATERIALS (12 Lectures)

Nano materials:- Introduction – Sol-gel method & chemical reduction method of preparation
– Characterization by BET method and TEM methods - Carbon nano tubes and fullerenes:
Types, preparation, properties and applications.
Liquid crystals: - Introduction, Types, Applications.
Super conductors: Introduction, Type-I & Type-II super conductors, properties and applications.
Green Chemistry: - Principles, 3or 4 methods of synthesis with examples and applications.
Text Books:
1. Engineering Chemistry by Jain and Jain; Dhanpat Rai Publication & Co.
2. Engineering Chemistry by Shikha Agarwal; Cambridge University Press.
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3. Physical chemistry by K.Bahl and Tuli
4. Elementary organic spectroscopy by Y.R. Sharma, S.Chand publications
5. Spectroscopic techniques by H.Kaur. Pragati Prakashan publications
Reference Books:
1. Engineering Chemistry of Wiley India Pvt. Ltd., Vairam and others.
2. Engineering Chemistry by Prasanth Rath, Cengage Learning.
3. A text book of engineering Chemistry by S. S. Dara; S. Chand & Co Ltd.,
Latest Edition
4. Applied Chemistry by H.D. Gesser, Springer Publishers
5. Text book of Nano-science and nanotechnology by B.S. Murthy, P. Shankar and others.
WEB REFERENCES:
1. http://jntuk-coeerd.in/
2. http://en.wikipedia.org/wiki/title
3. http://nptel.ac.in/coures/105106/.com
4. https://en.wikipedia.org/wiki/Electrochemistry
5. https://www.youtube.com/watch?v=WLyaZbT97EI&list=PLzW3l18TEXrpqo3jRarGr
9ao-61tB2184
6. http://encyclopedia.che.engin.umich.edu/Pages/Polymers/PolymerProduction/Polymer
Production.html
7. http://encyclopedia.che.engin.umich.edu/Pages/ProcessParameters/Spectrometers/Spec
trometers.html

Course: I B.Tech Unit wise 10 Marks questions

Sub: Applied Chemistry
Branch: common to ECE, CSE, IT, EEE
UNIT – 1
1. Define and explain addition polymerization and condensation polymerization
2. Explain the following terms
a) Emulsion polymerization b) Suspension polymerization?
3. Write the preparation, properties and uses of following synthetic Materials?
a) Buna-S b) Buna-N (c) Thiokol rubber d) Poly ethylene e) PVC
f) Teflon g) Bakelite
4. Discuss about compounding of plastics
5. Explain the process involved in vulcanization of natural rubber? What are its
advantages?
6. Distinguish between Thermoplastic and Thermosetting polymers?
7. With the help of a neat sketch explain the following fabrication techniques
a) Injection moulding b) Extrusion moulding c) Compression moulding
d) Transfer moulding
8. What is polymer? How they are classified? Give an account of the different types of
polymer with suitable examples
9 . What are the physical and mechanical properties of polymers.

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 10. what are the conducting polymers .Explain.
11. what is processing of natural rubber . what are the disadvantages of natural rubber.
12. What are the fiber reinforced plastics .Explain.

UNIT – 2
1. Construct galvanic cell. Explain
2. Define Emf and explain.
3. Write a note on concentration cells? What are its applications?
4. What are the chemical reactions involved in Ni-Cd cell.
5. Derive Nernst equation. What are the applications?
6. Discuss Electro chemical theory (Wet corrosion) of corrosion?
7. What is meant by cathodic protection? Explain sacrificial anodic and impressed current
cathodic protection?

8. Construct Std. Hydrogen electrode and saturated calomel electrode

9. What is electrochemical series and what are its applications
10. Discuss the Chemical theory (dry ) of corrosion with an example.
11. Write a note on galvanizing and tinning?
12. Discuss the process involved in electro plating of copper and electro less plating of
Nickel
13. Discuss about lead accumulator and Li ion cells
14. Write a brief note on differential aeration corrosion and Stress corrosion.

UNIT – 3
1. Write a note on optical isomerism of a) lactic acid b) tartaric acid
2. Write a note on a) Geometrical isomerism b) Optical isomerism
3. Differentiate between a) enantiomers and diastereomers b) racemic mixture and meso
compounds
4. Summarize the conformational isomers of n-butane
5. a) Allocate the symbol E or Z to each of the following compound and explain?
6.

b) Assign R or S configuration of each of the following compounds

7. Write notes on a) Enantiomers b) Racemisation c) Meso compounds d) Resolution of

racemic mixture.
8. Neat sketch and which among the following compounds show geometrical isomerism a) 2-
butane, b) 2-methyl-2-butane c)2-pentene d) 1,2-dichloro propane

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9. Describe Geometrical isomerism and optical isomerism of 4-coordination compounds.
10. Describe Geometrical isomerism and optical isomerism of 6-coordination compounds .
11. Explain Structural isomerism in coordinated complex compounds
UNIT – 4
1. Briefly explain principle and selection rules of vibrational spectroscopy.
2. Briefly explain principle and selection rules of Rotational spectroscopy
3. Briefly explain principle and selection rules of NMR spectroscopy
4. Briefly explain principle and selection rules of Electronic (UV Visible) spectroscopy
5. In relation to NMR spectra, explain the following terms.
a) Chemical shift b)Shielding c) De shielding
6. Discuss the magnetic resonance imaging.
7. Discuss some applications of UV spectroscopy.
8. With neat sketch discuss electronic transitions in UV spectroscopy.
9. What is principle of Beer- Lamberts law
10. Discuss the procedure involved in preparation of paracetomol.
11. Discuss the procedure involved in preparation of Aspirin & ibuprofen..

UNIT – 5
1. Discuss the process involved in Sol-gel Method and Chemical vapour deposition method for
preparation of Nano materials.
2. Discuss about BET, TEM methods.
3. Discuss about different types of carbon Nano tubes and their importance.
4. What are properties and engineering applications of Nano materials?
5. Explain the properties of Fullerenes and Explain any one synthesis method of carbon nano
tubes
6. What are liquid crystals? Explain the classification of liquid crystals?
7. Write a note on thermo tropic and Lyotropic liquid crystals
8. What are the principles of Green chemistry?
9. Explain any two synthetic method of green chemistry
10. Write briefly about engineering application of green chemistry
11. Differentiate Type I & Type II Super conductors.
12. Write the properties and applications of super conductors

ASSIGNMENT QUESTIONS

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 UNIT-1
1. Explain the emulsion and Suspension polymerization methods?
2. Write the preparation, properties and uses of following polymers?
A) Buna-S b) Bakelite C) Thiokol
3. Write notes on compounding of plastics.
4. How is rubber vulcanized? What are its advantages?
UNIT-2
1. Write a detail note on electro plating of copper and Electroless plating of Nickel
2. Explain the Ni-Cd battery?
3. Describe chemical theory of corrosion?
4. Explain sacrificial anodic and impressed current catholic protection?
UNIT 3
1. Differentiate the enantiomers and diastereomers
2. Write notes on optical isomerism of lactic acid?
3. Write notes on geometrical isomerism in six coordinated complex compounds
4. Explain the optical isomerism in four coordinated complex compounds..
Unit-4
1.Write the preparation of Paracetmol?
2. What is meant by chemical shift. Explain
3. What are the basic principles of electronic spectroscopy
4. Explain the preparation process of Aspirin
UNIT-5

1. Write a note on BET and TEM methods?

2. Write a note on properties and applications of liquid crystals?
3. Write a note on type-1&Type-2 super conductors?
4. Explain any two green synthesis methods?

HALL TICKET NUMBER

PACE INSTITUTE OF TECHNOLOGY & SCIENCES::ONGOLE

(AUTONOMOUS)
I B.Tech I Semester Regular Examinations, Nov/Dec - 2018

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 Applied chemistry
Time: 3 hours ( Common to ECE,CSE,IT) Max. Marks: 60
Note: Question Paper consists of Two parts (Parts-A and Part-B)
PART-A
Answer all the questions in Part-A (5X2=10M)
[
1 a) What are the functions of plasticizers [2M]
L1]
b) Illustrate the basic selection rules for corrosion control [2M] [L2]
c) Differentiate enantiomers and diastereomers [2M] [L2]
d) Write the principle involved in Vibrational spectroscopy [2M] [L1]
e) Differentiate type –I and type-II super conductors [2M] [L2]
PART-B
Answer One Question from each UNIT (5X10=50M)
UNIT-I
Choose any one moulding process for the fabrication of following resins,
2 a [10M] [L3]
a) Thermoplastics b) Thermosetting resins?
(OR)
Explain with examples the following terms [L2]
2 b [10M]
a) Emulsion polymerization b) Suspension polymerization?
UNIT-II
3 a Discuss the dry theory of corrosion with an example. [10M] [L2]
(OR)
3 b Construct Std. Hydrogen electrode and saturated calomel electrode [10M] [L5]
UNIT-III
4 a Explain the conformational isomers of n-butane [10M] [L2]
(OR)
4 b Explain optical isomerism of a) lactic acid b) tartaric acid [10M] [L2]
UNIT-IV
5 a Define chemical shift. Explain the factors influencing the chemical shift [10M] [L1, 2]
(OR)
5 b What is the process involved in Synthesis of paracetamol [10M] [L1]
UNIT-V
6 a Discuss the principles of green chemistry [10M] [L2]
(OR)
6 b Explain any two synthetic method of Carbon nano materials [10M] [L2]

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 UNIT 1 HIGH POLYMERS AND PLASTICS

Introduction
1. Polymer: A large macromolecule which is obtained by the combination of large number of
simple molecules is known as polymer. Polymers usually have high melting and boiling points.
Polymers consist of repeating molecular units which usually are joined by covalent bonds.

Examples: PVC , polystyrene, cellulose, polyethylene, Bakelite

Monomers: The repeating units which were present in the polymer back bone chain is called
monomers
Degree of polymerization: The number of monomers present in a polymer molecule is known
as the degree of polymerization (DP).
For a homopolymer, there is only one type of monomer unit and the number-average degree of
polymerization is given by

, where Mn is the number-average molecular weight and M0 is the

molecular weight of the monomer unit. For most industrial purposes, degrees of polymerization
in the thousands or tens of thousands are desired.
Functionality: The number of reactive sites or bonding sites present in a monomer is called its
functionality.
The monomer must be bi functional i.e.it must have at least two reactive sites to involve in
polymerization. Depending upon the functionality of monomer units, different types of polymer
structures can be obtained
n CH2=CH2 → -( CH2-CH2-)n
Hence, ethylene is bi-functional monomer.
Bi functional monomers can form linear or straight chain polymers. Tri functional monomers
can form cross linked polymers.
CLASSIFICATION OF POLYMERS:
Polymers are classified in a number of ways as
1) Classification based on source of availability.
2) Classification based upon structure.
3) Classification based upon molecular forces.
4) Classification based upon mode of synthesis.
1) Based on the source the polymers again classified as
a) Natural polymers b) synthetic polymers c) Semi synthetic polymers
a) Natural polymers: The polymers obtained from nature (plants and animals) are called
Natural polymers.
Ex. Starch, cellulose, Natural rubbers, proteins, Nucleic acid
b) Synthetic Polymers: The polymers which are prepared in the laboratories are called synthetic
polymers
E.g. Polyethylene, polyvinylchloride (PVC), Nylon, Teflon, Bakelite, Terylene etc.

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c) Semi synthetic polymers: These are the synthetic derivatives of the natural polymers.
E.g.: Cellulose acetate (Rayon), cellulose nitrate and synthetic rubber etc.

2) Based on the structure polymers are classified as

(a) Linear polymer (b) Branched chain polymer (c) cross–linked polymer
a) Linear polymer: In linear polymer the monomeric units are linked together to form linear
chain.
E.g. Polyethylene, Nylon, polyester etc.
b) Branched chain polymer: In branched chain polymers the monomeric units are joined to form
long chains with side chains (or) Branches of different length.
E.g. Glycogen, starch, L.D.P.E. etc.
c) cross–linked polymer: In cross linked polymers the monomer units are cross linked together to
form a three dimensional Network.
E.g. Bakelite, melamine– formaldehyde Resin polystyrene–Butadiene.
3) Based on the molecular forces polymers are classified as
a) Thermoplastic b) Thermosetting c) Elastomers d) Fibers
a) Thermoplastics: Thermoplastics are the polymers which soften on heating and harden on
cooling reversibly.
E.g. Polyethylene, polystyrene, PVC, Teflon, Nylon, sealing wax.
b) Thermosetting: Thermosetting plastics are the polymers which undergo permanent change
on heating (irreversible)
E.g. Bakelite, Polyester, Polysiloxanes.
c) Elastomers: Elastomers are the polymers which posses elastic character.
E.g. Natural rubber
d) Fibers: Fibers are polymers in which the chains are held by intermolecular forces like H–
bond, Dipole–dipole interaction.
E.g. Nylon, poly Acrylonitrile
4) Based on the mode of synthesis polymer are classified as
a) Addition polymers b) condensation polymers
a) Addition polymers: A polymer formed by direct addition of repeated monomer without the
elimination of by product molecules are called Addition polymer.
E.g. Polyethylene, polypropylene, PVC, Teflon, orlun, Neoprene, PVP (polyvinyl pyrolidone)
initiator
nCH2= CH2 → -(CH2 ─CH2)n-
b) Condensation polymers: A polymer formed by the condensation of two (or) more
monomers with the elimination of simple molecule like H2O, NH3, HCl, alcohol etc. are called
condensation polymer.
E.g. Terylene, Bakelite, Alkyl Resin, Nylon 6, 6.
Leather, cellulose, Rayon etc. are the example of organic polymer and Glass (Silicone rubber) is
the example of inorganic polymers.

2. What is polymerization? Give examples to different kind of polymerization.

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 POLYMERISATION: The process of a large macro molecule by the combination of large
no.of monomers is known as polymerization. Types :
a) Addition polymerization (or) chain growth polymerization.
b) Condensation polymerization (or) step growth polymerization.
a) Addition polymerization: The process of formation of a large macromolecule by the
addition of large no. of same type of monomers without the elimination of small molecules like
H2O, CH3OH, and NH3 are known as Addition polymers. This process is called Addition
polymerization.
The monomers which contains double bonds or triple bonds will be involved in addition
polymerization.
Characteristics
● The functionality of the monomer is bi functional
● The polymerization takes place by self-addition of the monomer to each other through
chain reaction.
● The polymer is an exact multiple of original monomer.
● The composition of polymer is as same as that of monomer.
● It is an exothermic reaction. The rate of reaction is fast.
● The reaction involved in three steps. i.e. a) chain initiation, b) chain propagation, c)
chain termination.
Examples: 1. Poly ethylene 2.Poly vinyl chloride 3.Teflon
1. Poly ethylene: It is obtained by the polymerization of large number of ethylene monomers.
n (CH2 = CH2) 🡪 --(-CH2--CH2)n–

2. Poly vinyl chloride: It will be obtained by the polymerization of vinyl chloride monomers

3. Teflon: It is obtained by the polymerization of large number of tetra fluoro ethylene

monomers

b) Condensation polymerization (or) step growth polymerization: - The process of

formation of a large macro molecule by the condensation of large no. of different type of
monomers with the loss of small molecules like H2O, CH3OH, and NH3 are known as
condensation polymerization.
Characteristics;
1.The monomer must contain simple polar functional groups like –OH, -COOH, NH2, RCOOR
etc.
2. The functionality of the monomer must be more than two.
3. It is a single step process. It is an endothermic reaction. The rate of reaction is very slow.

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4. The product of polymerization is not exact multiple of original monomer.The product of
polymer is known as condensation polymer.
Examples of condensation polymerization
1. Polyethylene terephthalate (PET), is obtained by condensation polymerization of ethylene
glycol and terephthalic acid monomers

2. Nylon-6, 6 is obtained by condensation polymerisation of adipic acid and hexa methylene

diamine

n HOOC–(CH2)4–COOH + n H2N–(CH2)6–NH2→ ─( HN(CH2)6 NH–CO–(CH2)4 –CO)n–+2n

H2O

(Adipic acid) (Hexa methylene diamine) (Nylon-6, 6)

3. Copolymerization: It is the polymerization reaction in which more than one type of

monomers polymerizes to form a copolymer. In this polymerization high molecular weight
compounds obtained.
Examples:
I) Buna-S: It is obtained by the co polymerization of 1,3 buta di ene and styrene in
presence of ‘Na’ as catalyst.

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 ii) Buna-N:. It is obtained by the co polymerization of 1,3 buta di ene and acrylo nitrile
in presence of ‘Na’ as catalyst.

3. Difference between Addition polymerization and Condensation polymerization

4.
Addition polymerization Condensation polymerization

1) It is also known as chain growth 1) It is also known as step growth

polymerization polymerization.

2) It takes place only in monomer 2) It takes place only in monomer having

having multiple bonds. reactive functional groups.

3) It does not involves the elimination of 3) It involves the elimination of simple

simple molecules like H2O, NH3 etc. molecules like H2O, NH3 etc.

4) High molecular weight polymer is 4) The molecular weight of polymer increases

formed. steadily throughout the reaction.

5) Mostly thermo plastics are produced. 5) Mostly thermo setting plastics are
produced.

6)Longer reaction time gives high yield 6) Longer reaction times are essential to obtain
high molecular weight.

7) Examples are polyethylene, 7)examples are Bakelite, urea-formaldehyde

polypropylene, poly vinyl chloride. resin, epoxy resins,etc.

4. Methods of polymerization.
Polymer substance (Resin) can be prepared in the following methods
1. Emulsion Polymerization 2. Suspension polymerization
1. Emulsion Polymerization:-
In emulsion polymerization there are some key “ingredients”:

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1. The monomer must be insoluble in water and polymerizable by free radicals
2. Water-soluble initiator
3. Water
4. Surfactant

1. in this process a monomer I soluble in water and forms relatively large droplets. To stabilize
these droplets the solution is mixed with surfactants. Then it can form micelles.
2. A water soluble initiator is added to the water phase where it diffuses into the micelles and
reacts with monomers to form polymer substance.
3. The concentration of micelles is increased to critical micelles concentration. At this stage the
monomer in the micelles quickly polymerizes and forms a large macromolecule called polymer.
4. The growing chain will be terminated at the end. Monomers which undergo free radical chain
polymerization will undergo emulsion polymerization.
5. Example polyethylene, poly styrene, PVC, TEFLON, Buna-S, Poly butadiene, acryl rubber
will undergo emulsion polymerization method.
Advantages: 1.High molecular weight polymers can be prepared in this method.
2. It is very fast. The final product can be directly used for fabrication.
2. Suspension polymerization:-
1. Suspension polymerization is a heterogeneous free radical polymerization that uses
mechanical agitation to mix a monomer or a mixture of monomers in a liquid phase, such as water
while monomers polymerize, forming spheres of polymer.
2. The process is used in the production of many commercial resins like polyvinyl chloride,
polystyrene, expanded polystyrene.
3. Suspension polymerization is carried out in two ways depending on the morphology of the
particles.
a. In bead polymerization the polymer bead produced is smooth and translucent.
b. In powder polymerization the polymer beads produced are porous and irregular.
4. In suspension polymerization method the monomer, bioactive material and initiator are
dispersed in water and stabilizer to produce monomer droplets 50-200 mill microns in diameter.
5. The dispersion is maintained by vigorous continuous agitation and the droplets are prevented
to coalesce by stabilizer. Thus polymer is produced in heterogeneous medium is separated and
dried.
6. The initiator used is dibenzoylperoxide. Silica nonoparticles and n-isopropylacrylamidein
n-hexane are used as stabilizers.
Advantages of the method are better heat control of the reactions and easy separation of the
polymer beads.
Disadvantage is that few monomers are water soluble.
Scheme:
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 MONOMER + BIOACTIVE MATERIAL + INITIATOR __ water + stabilizer
____DROPLET ____agitation + heat _____ POLYMERISATION ______ SEPARATION &
DRYING ________ POLYMER BEADS

What are the Physical and Mechanical Properties of polymers

All polymers are considered to be excellent engineering materials because of their physical and
mechanical properties.
Physical properties: The following are the physical properties of polymers...
1. Crystallinity: Crystalline and Amorphous Polymers
Polymeric molecules do not possess a definite crystalline structure like non polymeric
molecules. As the polymeric molecules are long chains the degree to which polymeric molecules
are arranged in orderly pattern with respect to each other is a measure of crystalline.
It can be defined as the small region in which larger molecules are linked to each other in some
regular way. No polymer is 100% crystalline or no polymer is 100% amorphous. As the
crystalline increases, the brittleness, strength, hardness and chemical resistance of a polymer
increases.
2. Molecular Weight:
The physical properties (such as transition temperature, viscosity, etc.) and mechanical
properties (such as strength, stiffness, and toughness) depend on the molecular weight of
polymer. The lower the molecular weight, lower the transition temperature, viscosity, and the
mechanical properties. Due to increased entanglement of chains with increased molecular
weight, the polymer gets higher viscosity in molten state, which makes the processing of
polymer difficult.
3. Solubility. When a polymer is dissolved in a suitable solvent, the polymer will absorbs that
solvent and swells in size. Slowly polymer goes into the solution as a viscous liquid and forms a
heterogeneous solution. Whereas non polymer molecule like NaCl is added to the solvent it will
ionizes and forms homogeneous solution.
Mechanical properties.
1. Toughness: The impact strength is measured the size of crystalline structure is also
determines the toughness. The small spherical crystalline masses increase toughness.
2. Strength: The strength of polymer depends upon the length of the polymer chain. The
strength of the polymer increases with the increase in molecular weight. The intermolecular
forces of attraction, presence of polar groups and chain length increases the strength of the
polymers.
3. Elasticity: Elasticity is the property of recovering the original shape after removing the
deformational stress. Natural rubbers possess high elasticity due to coiled structure.
5. Stereo specific polymer (Tacticity):-
polymers having definite tacticity are known as stereo specific polymers.
Tacticity: - The stereo chemical placement of the asymmetric carbon in polymer chain is called
tacticity. Tacticity do affect the physical properties. This orientation results in three types of
stereo specific polymers. 1) Isotactic polymer 2) Syndiotactic polymers 3) Atactic polymers
Isotactic polymer: -
In Isotactic polymers all the substituent’s are placed on the same side of the polymer chain.
Polypropylene formed by Ziegler-Natta catalysis is an Isotactic polymer. Isotactic polymers are

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usually semi crystalline and often form a helix configuration.

Syndiotactic polymers
In syndiotactic polymer the substituent’s have alternate positions along the chain.
Ex: Syndiotactic polystyrene, gutta percha is also an example for Syndiotactic polymer.

Atactic polymers: In Atactic polymer the substituents are placed randomly along the chain.
These types of polymers are formed by free radical mechanism.
Ex: poly styrene, poly vinyl chloride, polypropylene etc.

PLASTICS
Introduction:-
Plastics are high molecular weight organic polymers that show the property of plasticity and can
be moulded into any desired shape and dimensions by the application of heat and pressure.
Advantages (or) Merits of Plastics
1. Plastics have good shock absorption capacity compared with metals.
2. Plastics have high abrasion resistance.
3. Plastics are chemically inert.
4. Plastics have high corrosion resistance compared to metals.
5. Plastics are light in weight...
6. Plastics are having high dimensionally stablity.
7. Plastics does not swells in oils and water.
8. They show good thermal and electrical insulation capacity .
Types of plastics:
Thermoplastics: - The polymers which are capable of softening on heating and hardening on
cooling are called thermo plastics these are the linear long chain polymers. These polymers
possess inter molecular forces of attraction intermediate between Elastomers and fibers. They are
formed by addition polymerization
ex: polythene, polystyrene, polyvinyl etc
Thermo setting plastics: - The polymers which on heating do not soften and cannot be remolded
are called thermosetting polymers. On heating they undergo extensive cross-linking in moulds and

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 become infusible. They have three dimensional cross-linking network structures. They retain the
shape and structure even on heating. They are formed by condensation polymerization.
E.g. Bakelite, urea- formaldehyde resins etc

Differences between thermoplastics and thermosetting plastics

Thermoplastics
1. These are formed by addition Polymerization.
2. They having linear or branched chain structure Polymerization.
3. In between adjacent polymers they having
week vandarwaal’s forces of attractions .
4. These are weak ,soft and less brittle
5. They are soften on heating and harden on
cooling
6. They can be reuse or recycled.
7. They can be re-mould and re- shaped
8. They can be dissolved in some organic
solvents.
9. examples: poly ethylene, pvc, poly styrene etc.,
Thermo setting plastics
1. These are formed by condensation
2. They having cross linked structure
3.In between adjacent polymers they having
strong covalent bonds .
4. These are hard , strong and more brittle.
5.There is no response on heating or cooling
6. They cannot be reuse or recycle.
7. They cannot be re mould or re shape.
8. These are insoluble in any organic solvents.
9.examples:Bekalite, nylon-6,6, polyester etc.,

Compounding of plastics:
Compounding of the plastics may be defined as the mixing of different materials like
plasticizers, fillers or extenders, lubricants, dyes and pigments to the thermoplastic and
thermosetting plastics to increase their useful properties like strength, toughness etc.,
Ingredients used in compounding of plastics
Some of the ingredients used in compounding of plastics are i) Resin or Binder
iii) Plasticizers. iii) Fillers or extenders. iv) Dyes and pigments. V) Lubricants. Vi) catalyst
Vii) Stabilizers
i) Resin or Binder : It is the basic substance of plastic. The type of plastic depends upon type
of resin and the type of moulding treatment depends upon type of resin. There are two m types
of resins. One is thermo plastic resin and another one is thermo set resin.
ii). Plasticizers
Plasticizers are substances added to enhance the plasticity of the material and to reduce the
cracking on the surface. Plasticizers are added to the plastics to increase flexibility and
toughness. Ex: Dibutyle oxalate, Castor oil and Tricresyl phosphate.
iii) Fillers or Extenders
Fillers are generally added to thermosetting plastics to increase elasticity and crack resistance.
Fillers improve thermal stability, strength, non combustibility, water resistance, electrical
insulation properties and external appearance.
Ex: wood flour, Asbestos, Mica, Cotton, and Carbon black, Graphite, Barium sulphate etc.
iv) Colorants (Dyes and pigments)
These are added to impart the desired color to the plastics and give decorative effect.
EX: Carbon black-Black color, Anthraquinone.-Yellow; Azo dyes-Yellow, Red, Orange etc..
V) Lubricants

17
These are added to prevent the plastics from sticking to the moulds.
Ex: Oils, Waxes, Soaps etc.
Vi) catalyst: It is used to improve the rate of a reaction .For addition polymerization reactions
benzoyl peroxide is a common catalyst. For condensation polymerization reactions lewis acis or
bases , Na, Zn, Fe, Co, Copper, Ni, are general catalyst.
Vii) Stabilizers:
These are added to the plastics to improve thermal stability during moulding.
EX: White lead, Lead chromate, Red lead are commonly used as stabilizers.
Fabrication of plastics (or) Moulding of Plastics
Many methods of fabricating plastics into desired shaped articles are employed. This
Production of plastics is known as fabrication of plastics. The method of moulding depends upon
the type of resins used
1). Compression Moulding:
Compression moulding is one of the original processing methods for manufacturing plastic parts
developed at the very beginning of the plastics industry..
Although it is also applicable to thermoplastics, compression moulding is commonly used in
manufacturing thermoset plastic parts. The raw materials for compression moulding are usually
in the form of granules. They are first placed in an open, heated mould cavity. The mould is then
closed and pressure is applied to force the material to fill up the cavity. A hydraulic ram is often
utilized to produce sufficient force during the moulding process. The heat and pressure are
maintained until the plastic material is cured. The advantages of compression moulding are
lowest cost moulds, lower labor cost, minimum amount of wasted material and minimum
internal stress.

2) Injection Moulding:
The plastic Materials such as polystyrene, nylon, polypropylene and polythene can be used in a
process called injection moulding.
In this process Granules of plastic powder are poured or fed into a hopper which stores it until it is needed.
A large screw thread is turned by a motor which feeds the granules through a heated section. .
In this heated section the granules melt and become a liquid and the liquid is forced into a mould
Where it cools into the desired shape (in this case a sphere). The mould then opens and the sphere is removed

18
 Injection Moulding
3. Transfer Moulding: This method is applied for thermosetting plastics and this technique is
Similar to injection moulding. The sample (plastic material) is kept in a heated chamber then
Injected through an Orifice (nozzle) into the mould by a piston plunger at very high pressure.
As the sample( plastic mass ) passes through the orifice, due to friction, temperature
of the material increases and moulding powder becomes liquid and drops quickly to the mould.
Now curing takes place under the Influence of heat and pressure and required shaped product is obtained

Transfer mould
4. Extrusion moulding: The extrusion process is similar to injection moulding
This process is useful in the preparation of continuous wires with uniform cross section.
The plastic granules are heated in a hopper and a screw thread forces the material through a die.
The material is then cooled. Extrusion moulding can only be used for simple shapes and the end product
generally has a poor quality finish

19
 5. Blow Moulding: Blow moulding is used for the production of plastic bottles.
The plastics normally used in this process are; polythene, PVC and polypropylene.
The process is similar to injection and extrusion mouldings.
1. The plastic is fed in granular form into a 'hopper' that stores it.
2. A large screw thread is turned by a motor which feeds the granules through a heated
section.
3. In this heated section the granules melt and become a liquid and the liquid is forced into a
mould.
4. Air is blow into the mould which forces the plastic to the sides, giving the shape of the
bottle.
5. The mould is then cooled and is removed can only be used for simple shapes.

Blow moulding process

8. Preparation and properties of some plastics

1. Poly ethylene (PE): It is obtained by the polymerization of ethylene. It is divided into two
types.
Low density poly ethylene: It is obtained by free radical polymerization of ethylene using
oxygen as initiator with pressure of 1500 Atm at temperature range of 180-2500c.

Properties: LDPE has a density 0.91 to 0.925 g/cm3

● The m.p is 110-125oc It is 40%crystaline.
Uses: LDPE is used in making films, sheets, Pipes. Table cloths, packing materials etc.,
High density polyethene (HDPE) : Preparation: It is obtained by coordination polymerization
of ethylene using zeiglar-natta catalyst under low pressure.

20
Properties:
● Its m.p is 144-1500C
● HDPE has a density 0.941 to 0.965 g/cm3
It is 90% crystalline
It is chemically more resistant than LDPE
It has excellent electrical insulator.
Uses:
HDPE is used in manufacture of films, detergent bottles, pipes, toys and other household articles
etc.

2. Poly vinyl chloride (PVC):

Poly Vinyl Chloride is obtained by the free radical chain polymerization of vinyl chloride in
presence of benzoyl peroxide or hydrogen peroxide as initiator.

Vinyl chloride poly vinyl chloride

Properties:
It is colorless, non inflammable material.
It is having high density.
It is resistant to light, atmospheric oxygen, inorganic acids and alkalis.
It is strong brittle.
Uses:

● It is mainly used in cable insulation, leather cloth, packing and toys.

● It is used for manufacturing of film, sheet and floor covering.
PVC pipes are used for carrying corrosive chemicals in petrochemical factories.

3. TEFLON OR Poly tetra fluoro ethylene Or Fluon:

Teflon is obtained by chain polymerization of tetra fluoroethylene, under pressure in presence of benzoyl
peroxide as catalyst.

Properties: It is colourless transparent. It has good strength. It has good mechanical properties.
It is a good electrical insulator. It is very good abrasion resistance.
Uses:
● It is used as insulating material for motors, transformers, cables, wires, etc;
● It is used for making gaskets, packing, pump parts, tank linings, chemical-carrying pipes, etc

4. Bakelite:

21
It is prepared by condensation of phenol with formaldehyde in presence of acidic/alkaline
Catalyst. The initial reaction results in the formation of O- and P- hydroxyl methyl phenol which
reacts to form linear polymer which is called Novalac.
On further heating with HCHO, novalac undergoes cross-linking to form infusible solid
called Bakelite.

RUBBERS AND ELASTOMERS

9. What is natural rubber? How is it extracted from latex? What is its composition?

RUBBER; It is natural polymer of isoprene. It is obtained from the milk of rubber tree called
Latex.

Preparation of natural rubber:

1. Natural rubber is obtained from nearly 500 different plants, but the main source from which
the commercial natural rubber is obtained is the tree Hovea brazilianesis.
2. Rubber is obtained from latex (milky sap) collected from the cuts made in the bark of the tree.

22
3. The obtained latex contains hydrocarbon with impurities such as fatty acids, proteins and
resins an emulsified form.
4. The latex is then coagulated with acetic acid or formic acid. The Crude or raw rubber is
composed of 95% hydrocarbons, 4% protein and 1% of resins...
5. The precipitated rubber is collected and passed through rollers to get sheets of rubber.
Rubber sheets are finally dried by smoking. This rubber is called "smoked rubber"
6. During the coagulation of latex with acetic acid or formic acid; retardants like sodium
bisulphate (NaHSO3) are added to prevent oxidation of rubber. The is called "creep rubber"

Structure of natural rubber:

● M.F of natural rubber is C5H8

● On strong heating in presence of air or O2 it gives CO2, H2O. Hence it contains C, H.
● When heated in absence of air or O2 gives isoprene

● So natural rubber is the polymer of isoprene.

● It is a linear polymer, isoprene unit are joined head to – tail by 1, 4 links. X-ray studies
indicate that in natural rubber isoprene units are arranged in cis form
● It contain 11,000 to 20,000 isoprene units with molecular wt. 13,0000 to 34,0000

● Gutta percha rubber is also a natural rubber in which isoprene units are arranged in the
Trans manner.

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10. A) Compounding of rubber:

Natural rubber is compounded with some substrates to get quality rubber.

1. Reinforcing agent; they are added to get hard rubber.
Examples: carbon Powder, zinc oxide etc.
2. Softeners: They are added to get soft spongy rubber.
Example; vegetable oil, stearic acid, paraffin oil etc.,
3. Anti oxidants; they are added to prevent oxidation of rubber.
Examples; Naphtha
4. Vulcanization; vulcanization is compounding of rubber with sulphur, H2S, so2, Cl2, etc.
5. Coloring matter; they are added to impart desired colored to rubber.
Examples: zinc oxide: white, Lead chromate: yellow
Chromic oxide: green, carbon black: black.
6. Accelerator: They are added to speed up the vulcanization of rubber.
Examples; Lime-magnesia, White lead etc.,
7. Fillers: Fillers are added to reduce cost, increase strength, and introduce new characters.
Examples: Asbestos, Mica, Gypsum, Talc etc.

B) Vulcanization:
1. The process of heating raw rubber with sulphur at 373K to 415K temperatures to improve its
physical properties is known as vulcanization
2. This process was discovered by Charles Good year and name was given by Thomas Hamcock.
3. Vulcanization process is slow process and it can be accelerated by addition of zinc oxide, zinc
stearate etc.
4. The stiffness of vulcanized rubber increases with increasing the percentage of sulphur in it.
About 5% sulphur is used for making tyre rubber and 30% of sulphur is used for making battery
case rubber.
5. The rubber becomes cross linked with sulphur during vulcanization. The formation of cross
links at the reactive sites of double bonds and thus rubber gets stiffened
Advantages of Vulcanized Rubber
1. Vulcanized rubber has good tensile strength.
2. It has low water absorption capacity
3. The working temperature of vulcanized rubber is enhanced up to 100°C.
4. The elasticity of vulcanized rubber is very low

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11. Synthetic rubbers:

Buna-S (Styrene Butadiene Rubber: SBR): Buna is a copolymer of 75% butadiene

(CH2=CH–CH=CH2) and 25% of styrene (C6H5CH=CH2). The polymerization is carried out at
50°C in the presence of peroxide catalyst; it is also called SBR or GRS rubber.

Properties:
● It can be vulcanized like natural rubber with sulphur and compounded with carbon black
● It has excellent abrasion resistant and high load bearing capacity’
● It is sensitive to oil, waste water and ozone.
Uses:
● It is used in the manufacture of motor tires.
● It is used as electrical insulator. It is used in making conveyor belts, gaskets and foot wear
components, etc.
Buna-N or NBR (Nitrile-Butadiene Rubber): It is a polymer of butadiene and acrylonitrile

25
Properties: It is very rigid . It is excellent resistant to action of petrol, lubricating oil and many
organic solvents. It posses excellent resistant to heat, sunlight and acids
● It has good tensile strength and abrasion resistant.
Uses: It is mainly used for making automobile parts and tank lining, conveyor belts, gaskets,
printing rollers, oil-resistant foams etc.,
Thiokol (Polysulphide Rubber or GR-P): Polysulphide rubbers are the condensation product
of ethylene dichloride and sodium tetra sulphide.

Properties:
▪ Thiokol is resistant to the action of oxygen and ozone.
▪ It is also resistant to the action of petrol lubricants and organic solvents
▪ Thiokol films are impermeable to gases to a large extent.
▪ Thiokol’s are vulcanized with metal oxides such as zinc oxide.
▪ But Thiokol has poor heat resistance and low tensile strength.
Uses:
▪ Thiokol mixed with oxidizing agents in used as a fuel in rocket engine.
▪ It is used to engine gaskets.Thiokol’s are used for hoses and tank lining for
the handling and storage of oils and Solvents
12. COMPOSITE MATERIALS
[A] CONDUCTING POLYMERS:
A polymer which can conduct electricity is termed as conducting polymer. It is classified into
following types 1. INTRINSICALLY CONDUCTING POLYMERS: These polymers have
extensive conjugation in the backbone which is responsible
These are two types:
a). CONDUCTING POLYMERS HAVING CONJUGATION π- electrons in the back bone:
Polymers have alternating double and single bond along the polymer chain and each carbon atom
is in sp2 hybridized state. One valence electron (π) on carbon is pz orbital. The orbital’s of
conjugated π electrons overlap the entire backbone of the polymer and result in the formation of
valence bond and conduction bond.

26
The valence bond is filled bond and conduction is empty. When the energy gap between them is
low the electron from valence band are excited to conduction band and become mobile through
the polymer and shows conductivity.
Examples

b). DOPED CONDUCTING POLYMERS: polymers conductivities are increased by oxidation

or reduction process as they have low ionization potential and high electron affinity. Oxidation
process undergoes by adding some alkali metal ion or electron acceptor conducting is enhanced
by p-doping. Reduction process undergoes by adding reducing agents of electron donor
conductivity is enhanced by n-doping.

P-Type doping: It is done by oxidation of a conducting polymer like polyacetylene with a Lewis
acid .This is also called oxidative doping.
During oxidation process the removal of one pi bond leads to formation of delocalized radical
ion called polaron having a hole in between the valence band and conduction band. The second
oxidation of the polaron results in two positive charge carriers in each chain called bipolaron
which are mobile because of delocalization. These delocalized charge carriers are responsible for
conductance.

N-Type doping: It is done by reduction of a conducting polymer like polyacetylene with a

sodium naphthalide .This is also called reductive doping.
During reduction process the gaining of one electron leads to formation of delocalized radical ion
called polaron having an excess electron in between the valence band and conduction band. The
second reduction of the polaron results in two negative charge carriers in each chain called
bipolaron which are mobile because of delocalization. These delocalized charge carriers are
responsible for conductance.
-[--CH = CH-- CH = CH-- CH = CH-]-n ------Na+ (C10H8)- 🡪 -[--CH = CH-- CH – (CH)--- CH =
CH-]n-
Poly acetylene Reduction Polaron radical anion
2. EXTRINSICALLY CONDUCTING POLYMERS: These polymers owe their conductivity
due to the presence of externally added ingredients in them. These are of two types:

27
a). CONDUCTIVE ELEMEMT FILLED POLYMERS: the polymer acts as the binder to hold
the conducting element together in the solid entity. These polymers possess reasonably good
bulk conductivity and are low in cost light in weight mechanically durable and strong and easily
process able in different forms shapes and size.

b). BLENDED CONDUCTING POLYMERS: it is obtained by blending a conventional

polymer with conducting polymer either by physical or chemical change. Such polymer can be
easily processed and possess better physical, chemical, electrical and mechanical properties.
Applications of conducting polymers:
a. In rechargeable batteries: These batteries are small in size, longer lasting and can produce
current density up to 50mA/cm2.
b. In analytical sensors: Conducting polymers are also used for making sensors for pH, O2,
NOx, SO2, NH3 and glucose.
c. For making Ion-exchangers: Membranes made up of them can show boundary layer effects
with selective permeability for ions, gases, etc. They are useful for ion-exchangers and controlled
release of drugs.
d. In electro-chromic displays and optical filters: ICP’s can absorb visible light to give
colored products so can useful for LED’s and data storage.
[B].FIBER REINFORCED PLASTICS (FRP)
Fiber reinforced plastics are produced by reinforcing a plastic matrix with a high strength fiber
materials such as glass, Graphite, alumina, carbon, boron, beryllium and aromatic polyamide.
Natural fibers such as sisal, asbestos are also used for reinforcement. Glass fiber is the most
extensively used reinforced fiber because of durability, acid proof, water proof, and fire proof
nature of glass.
Glass is drawn into threads or fibers in the form of filaments fine cotton or silk thread. Then the
filaments are woven in the form of mats. The fiber material is suitably bonded with plastics
materials to be reinforced. The common plastics resins used are polyester, epoxy, silicone,
melamine, vinyl derivatives and polyamides. The following are the various processing
techniques adopted.
a. Matched metal die moulding: This is the most efficient and economical method for mass
production of high strength parts. It is press moulding under a temperature of 235 – 260 F and
200 – 300 psi pressure. The upper mould containing the resin and reinforcing fiber is pressed on
the lower mould.
b. Injection Moulding: This method is for reinforced thermoplastics. A mix of short fiber and
resin are forced by a screw or plunger through a nozzle into the heated mould and allowed to
curve.
c. Hand-lay-up: Mostly used thermoset plastic resins the reinforcing mat fiber is cut to fit in a
mould and saturated with resin by hand using a brush. Roller or spray gun. Layer built up gives
the thickness of the articles.
d. Continuous lamination: reinforcing mats or fabrics are impregnated with resin, run through
Laminating rolls between cellophane sheets to control the thickness and resin continent. They are
then cured in heating chamber.
e. Centrifugal casting: Chopped fibers and resin are placed inside a mandrel and uniformly
distributed as mandrel is rotated inside an oven.

28
f. Spray up: Short length of reinforcement and resin are projected by a specially designed spray
gun so that they are deposited simultaneously on the surface of the mould. Curing is done with a
catalyst at room temperature.
Applications of FRP: Fiber reinforced plastics find extensive use in space crafts, aeroplanes,
boat nulls, acid storage tanks, motor cars and building materials. Melamine FRP is used for
insulation and making baskets.
Advantages of FRP: The fiber reinforced plastics have the following advantages.
● Low efficient of thermal expansion, High dimensional stability , Low cost of
production
● Good tensile strength . Non inflammable and non-corrode and chemical resistance.

UNIT – 2: ELECTRO CHEMISTRY AND CORROSION

*Introduction: Electrochemistry is a branch of Physical Chemistry which deals with the
transformation of Electrical Energy into Chemical Energy (or) Chemical Energy into Electrical
Energy.

Electrochemical Cells: It is of 2 types.

● Electro Chemical Cell /Galvanic Cell: Chemical energy Electrical

energy
● Electrolytic Cell : Electrical energy Chemical
energy.

Electrode: An electrode is a small piece of metal or other substance that is used to take an
electric current to or from a source of power. It is of 2 types:

● Anode: It is an electrode where oxidation takes place. As reaction proceeds anode

appears to become smaller with time because it’s metal become ion and falls into
electrolytic solution
● Cathode: It is an electrode where reduction takes place. As reaction proceeds cathode
appears to become larger with time because the metallic ions in its cell receive electron
and get neutral metallic atom which will go and plate on it.
Electrode potential :
The ability of an electrode to lose or gain electrons, when it is electrically contacted with its own
ionic salt solution is called electrode potential. It is represented by E.
Standard electrode potential: The ability of an electrode to lose or gain electrons, when it is
electrically contacted with its own ionic salt solution of 1M concentration ,1 atmosphere pressure
and at 298K temperature, and is known as standard electrode potential. It is represented by E0.
EMF of Electrochemical cell:
The difference of potential, which causes flow of electrons from the electrode of higher potential
to the electrode of lower potential, is called electromotive force (EMF). The emf of galvanic cell
is calculated from the reduction half-cell potentials using the following relation.
E (cell) = ERHS – ELHS (or) E cathode- E anode

29
Where E (cell) = emf of cell
E (right) = reduction potential of right hand side electrode
E (left) = reduction potential of left hand side electrode

Applications:
● Potentiometer titrations can be carried out.
● Transport number of the ions can be determined
● Measurement of pH using hydrogen, quinhydrine and glass electrode
● From the EMF data the free energy changes, equilibrium constant of a reaction can be
found

1. Galvanic Cells or Electro-chemical Cells: The cell in which electrical energy is produced by
spontaneous redox reaction takes place is known as Galvanic cell.

Electro-
chemical cells are entirely
different from
electrolytic cells. In
electrolytic cell electrical
energy is converted to
chemical energy. But in
electro chemical cells or voltaic cells or galvanic cells chemical energy is converted to electrical
energy. Daniel cell is an example for the galvanic cell.

Cell construction:-
It consists of Zinc electrode dipped in ZnSO4 solution. Where oxidation takes place,
known as oxidation half cell and copper electrode dipped in CuSO4 solution. Where reduction
takes place, known as reduction half cell. These two solutions are separated by a salt bridge (U-
tube containing concentrated solution of KCl or NH4NO3 in an agar-agar gel). Or porous pot, it
provides an electrical contact between two solutions. The following chemical reactions take
place
At Anode: Zn --> Zn2+ + 2e- (Oxidation Half Reaction)
At Cathode: Cu+2 + 2e- --> Cu (Reduction half reaction)
Net cell reaction Zn + Cu --> Zn2+ +Cu
2+

Representation of Galvanic cells or cell diagram: It consists of two electrodes anode &
cathode. It is represented by keeping in view the following points.

⮚ Anode must be written on the left hand side, cathode on the right hand side.
⮚ Left hand side electrode is written by writing the metal first and then electrolyte.
⮚ These two are separated by vertical line or a semicolon. The electrolyte may be written by
the formulae of the compounds or by ionic species.

30
 Zn/Zn2+ (or) Zn; Zn2+ (or) Zn; ZnSO4

⮚ Cathode is written on the right hand side. In this electrolyte is written first and then metal;
these two are separated by a vertical line or a semicolon

Cu2+ / Cu (or) Cu2+; Cu (or) CuSO4 / Cu

⮚ A salt bridge is denoted by two vertical lines, which separates the two half cells.

E.g.: Daniel cell

Cell representation for Daniel cell: Zn/ Zn2+ || Cu2+/ Cu
2. Nernst Equation: The equation that gives the relation between electrode potential and
concentration of electrolyte is known as Nernst equation.
Derivation: Nernst equation is a general equation that relates the Gibbs free energy and cell
potential in electrochemistry. For a reaction, A+B----------🡪 C+D

The change in Gibbs free energy change is given as,

ΔG =-nFE
Where, ΔG= Gibbs free energy, n = number of electrons transferred in the reaction, F = Faradays
constant (96,500 C/mol) and E= cell potential. Under standard conditions, the above equation
can be given as,

ΔGo = -nFEo
ΔG=ΔGo + RT lnKEq
(From Thermodynamic Gibbs free Energy Change)
-nFE = -nFE0 + RT lnKEq
nFE =nFE0 - RTlnKEq
E = E0 – (RT/nF) lnKEq
The above equation is known as the Nernst equation.
E = Eo − (2.303RT/nF) log10KEq (ln = 2.303 log10)

Applications of Nernst –Equation:

● It is applied for the determination of single electrode potentials.
E=E0-(0.059/n) log10 [Mn+]
● It is applied for the determination of EMF of cell (E-cell)
Consider Daniel cell Zn/Zn2+// Cu2+/Cu EMF of Cell = E RHS – E LHS
● Nernst equation is in determining ion concentration
● It is used in oxygen and the aquatic environment.
● It is also used in solubility products and potentiometric titrations.
● It is also used in pH measurements.

3. Reference Electrodes: The electrode of standard potential, with which we can compare
the potentials of another electrode, is called a “Reference Electrode”. The best “Primary reference

31
electrode” used as standard hydrogen electrode, whose electrode potential is taken as 0.00V. The
“Secondary reference electrode” used as saturated calomel electrode, whose electrode potential is
0.2422V.
1. Standard Hydrogen Electrode / Normal Hydrogen Electrode (SHE):

It is also known as primary reference electrode. Its value is taken as 0.00V.

Construction: It consists of a small Pt foil coated with Pt black which absorb H2 gas. A Pt wire
connected to Pt foil. The electrode is sealed in glass tube. The Pt foil is surrounded by outer glass
tube having an inlet at the top to pass H2 gas, and holes present at the base.
The electrode is placed in1M HCL solution. Pure H2 gas is passed at 1atm
through the inlet at the top. A small amount of the gas is absorbed by the Pt electrode, while the
remaining escapes through the lower holes provided at the base of the glass tube.

Working:
When this electrode act as anode following reaction takes place;
H2→2H++2e-
When the hydrogen electrode act as cathode following reaction takes place;
2H++2e-→H2
Thus hydrogen electrode is the reversible with respect to H+ ions.
This electrode is represented as : Pt, H2 (1atm)/H+ (1M)

Standard electrode potential of hydrogen electrode Eo cell is 0.0 ev ( E cell = E cathode – E anode )

2. Standard Calomel Electrode (SCE):

The standard calomel electrode is secondary reference electrode. Its value is

0.2422V.
It consists of mercury, solid mercurous chloride and potassium solution. Mercury is
placed at the bottom of a glass tube with a side tube on both sides.
It is connected to the outer circuit by means of a Pt wire sealed in a glass tube. The
surface mercury is covered with a paste of mercurous chloride (calomel).A saturated,
normal KCL solution is introduced through the side tube present in the right side
32
Working:
When it acts as anode: - (oxidation)
2Hg (l) → 2Hg++2e-
Then these ions combine with chloride ions
to form sparingly soluble mercurous chloride.
2Hg++2cl-→Hg2cl2
When it acts as Cathode: - (Reduction)
Hg2cl2 + 2e- → 2Hg +2cl-
Cell Representation:-
Pt,Hg/Hg2cl2/Kcl
Standard electrode potential of saturated calomel electrode is 0.2422 ev (E0 cell)

4. Galvanic series (or) Electro chemical series: When the metals are arranged in the order of
increasing reduction potentials (or) decreasing oxidation potentials which are determined with
respect to one molar solution of their ions and measured on the hydrogen scale, along series is
called electro chemical (or) galvanic series.
Element Electrode Standard Electrode
Reaction (Reduction) Reduction potential Eo, volt
Li Li+ + e- → Li -3.05
K K+ + e- → K -2.925
Ca Ca2+ + 2e- → Ca -2.87
Na Na+ + e- → Na -2.714
Mg Mg2+ + 2e- → Mg -2.37
Al Al + 3e → Al
3+ - -1.66
Zn Zn2+ + 2e- → Zn -0.7628
Cr Cr3+ + 3e- → Cr -0.74
Fe Fe2+ + 2e- → Fe -0.44
Cd Cd2+ + 2e- → Cd -0.403
Ni Ni + 2e → Ni
2+ - -0.25
Sn Sn2+ + 2e- → Sn -0.14
H2 2H+ + 2e- → H2 0.00
Cu Cu2+ + 2e- → Cu +0.337
I2 I2 + 2e- → 2I- +0.535
Ag Ag + e → Ag
+ - +0.799
Hg Hg2+ + 2e- → Hg +0.885
Br2 Br2 + 2e- → 2Br- +1.08

33
 Cl2 Cl2 + 2e- → 2Cl- +1.36
Au Au3+ + 3e- → Au +1.50
F2 F2 + 2e- → 2F- +2.87

Advantages:
* The higher a metal in the series, the greater is tendency to be oxidized.
The metals high up in the series are strong reducing agents, and their ions are stable than
metals. Whereas those metals near the bottom of the series are inactive & stable metals, their ions
are easily reduced to metals (i.e. the lower a metal in the series, the greater is the tendency to be
reduced).
Ex: Zn oxidizes to Zn2+ and Zn reduces the Cu2+ to Cu.
*In the series any metal above the hydrogen will displace H2 gas from dilute acid.
Ex: Na reacts with water to liberate hydrogen, because the E0 (Na+/Na) = -2.714 V is less than E0H+/H2
= 0.
Any metal below the hydrogen in the series will be reduced by hydrogen.
*The metals above the hydrogen in the series can easily displace the metal from its
salt solution. Because E0 (Zn+2/Zn) = -0.763 V is less than E0Cu+2/Cu = 0.337V.
Ex: Zn + CuSO4 --------------🡪 ZnSO4 + Cu
Applications of Electro Chemical Series:
⮚ The relative corrosion tendencies of the metals and alloys.
⮚ Relative case of oxidation (or) reduction of metals.
⮚ Replacement tendency of metals. Predicting spontaneity of redox reactions.
⮚ Calculating the equilibrium constant as given below.
2.303 𝑅𝑇 𝑛𝐹𝐸
𝐸0 = 𝑙𝑜𝑔Keq Log Keq = 2.303 𝑅𝑇 at 250c R = 8.314 J mol-1K-1
𝑛𝐹

CONCENTRATION CELLS
In concentration cells, the EMF arises because of a difference in the concentration of the
species involved. Concentration cells are of two types. (a)Electrode concentration cell.
(b)Electrolyte concentration cell.
a) Electrode concentration cell In these cells, two same electrodes at different
concentration are dipping in the same solution. Two hydrogen electrodes at unequal gas pressure
immersed in the same solution of hydrogen ions constitute an electrode-concentration cell.
This may be represented by Pt, H2 / H+ // H+ / H2, Pt

b) Electrolyte concentration cells

In these cells, both the electrodes are of the same metal (Zn) and these are in contact with
solutions of the same ions (Zn2+ ). The concentrations and hence activities of the ions are,
however different.
Let (a1) and (a2) be the activities of zinc ions in the two electrolytes surrounding the electrodes.
One such cell is represented as Zn / Zn +2 // Zn +2 / Zn

34
 C1 C2

Ecell= 0.0591/n log(C2/C1)

Batteries
Introduction:

A device which converts a chemical energy to electrical energy is called battery, a group
of two (or) more electrical cells, connected together electrically in series are called battery.
Batteries are commercial electrochemical cells.

Requirements for Batteries:

⮚ High capacity, which is small variation of voltage during discharge.
⮚ High energy efficiency.
⮚ % of efficiency = energy released on discharge/energy required for charge X 100
⮚ High cycle life is required which is the number of charging and discharging cycles before
failure.
⮚ Long life is required.

Batteries are classified into 3 types.

1. Primary batteries.
2. Secondary batteries.
5. Primary batteries:

35
 The cells in which the cell reaction is not reversible, thus when the reactants have
been converted to products, no electricity is produced and the cell becomes dead and after that
cannot be used. The batteries are used as a source of dc power.
* Leclanche Cell (Or) Zinc – Carbon Cells (Or) Dry Cell:

⮚ Dry (Or) Leclanche Cell. I.e. A Cell Without Fluid Component Is A Primary Cell.
⮚ Zinc Container acts as anode Containing an Electrolyte NH4Cl, Zncl2 &Mno2 in paste
form, and Starch Is Added to Prevent Leakages.
⮚ A Carbon (Graphite) Rod acts as A Cathode.
⮚ The Zinc Anode Of The Cell Is Shaped Into Cylindrical Container Containing the
Pasty Electrolyte Into Which A Carbon (Graphite) Rod Is Immersed At The Centre.

Cell representation: Zn/Zncl2, NH4Cl // Mno2/C

Anode: Zn container. A thin zinc cylinder serves as anode and it undergo oxidation.
Zn → Zn2+. + 2e-

Cathode: Graphite rod act as cathode, the reduction reaction occurs within the moist paste.
2MnO2 +2 H2O + 2 e- → Mn2O3 +2 OH-

Electrolyte: A paste of NH4Cl and Zncl2

The OH- generated in the above reaction causes further secondary reactions
NH4Cl+OH- → NH3+Cl-+H20
ZnCl2+NH3+Cl- → [Zn (NH3)2]Cl2
The EMF of cell is 1.5V

Applications: Dry cells are used in radios, watches, torch lights, telephones, door bells etc.
*Lithium ion Cells :
Rechargeable Li - cells

36
 Lithium ion cells belong to secondary cells. The cells having lithium anodes
are lithium cells, irrespective of the cathode used. Lithium cells can be classified into
following.
Liquid Cathode Lithium (Li – Ion) Cells:
⮚ Anode: Li
⮚ Cathode: SOCl2
⮚ Electrolyte: LiAlCl2
The reactions of the cell are:

Reaction at anode: 4 Li→4 Li+ +4 e-

Reaction at cathode:
4Li++4 e-+2SOCl2→ 4 LiCl + SO2+S
Net reaction: 4 Li +2SOCl2 → 4LiCl + SO2+S

Due to nature of reaction lithium thionyl chloride cell possess very high energy density. The
reaction involves to electrons per thionyl chloride. Further the SO2 liberated as product is a liquid
under the internal pressure of the cell. No CO- solvent is required for the solution as thionyl chloride
is a liquid having moderate vapor pressure; the discharging voltage is 3.3 to 3.5 volts.

Applications:
⮚ Li – SOCl2 cells are used on electronic circuit board for supplying fixed voltage for memory
protection and other stand by functions.
⮚ These cells are also used for military space applications.
⮚ These cells are also used in medical devices such as neuro stimulators, drug -delivery
systems.

Solid Cathode Lithium Cells: (Non rechargeable cells)

⮚ The systems may have solid (or) liquid electrolyte. Lithium – manganese dioxide (Li –
MnO2) is emerging as most widely used 3V solid cathode in lithium primary battery.
⮚ The cathode MnO2 should be heated to >3000C to remove water before incorporating it in
the cathode.
⮚ It is very important to improve the efficiency of the cells.
⮚ Anode: Li
⮚ Cathode: Heated- treated MnO2
⮚ Electrolyte: A mixture of propylene carbonate and 1, 2 di-methoxy
ethane
⮚ Reaction at anode: Li→ Li+ + e-
⮚ Reaction at cathode: Li++ e-+MnO2 → LiMnO2
⮚ Net reaction: Li + MnO2 → LiMnO2
Applications:

37
 ⮚ The cylindrical cells are used in fully automatic cameras.
⮚ These cells are widely used in electronic devices such as calculators and watch.
6. Secondary Batteries /Storage Cells:
The cells in which the cell reaction is reversed by
passing direct current in opposite direction. These cells are rechargeable and reusable. The
secondary batteries can be used through a large number of cycles of discharging.
A combination of all reversible electro chemical cells
gives secondary batteries. For example lead acid storage cells, Nickel- Cadmium are widely used
as storage cells.

*Lead – Acid Storage Cell

(Lead Storage Battery):
The cell in which original reactants are
regenerated by passing direct current from external source, i.e., it is re-charged, is called secondary
cell. Lead storage battery is the example of this type.
⮚ A storage cell that can operate both as a voltaic cell and as an electrolytic cell.
⮚ In this cell sponge metallic lead is anode and lead dioxide (PbO2) is a cathode.
❖ Construction:
It consists of a group of lead plates (-Ve plates) bearing compressed spongy
lead, alternating with a group of lead plates bearing lead dioxide, PbO2. These plates are immersed
in a solution of about 20% H2SO4.
Pb (anode)

PbO2 (cathode)

⮚ Anode: Pb 20%H2SO4
⮚ Cathode: Pb coated with Pbo2
⮚ Electrolyte: 20% solution of H2SO4
⮚ Cell representation: Pb/PbSO4(s),H2SO4,Pbo2/Pb

The electrolyte is dissociated as, H2SO4→2H++SO42-

❖ Discharging:
When the storage cell is operating as a voltaic cell (i.e. chemical energy into
electrical energy). It is said to be discharging. The lead electrode loses e-s, which flow through the
wire
Pb -------> Pb2+ + 2e- (Anode reaction)

38
 Pb2+ ions combine with sulphate ions to form insoluble lead sulphate, PbSO4, which begins to
coat lead electrode
Pb2+ + SO42- --------->PbSO4 (Precipitation)
Complete Anode Reaction: Pb + SO42- PbSO4 + 2e- (Anode reaction)

The e- released from the anode (lead plate-Pb) flows to the cathode (lead dioxide- PbO2). Here
PbO2 gains e-s to form Pb2+ ions.
PbO2 + 4H+ + 2e- ---
Pb2+ + 2H2O
Pb2+ + SO42- PbSO4 (Cathode reaction)

Overall cell reaction: Pb + PbO2 + 4H+ + 2 SO42- 2PbSO4 + 2H2O + energy

It may be noted that lead sulphate (PbSO4) is precipitated at both the

electrodes. The voltage of each cell is about 2V at a concentration of 21.4% H2SO4 at 250C. Lead
commonly used in automobiles is a combination of six such cells in series to form a battery with
an emf of 12V.
❖ Charging:
When both anode and cathode become covered with PbSO4, the cell ceases to
function as a voltaic cell. To recharge a lad storage cell, the reactions taking place during
discharging are reversed by passing an external emf greater than 2 volts from a generator.
Reaction at anode:
PbSO4 + 2H2O + energy PbO2 + 4H+ + SO42- +2 e-
Reaction at cathode:
PbSO4 +2e- Pb + SO42-
Net reaction during charging is
2PbSO4 + 2H2O + energy Pb + PbO2 + 4H+ + 2 SO42-
Ecell is 2.041 volt.
During the process of charging, the electrodes of the cell are restored to their
original conditions (i.e. Pb and PbO2 respectively). It may also be noted that during discharging
operation, the concentration of H2SO4 decreases, while concentration of acid increases during the
charging operation.
❖ Applications of Lead – Acid Storage Battery:
The lead acid storage cells are used to supply current for
electrical vehicles, gas engine ignition. In telephone exchanges, electric trains, mines,
laboratories, hospitals, broad casting stations, automobiles, power stations.
❖ Advantages of Lead Batteries:
☞ The lead acid storage battery is both a voltaic cell and electrolytic cell. When electricity
is being drawn from the cell, to start the car it acts as voltaic cell, when the car is running the cell
is being recharged as electrolytic cell.
☞ It has relatively constant potential i.e. 12V
☞ It is portable and cheap.
*Nickel – Cadmium Cells:

⮚ Anode: Cd

39
 ⮚ Cathode: Nickel oxy hydroxide ( NiO(OH))
⮚ Electrolyte: KOH

The battery consists of a cadmium anode (-Ve electrode) and a

cathode is a composed paste of NiO (OH) ((+Ve electrode). Electrolyte is KOH.

❖ Discharging:
Reaction at anode: Cd(S) + 2OH- -------------🡪 Cd(OH)2 + 2e-
Reaction at cathode:
2 NiO (OH) +2H2O +2 e- ---------------🡪2Ni (OH) 2 + 2 OH-
Net reaction:
2 NiOOH +Cd+2H2O -------------------🡪 Cd(OH)2+ 2Ni(OH)2

This reaction can be readily reversed, because the reaction products

Ni (OH) 2 and Cd (OH)2 adhere to the electrode surfaces.

❖ Charging:
Reaction at cathode: Cd(OH)2 + 2 e- ---------🡪 Cd +2OH-
Reaction at anode:
2Ni (OH)2 + 2 OH- -----------🡪 2 NiO(OH) +2H2O +2e-
Net reaction: Cd(OH)2 + 2Ni(OH)2 +2 OH- --------------🡪 2 NiO(OH) + Cd
+ 2H2O
Emf of the cell is 1.4V
❖ Applications:
It is used in electronic calculators, electronic flash units, cordless electronic
shavers, transistors and other battery pored small tools.
Corrosion
Introduction: The gradual disintegration of a metal due to chemical or electrochemical attacking
in its environment “is known as corrosion.
Eg: Yellow rust, actually corresponds to Fe2O3. 3H2O on the surface of iron.
Greenish layer formation on the surface of Copper.

*Causes of corrosion: The metals exist in nature in the form of their minerals or ores, in the
stable combined forms as oxides, chlorides, silicates, carbonates, sulphides etc.
During the extraction of metals, these ores are reduced to metallic state by
supplying considerable amounts of energy. Hence the isolated pure metals are regarded as excited
states than their corresponding ores. So metals have natural tendency to go back to their combined
state (minerals/ores).

When metal is exposed to atmospheric gases, moisture, liquids etc., the metal surface
reacts
and forms more thermodynamically stabled compounds.

40
 E.g.: Rusting of iron when exposed to atmospheric conditions. Rust is hydrated oxide
(Fe2O3.xH2O).

7. Theories of corrosion: There are two theories of corrosion:

I. Chemical corrosion (Dry Corrosion)
II. Galvanic or electrochemical or wet corrosion.

I. Chemical corrosion (Dry Corrosion)

The gradual disintegration of a metallic material by direct attacking of chemical through its dry
atmosphere is called dry corrosion .
There are three main types of dry corrosion.

(I) Oxidation corrosion (Reaction with oxygen): Some of the metals directly react with oxygen
in the absence of moisture. Alkali and alkaline earth metals react with oxygen at room
temperature and form corresponding oxides, while some metals react with oxygen at higher
temperature. Metals like Ag, Au and Pt are not oxidized as they are noble metal.

During oxidation of a metal, metal oxide is formed as a thin film on the metallic surface which
protects the metal from further corrosion. If diffusion of either oxygen or metal is across this
layer, further corrosion is possible. Thus, the layer of metal oxide plays an important role in the
process of corrosion.

⮚ Oxides of Pb, Al and Sn are stable and hence inhibit further corrosion. They form a stable,
tightly adhering oxide film.
⮚ In case of porous oxide film, atmospheric gases pass through the pores and react with the
metal and the process of corrosion continues to occur till the entire metal is converted into
oxide. Porous oxide layer is formed by alkali and alkaline earth metal.
⮚ Molybdenum forms a volatile oxide film of MoO3 which accelerates corrosion.
⮚ Au, Ag, Pt form unstable oxide layer which decomposes soon after the formation, thereby
preventing further corrosion.

41
Pilling Bed worth Rule: The protective or non protective nature of metal oxide film is determined
by ratio of volume of metal oxide formed on the surface to the volume of metal consumed is
called pilling Bed worth ratio.

Pilling Bed worth Ratio = the volume of metal oxide formed on the surface / the volume of metal
consumed is called pilling Bed worth ratio.
According to this rule,
If volume of metal oxide on the surface of a metal is more than or equal to the volume
of metal, the oxide layer will be protective. The metal oxide will be protective and non porous.
For example, for Al2O3, Fe, Ni, Zn, W, Cr forms.
If volume of Metal oxide is less than volume of metal. The metal oxide will be non protective
and porous.

(ii) Corrosion by other gases such as Cl2, SO2, H2S, and NOx: In dry atmosphere, these gases
react with metal and form corrosion products which may be protective or non-protective. Dry Cl2
reacts with Ag and forms AgCl which is a protective layer, while SnCl4 is volatile. In petroleum
industries at high temperatures, H2S attacks steel forming FeS scale which is porous and interferes
with normal operations.

(iii) Liquid metal corrosion: In several industries, molten metal passes through metallic pipes
and causes corrosion due to dissolution or due to internal penetration. For example, liquid metal
mercury dissolves most metals by forming amalgams, thereby corroding them.

II. Electrochemical or wet corrosion: The gradual disintegration of a metallic material by direct
attacking of Electro chemical through its wet atmosphere is called wet or electro chemical
corrosion .
This type of corrosion occurs when the metal comes in contact with a conducting liquid or
when two dissimilar metals are immersed or dipped partly in a solution. According to this theory,
there is the formation of a galvanic cell on the surface of metals. Some parts of the metal surface
act as anode and rest act as cathode. The chemical in the environment and humidity acts as an
electrolyte. Oxidation of anodic part takes place and it results in corrosion at anode, while
reduction takes place at cathode. The corrosion product is formed on the surface of the metal
between anode and cathode.

To understand the wet theory, let us take the example of corrosion of iron. Oxidation of metal
takes place at anode while the reduction process takes place at cathode. By taking rusting of iron
as an example,
At anode: iron undergoes oxidation.

The reduction reaction can be of two types (i) evolution of hydrogen and (ii) absorption of
oxygen.
At cathode:
❖ Case I: Evolution of H2

42
 The hydrogen ions (H+) are formed due to the acidic environment and the following
reaction occurs in the absence of oxygen.
2H+ + 2e→ H2 ↑ (reduction)
The overall reaction: Fe + 2H+→ Fe+2 + H2
In this case, metals react in the acidic environment and are dissolved
(undergo corrosion) to release H2 gas. All metals above hydrogen in electrochemical series can
show this type of corrosion. In hydrogen evolution type of corrosion, anodic area is large as
compared to its Cathodic area.

❖ Case II: Absorption of O2

This type of corrosion takes place in neutral or basic medium in the presence of
oxygen. The oxide of iron covers the surface of the iron.

The following chemical reactions occur at anode and cathode.

At anode Fe → Fe2+ + 2e¯ (oxidation)
At cathode 1/2O2+H2O+2e¯ → 2OH-(Reduction)

Net reaction Fe +1/2 O2+H2O → Fe2++ 2OH- (or) Fe(OH)2

Ferric hydroxide is actually hydrated ferric oxide, Fe2O3.H2O, which is yellowish rust.

Fe (OH)2+O2+H2O→Fe (OH)3 or Fe2O3.H2O

8. Type’s of corrosion:
There are different types of corrosions based on the reactions and physical states.
They are: (I) Galvanic Corrosion.
(II) Differential aeration Corrosion.

43
(I)Galvanic corrosion: This type of electrochemical corrosion is also called bimetallic corrosion.
When two dissimilar metals are connected and exposed to an electrolyte, they will form a
galvanic cell. The anodic metal will be oxidized and it will undergo corrosion.
E.g., Zinc and copper metals connected with each other in an electrolyte medium
form a galvanic cell. Zinc acts as anode and undergoes corrosion while cathode will be
unaffected.

At anode:
Zn→ Zn2+ +2e– [Oxidation] corrosion
At cathode:
1/2O2+H2O+ 2e–--->2OH-[Reduction] unaffected

(II) Differential aeration corrosion: If a metal rod is dipped in an electrolyte, the portion dipped
in water is poor in oxygen concentration and act as anode which gets corroded and the portion
above water acts as cathode which is protected.

(III) Stress corrosion:

In a metallic structure, if there is a portion under stress, it will act as anode and rest
part of the structure will act as cathode. It is now a galvanic system and hence anodic part which
is small in area will corrode more. Stress corrosions are observed in the following systems:

44
⮚ Caustic embrittlement is a type of stress corrosion occurring in steel tank (Boiler) at high
temperature and in alkaline medium. Boiler water has Na2CO3; it will be hydrolyzed at high
temperature to give NaOH. It flows into hair cracks and crevices. There it reacts with iron
and forms Na2FeO2 (sodium ferroate) which decomposes to give Fe3O4 (Ferric oxide) and
NaOH.
3Na2FeO2 + 3H2O 🡪 Fe3O4 + H2 + 6NaOH
NaOH thus formed further reacts with iron to cause corrosion. It is called caustic
embrittlement.

10. Corrosion control methods – (a) selection rules

Due to corrosion, there is a great loss of material and money. Therefore, it

is essential to protect metals from corrosion. Since, there are two components involved in
corrosion the metal and environment both are considered in corrosion protection. Following
methods have been adopted for the protection of metal from corrosion.
(i) Proper designing of an object helps in prevention of corrosion.
(ii) Contact of two dissimilar metals must be avoided
(iii) Two different metals used in the structure should be such that they are occupying near
positions in galvanic series.
(iv) Putting an insulator between two metals resists corrosion.
(V) As far as possible, metal used in a structure should be extremely pure. Small amount of
impurity causes corrosion.
(vi) While using an alloy, it should be completely homogeneous.
Corrosion can be prevented by 1) Cathodic Protection 2) Surface coatings
1. Cathodic Protection:
The Cathodic protection of metals is used to control corrosion metals. The principle
involved in this method is to protect metals and alloys from corrosion by making them completely
Cathodic.
The following are two types of cathodic protections.
1. Sacrificial anodic protection
2. Impressed current cathodic protection
*Sacrificial anodic protection:
In this method, the metal structure can be protected from corrosion by connecting it with wire to a
more anodic metal so that all the corrosion is concentrated at this more anodic metal. The more
anodic metal itself gets corroded slowly, while the parent structure (Cathodic) is protected. The
more active metal so employed is called sacrificial anode. The corroded sacrificial anode is

45
replaced by a fresh one, when consumed completely. The metals which are commonly used as
sacrificial anodes are Mg, Zn, Al and their alloys. The important applications of this method are

1. Protection of underground cables and pipelines from soil corrosion.

2. Protection of ships and boat hulls from marine corrosion.
3. Prevention of rusty water by inserting Mg sheets or rods into domestic water boilers or tanks

.
* Impressed current Cathodic protection: In this method current from an external source is
impressed (applied in the opposite direction) to nullify the corrosion current. This is done to
convert corroding metal from anode to cathode. Once the metal become Cathodic it is protected
from corrosion. The anode may be either inert material or active material. The anodic materials
are Platinum, Graphite, Stainless steel, etc. The anode is buried in Backfill such as Gypsum to
increase the electrical contact between itself and surrounding soil.

This protection method is well suited for large structure such as buried pipe lines, tanks, marine
pipes etc.

2) Surface Coatings: Iron and steel structures can be protected from corrosion by covering thier
surfaces with metallic coatings. The metallic coatings often used are Zn , Al , Tin , Cu , Cd , Cr
etc ., these coatings separate the base metal from corrosive environment and also functions as an
effective barrier for the protection of base metal .

46
 Types of Surface coatings:

* Anodic coatings: In these coatings the metal which is used for coating is more anodic than
the metal which is to be protected. Anodic coatings protect the underlying base metal sacrificially.
Example: coating of zinc on steel surface is called galvanizing.

*Cathode coatings: These coatings protects the underlying base metal due to thier noble
character and high corrosion resistance
Example: coating of Tin over the iron or steel articles is called tinning
Methods for applications of Metallic coatings:

* Hot dipping: It is the process of coating of low melting point metals on the surface of high
melting point materials like iron, steel. This is of two types:-

*Galvanizing: It is the process of coating of Zinc on the surface of iron or steel. In this
process iron or steel is first cleaned by acid picking with dil.H2SO4 for 15-20 minutes and 60-90°
c. The article is then washed with water and dries in a dry chamber. It is then dipped in bath of
molten Zinc at 425-430°c. The surface of the bath is kept covered with NH3Cl flux to prevent
oxide formation. When the article is taken out, the article is coated with a thin layer of Zinc. It is
then passed through a pair of hot rollers. This process removes any excess of Zinc on the articles.

Uses: It is widely used for protection of iron and steel from atmospheric corrosion in the
form of roofing sheets, wires, pipes, screws, buckets, sheets. Zinc dissolved in dil. Acids to form
highly toxic compounds. Hence Galvanized utensil cannot be used for storing of food stuff.

* Tinning: It is coating of Tin over the iron or steel articles. In this process first treating steel
sheet in Dil.H2SO4 to remove any oxide film after this it is passed through a bath of molten tin. It
is covered by a Zncl2 flux. This flux helps the molten metal to adhere on the metal sheet and helps
to prevent oxidation of molten tin. Finally the metal sheets passed through a series of rollers from
underneath the surface of a layer of palm oil. The palm oil protects the hard tin coated surface
again. The rollers remove any excess of tin and produce a tin film of uniform thickness on the
steel sheet.

Uses:
1) Tin coated iron or steel articles are used for storing and preparing of food stuffs.

47
 2) It is most widely used for protection of iron or steel from atmospheric corrosion in the
form of roofing sheets, pipes, etc.
11. Electroplating: It is the process of coating of base metal by a dense homogeneous layer of a
coating material by passing a direct current through electrolytic solution consists of soluble salts
of coating metal. Or

Coating of a metallic material with another metal in presence of electric current is called electro
plating

Process: It is an electrochemical process in which a base metal is coated by Zn, Ag, Cr, Au, Sn,
etc. To protect it from corrosion
and also to make it shining and
decorative. The base metal is made
cathode, dipped in a suitable
electrolyte, and the metal to be
deposited is made the anode. Anodized
coating is done for non-ferrous metals,
such as Zn, Mg and Al.

Reactions takes place at anode M--------> M+n. +n elec

Reaction takes place at cathode

M+n +n ele-------> M deposited on cathode

12. Electroless Plating:

Definition: The process of producing a thin, uniform and hard deposit of metal on an
activated substrate (Metal or non-metal) by using suitable soluble reducing agents without any
electrical energy is called electro less plating.

The reducing agent reduces the metallic ions to metal, which gets plated over the catalytically
activated surface giving a uniform thin coating.

Metal ions + Reducing agent →Metal + Oxidized products

Process:
The process involves
1. Pretreatment or activation of work piece to be plated.
2. Preparation of bath composition.
* Electroless Plating of Nickel:

The base objects, a plastic material like acrylonitrile-butadiene styrene (ABS) can be coated
with nickel.

The base metal surface is activated by stannous chloride followed by palladium chloride
to get a layer of pd and the surface is dried and dipped in a solution of nickel chloride, sodium
hyposulphite (reducing agent), sodium acetate buffer, sodium succinate (complexing agent) pH

48
of the bath maintained is 4.5 and temperature maintained is 93oc. the following reaction take
place and Ni get plated electrolessly on the surface of the base object.

Ni2+ + H2PO2- +H2O ----🡪 Ni + H2PO3 + 2H+

Application:-

Electroless Ni coating are used extensively in electronic application providing a

non magnetic underlay in magnetic components.

* Electroless Plating of copper:

The printed circuit boards, plastics and glasses are used as base objects
and treated by Stannous Chloride & Palladium Chloride and electroplated through hole technique.

The solution made up of copper sulphate, formaldehyde (Reducing

Agents), Sodium hydroxide and Rochelle salt (Buffer), EDTA (complexing Agent).

The PH of the bath solution is 11 and temperature maintained is 250C.

The Overall Reaction is:

Cu2+ + 2HCHO + 4 OH- HCOO + 2H2O + Cu (Electroplated on the base

object)

Application: Cu Electroless plating is used for making printed circuit boards.

F SCIENCE

49
 UNIT 3 STEREOCHEMISTRY
Stereochemistry:-

The same molecular formula and sequence of bonded atoms (constitution) but differ in
the three-dimensional orientations of their atoms in space.

It is also known as 3D chemistry the prefix "stereo-" means "three-dimensionality".

An important branch of stereochemistry is the study of chiral molecules.

Stereochemistry spans the entire spectrum

of organic, inorganic, biological, physical chemistry.

50
ISOMERISM

Isomers are compounds having same molecular formula but differ in physical or
chemical or both physical and chemical properties. This phenomenon is known as isomerism.
Isomerism is of two types –

(i) Structural isomerism

(ii) Stereoisomerism.

i) Structural isomerism arises out of the difference in the arrangement of atoms in a molecule,
(without referring to space), type of linkage and the atoms which are linked to each other in the
molecule.

Ii) Stereoisomerism arises out of the difference in the arrangement of atoms in the molecule, with
reference to each other in space. Stereo isomers (have the same structure) differ in the way the
atoms are oriented in space. They have the same structure and hence do not differ much in
properties.

Two types of Stereoisomerism.

(i) Geometrical isomerism

(ii) Optical isomerism.
(i) Geometrical Isomerism :

Isomerism that arises out of difference in the spatial arrangement of atoms or

groups about the doubly bonded carbon atoms is called Geometrical isomerism. These isomers
are not mirror images of each other. Rotation about C=C is not possible at normal conditions and
hence the isomers are isolable. If different atoms or groups are bonded to the ‘C=C’ bond in a
molecule, more than one spatial arrangement is possible. For example, 2-butene exists in two
isomeric forms.

51
The isomer in which similar groups lie on the same side is called ‘cis isomer’ (I). The other in
which similar groups lie in opposite direction is called ‘Trans isomer’ (II). This isomerism is
called ‘Cis-Trans’ isomerism. The two groups attached to the carbon atoms need not be same, it
may be different also.

This isomerism arises out of the hindrance to rotation about the C=C bond in
such molecules. The cis-trans isomers do not differ much in chemical properties. They differ in
physical properties like boiling point, melting point, crystal structure, solubility and refractive
index. Highly substituted olefin is more stable than less substituted olefin. Among substituted
olefins, Trans olefin is more stable than cis olefin. In the cis isomer because similar groups are
very near each other, Vander Waals repulsion and steric hindrance make the molecule much
unstable.

In the trans isomer, similar groups are diagonally opposite to each other. Hence
there is no such steric interaction. Generally trans isomer is more stable than cis isomer. Hence
reactivity of cis isomer may be little higher than the trans isomer. The energy of the cis isomer is
greater than that of trans isomer. Though at room temperature, cis and trans isomers are stable and
are not inter convertible, on heating to a certain temperature, trans isomer can be converted to cis
isomer and vice-versa. ‘Breaking of carbon-carbon p-bond and its reformation is responsible for
the inter conversion.’

Consider unsaturated dicarboxylic acid - Maleic acid and Fumaric acid. These are geometrical
isomers.

52
‘Cis-trans’ system of nomenclature may not be suitable for many substituted olefins.

A newer system based on the priority of groups is the Cahn-Ingold- Prelog

convention. This system is called the (E-Z) system, applies to alkene diastereomers of all type. If
the two groups of higher priority are on the same side of the double bond, the alkene is designated
‘Z’ (from the German word Zusammen-meaning together). If the two groups of high priority are
on opposite sides of the double bond, the alkene is designated ‘E’ (from the German, entgegen,
meaning opposite) The priorities follow the order of decreasing atomic number of the atom directly
bonded to the carbon.

For some compounds the priority is shown by numbers as

Dipolemoment studies is one of the best methods of identifying cistrans isomers. Generally cis
isomers have larger dipolemoment than trans isomers. Often DPM of trans isomer is zero. e.g.,
Trans 2-butene and Trans 2,3-dibromo-2-butene. (Refer Chapter on disubstituted benzene)

53
Geometrical isomerism of 1,3 - butadiene

This molecule can exist in two forms.

Though these two forms do not differ very much in their energy and stability, the (I) form,
which is similar to ‘trans’ is more stable than (II) form which is similar to ‘cis’. These two forms
do not arise out of the hindrance to rotation about C=C, instead the restricted rotation about C–C.
In order to indicate that, this cis-trans isomerism is due to restricted rotation about C–C bond, they
are named as,

These are easily interconvertible and exist in equilibrium.

S-trans form is also called ‘transoid form’ S-cis form is also called ‘cisoid form’. The
energy of S-trans form is 3 Kcals less than the S-cis form. These two forms differ in chemical
reactivity. Very often they give different products in reactions.
Conformation analysis of n-Butane
In the case of ethane, conformational changes are very subtle, but in others they are more obvious.
Butane (CH3CH2CH2CH3) has four tetrahedral carbons and three carbon-carbon bonds connecting
them together. Let's number the carbons along the chain C1, C2, C3 and C4. Rotating around the
C-C bonds connected to the terminal carbons -- C1-C2 and C3-C4 -- only subtle changes in shape
would be apparent. However, rotating about C2-C3 produces some pretty obvious shape changes.
Pay attention to where the two methyl groups are with respect to each other. If we call C1-C2-C3-
C4 the dihedral angle, then at 0 degrees the molecule is in an eclipsed conformation, apparent
when looking at the Newman projection. Looked at from other vantage points, the molecule is
curled up into the shape of a letter C.

54
 Figure CA3.2. Newman projection of butane in the "least-stable eclipsed" conformation.

Figure CA3.4. Newman projection of butane in the "gauche" conformation.

At 120 degrees the molecule is eclipsed again , but from the side it has now twisted almost into a
shape like the letter Z. It is clearly different from the other eclipsed conformation. This one is a
little more stable than the other eclipsed conformation, for reasons that we will look into shortly. It
is called the "more stable eclipsed conformation".

Figure CA3.6. Newman projection of butane in the "more-stable eclipsed" conformation.

The "least stable eclipsed" conformation is described that way because there are two different
eclipsed conformations; we will see the other one soon. Of the two eclipsed conformations, this
one is less stable than the other one. In an eclipsed conformation, bonds coming from two
neighbouring atoms are lined up with each other. The dihedral angle between these bonds -- the
C1-C2 bond and the C3-C4 bond in the case of butane's least stable eclipsed conformation -- is 0
°. That situation introduces torsional strain. As a result, neither one of these eclipsed
conformations is very stable.
At 60 degrees, the molecule is no longer eclipsed, and just as in ethane the energy is a little bit
lower, but the overall shape when viewed from the side is still a sort of twisted C. This shape is
one of two possible staggered conformations, in which there is no torsional strain.

55
At 180 degrees, the molecule is staggered again and has settled into a regular, zig-zag, letter Z
shape. There is no torsional strain, so this is one of the more stable shapes that the molecule can
adopt. However, it is not the same shape as the other staggered conformer (the one we called
"gauche"). This one is called the "anti" conformer.

Figure CA3.8. Newman projection of butane in the "anti" conformation.

These conformations of butane are really pretty different. Which shape would the molecule prefer?
From what we learned about ethane, we could probably rule out the eclipsed conformations. Each
of those would have 3 kcal/mol of torsional strain.

However, there is another factor that destabilizes the initial conformation at 0 degrees, in favour
of the Z-shaped one with the methyl groups 180 degrees apart from each other. This factor is called
"sterics" and it refers to the idea that molecules, or parts of molecules, take up space, and so two
parts of the butane can't occupy the same place at the same time. Put more simply, sterics refers to
crowdedness. When the two methyl groups in butane are too close together, they are too crowded,
and they are at higher energy. When they get farther apart, crowding subsides and the energy in
the molecule goes down.

● Torsional strain forces bonds on neighbouring carbons to be staggered.

● Steric strain forces groups away from each other to relieve crowding.
● Torsion and sterics both contribute to strain energy.
● Strain can be released by getting the molecule in a lower energy conformation.

For butane, that means getting those two methyl groups away from each other and keeping the
bonds staggered.

There is some additional jargon that is used to describe these butane conformations:

● In an anti conformer, the largest groups are 1800 from each other.
● In a gauche conformer, the bonds are staggered but the largest groups are 60 0 from each
other.

56
Because of different steric interactions, the most stable conformer is the anti conformer. The
second-most stable conformer is the gauche conformer. The other shapes we have looked at, the
two eclipsed conformations, are not very stable at all. At room temperature, a bottle of butane gas
has enough energy that the individual molecules can allow their bonds to spin around, sampling
different shapes. However, at any given time, most of the molecules will be found in the anti
conformer, because each of those molecules will spend most of its time in the most stable
conformation. Some of the molecules will be found in the gauche conformer, because that is the
second-most stable conformation. None of the molecules will be found in the eclipsed
conformations, because those are points of maximum energy. The molecules have enough energy
to rock back and forth a little bit, and sometimes they will not rotate all the way through an eclipsed
conformation, but they won't stop there. Instead, they will keep rotating until they get to another
staggered conformer.

● A butane molecule spends most of its time in the anti conformer.

● A butane molecule spends some of its time in the gauche conformer.
● A butane molecule spends almost noe of its time in eclipsed conformations.

Optical activity and optical isomerism:

Light is propagated in the form of waves. Ordinary monochromatic light is supposed to
consist of waves vibrating in all planes. If such a light is passed through a Nicol prism, the
emergent light is found to consist of waves vibrating in only one plane. Such a light is called plane
polarised light.

When the plane polarised light is passed through certain substances or solutions (such as
lactic acid), the emergent light is found to be vibrating in a different plane. This is called optical
rotation.

57
 Such substances are called optically active substances. This property of such substances is
called ‘Optical activity’. If the rotation is towards the right side [clockwise] it is called
dextrorotation and the substance is said to be dextrorotatory. Dextrorotation is indicated by the
symbol (+) or ‘d’. If the rotation is towards the left side [Anticlockwise] it is called laevorotation
and the substance is said to be laevo rotatory. Laevorotation is indicated by the symbol (–) or ‘l’.
Conditions of optical activity :
Not all substances are optically active. For example substances like CHCl3, CH3CH2OH,
CH3CH2CH=CH2, CH3CH2COCH3 are not optically active. On the other hand substances like
CHIBrCl, CH3CHBr–CH=CH2, CH3CH (OH) COCH3, CH3CHDOH is found to be optically
active.
When the structures of the compounds which are optically inactive and optically active,
are compared, one thing is clear. All the optically active compounds, mentioned above have at
least one carbon atom that is bonded to four different atoms or groups.
A carbon atom attached to four different atoms or groups is called ‘‘asymmetric carbon
atom’’.
Pasteur suggested that optical activity arises from molecular dissymmetry which is
supported by Vant-Hoff and LeBel. According to them, a carbon atom has its four valencies
directed towards the four corners of a regular tetrahedron. In this situation a molecule with an
‘asymmetric carbon atom’ becomes asymmetric.
It so happens that an asymmetric molecule is not superimposable on its mirror image. That
means an optically active molecule has more than [atleast two] one configuration. [configuration
refer to three dimensional arrangement of atoms in a molecule] that is, an optically active molecule
exhibits isomerism which is called optical isomerism.
Consider ethanol and deuterated ethanol

58
 The isomers-called optical isomers have configurations which are non super imposable.
Hence the criteria for a molecule to be asymmetric (hence optically active) is that its
configuration is non super imposable on its mirror image. Such molecules are also called ‘chiral’
molecules.
‘Chirality’ is ‘the essential and the sufficient’ condition for a molecule to be optically
active.
Chirality means handedness or non superimposability. Right hand and left hand, Right leg
shoe and left leg shoe are examples of objects having handedness or the property of Chirality and
non superimposability.
The molecules which are optically inactive are ‘achiral’.
Simple optically active molecules like lactic acid, are said to have ‘‘chiral carbon’’ or
‘‘chiral center’’.

The carbon with ‘‘astreik’’ is called the chiral carbon.

All the a-amino acids (except glycine) have chiral centres (chiral carbon) and are optically
active.

Optical isomers:
Chiral molecules can have two different configurations. Each configuration stands for one
optical isomer. Thus dextrorotatory isomer has configuration which is the mirror image of the
laevorotatory isomer. Such optical isomers which differ only in the sign of (or direction of) optical
rotation are called ‘‘enantiomers’’. When equal amounts of d-isomer and l-isomer are mixed one
gets a ‘‘racemic mixture’’ and this process is called racemisation. A racemic mixture becomes
optically inactive. Because, in this mixture rotation towards clockwise direction by the dextro
isomers is compensated by the rotation towards the anticlockwise direction by the laevo isomers.
The optical inactivity of a racemic mixture is said to be due to ‘external compensation’.
Any how an optically inactive racemic form can be separated into two active forms. This process
of separation is called ‘‘resolution of the racemic mixture’’.
A molecule with more than one chiral carbon
A molecule can have more than one chiral centres. Correspondingly the number of isomers
is increased. In general for a molecule with n-different chiral centres, 2n-isomers are possible. A
molecule can have more than one identical asymmetric carbon atoms. (e.g.,) butane -2,3-diol and
tartaric acid.
59
 In such cases the number of optical isomers is not 22 = 4, it is less than 4 (i.e.,) 3.
Isomerism in Tartaric acid :
Tartaric acid is dihydroxy dioic acid, having two identical chiral carbon atoms.

The enantiomers of tartaric acid, have the same magnitude but different sign of optical
rotation. They have object-mirror image relationship.
In the d-isomer, each of the two asymmetric carbon atoms rotate the plane of the polarised
light towards right leading to overall dextro rotation. In the same way in the l - isomer, the overall
rotation is laevo.
There is another optical isomer for tartaric acid in which one asymmetric carbon atom is
dextrorotatory and the other laevorotatory-both rotating to the same extent in opposite directions.
The net result is, that this isomer becomes optically inactive and is called the ‘‘Meso’’ isomer.

Though the Meso isomer has two asymmetric carbon atoms the configuration of one carbon
is the mirror image of the other, the net result being the molecule as a whole becomes symmetric.
This molecule is said to have a symmetric plane, which divides the molecule into two equal halves.
The molecule becomes ‘‘achiral’’. It has configuration which is superimposable on its mirror
image.

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 The optical inactivity of the ‘Meso’ isomer is due to the internal compensation. It is due to
the inherent symmetry in the molecule. Mesoform cannot be separated into optically active
enantiomeric pairs. This form is a single substance and not a mixture.

When equal amounts of d-tartaric acid and l-tartaric acid are mixed, we get racemic tartaric
acid which is an optically inactive mixture. This can be separated into two optically active forms.
d- and l-isomers have the same magnitude but different sign of optical rotation, hence they
are called enantiomers. The Meso tartaric acid differs in the magnitude of optical rotation from the
d- or l- isomer. Hence Mesoform is said to be a ‘‘diastereomer’ of the active form.

Representation of configurations of the molecule:

In order to indicate the exact spatial arrangement of atoms or groups in a molecule having
asymmetric carbon atom, Fischer proposed DL-system of nomenclature. Glyceraldehyde was
taken as the standard. The dextro isomer and laevo isomer of glyceraldehyde are designated as D
and L as follows. These are Fischer’s projection formulae.

61
 In general more oxidised group is shown at the top and the reduced group at the bottom.
The chiral molecule is viewed in such a way that H, Xlie above the plane of the paper and R1, R2-
lie below the plane of the paper. The D, L-configurations are shown as :

The above projection formulae can be understood from the following diagram.

Thus D and L lactic acids are

62
and tartaric acid - (R-stands for the remaining half portion of the molecule)

This system of designating configuration is of limited applicability.

In Fischer’s projection formula any two exchanges of groups attached to the asymmetric
carbon atom, are allowed, then the configuration is not changed.

Though I and II appears to be different but both represent the same configuration. Both are
identical.
Absolute Configuration: R and S Notations

Each stereogenic center is assigned a configuration, based on the following rules 1. Use the Cahn-
Ingold-Prelog priority rules to assign priority (one through four) to the four groups on the chiral
carbon atom.

63
2. Orient the molecule so that the lowest priority atom is in the back (away from you). Look
at the remaining three groups of priority 1-3. If the remaining three groups are arranged so
that the priorities 1→2→3 are in a clockwise fashion, then assign the chiral center as R (“rectus”
or right). If the remaining three groups are arranged 1→2→3 in a counterclockwise manner,
then assign the chiral center as S (“sinister” or left)

Orienting a Tetrahedron – The Double Switch

Interchanging any two groups inverts the stereochemistry. So switch the lowest priority group to
the desired position. Then switch any other two groups. The “double-switch” does not change the
stereochemistry.

Fischer Projections

Representation of a three-dimensional molecule as a flat structure. A tetrahedral carbon

64
is represented using just two crossed lines:

Horizontal line is coming out of the plane of the page (towards you) and vertical line is
going back behind the plane of the paper (away from you)

Manipulation of Fischer Projections

Rotating a Fischer projection by 180° retains the configuration

Rotating a Fischer projection by 90° inverts the configuration

If one group of a Fischer projection is held steady, the other three groups can be rotated clockwise
or counterclockwise without altering the configuration.

65
Assigning R and S Configurations to Fischer Projections

1. Assign priorities to the four substitutents according to the Cahn-Ingold-Prelog rules

2. Perform the two allowed manipulations of the Fischer projection to place the lowest priority
group at the top (or bottom).

3. If the priority of the groups 1→2→3 are clockwise then assign the center as R, if 1→2→3 are
counterclockwise then assign the center as S.

Molecules with more than one Stereocenter

If a molecule has one stereocenter it exists as R and S isomers, which are enantiomers. If a molecule
has two stereocenters, each of them can exist as R and S, independent of the other center. The
maximum number of stereoisomers for a molecule having n stereocenters is 2n

Absolute Configuration: R-S Sequence Rules

Introduction

The method used for assigning the handedness of molecules was originated by three chemists: R.S.
Cahn, C. Ingold, and V. Prelog and, as such, is also often called the Cahn-Ingold-Prelog rules. In
addition to the Cahn-Ingold system, there are two ways of experimentally determining the absolute
configuration of an enantiomer:

66
 1. X-ray diffraction analysis. Note that there is no correlation between the sign of rotation and
the structure of a particular enantiomer.
2. Chemical correlation with a molecule whose structure has already been determined via X-
ray diffraction.

However, for non-laboratory purposes, it is beneficial to focus on the R/S system. The sign
of optical rotation, although different for the two enantiomers of a chiral molecule, at the same
temperature, cannot be used to establish the absolute configuration of an enantiomer; this is
because the sign of optical rotation for a particular enantiomer may change when the temperature
changes.

Stereocenters are labeled R or S

The "right hand" and "left hand" nomenclature is used to name the enantiomers of a chiral
compound. The stereocenters are labeled as R or S.

Consider the first picture: a curved arrow is drawn from the highest priority (1) substituent to the
lowest priority (4) substituent. If the arrow points in a counterclockwise direction (leftwhen
leaving the 12 o' clock position), the configuration at stereocenter is considered S ("Sinister" →
Latin= "left"). If, however, the arrow points clockwise,(Right when leaving the 12 o' clock
position) then the stereocenter is labeled R ("Rectus" → Latin= "right"). The R or S is then added
as a prefix, in parenthesis, to the name of the enantiomer of interest.

Sequence rules to assign priorities to substituents

Before applying the R and S nomenclature to a stereocenter, the substituents must be prioritized
according to the following rules:

Rule 1 First, examine at the atoms directly attached to the stereocenter of the compound. A
substituent with a higher atomic number takes preference over a substituent with a lower atomic
number. Hydrogen is the lowest possible priority substituent, because it has the lowest atomic
number.

1. When dealing with isotopes, the atom with the higher atomic mass receives higher
priority.

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 2. When visualizing the molecule, the lowest priority substituent should always point away
from the viewer (a dashed line indicates this). To understand how this works or looks,
imagine that a clock and a pole. Attach the pole to the back of the clock, so that when
looking at the face of the clock the pole points away from the viewer in the same way the
lowest priority substituent should point away.

3. Then, draw an arrow from the highest priority atom to the 2nd highest priority atom to
the 3rd highest priority atom. Because the 4th highest priority atom is placed in the back,
the arrow should appear like it is going across the face of a clock. If it is going clockwise,
then it is an R-enantiomer; If it is going counterclockwise, it is an S-enantiomer.

When looking at a problem with wedges and dashes, if the lowest priority atom is not on the
dashed line pointing away, the molecule must be rotated.
Remember that

● Wedges indicate coming towards the viewer.

● Dashes indicate pointing away from the viewer.

Rule 2

If there are two substituents with equal rank, proceed along the two substituent chains until there
is a point of difference. First, determine which of the chains has the first connection to an atom
with the highest priority (the highest atomic number). That chain has the higher priority.

If the chains are similar, proceed down the chain, until a point of difference.

For example: an ethyl substituent takes priority over a methyl substituent. At the connectivity of
the stereocenter, both have a carbon atom, which are equal in rank. Going down the chains, a
methyl has only has hydrogen atoms attached to it, whereas the ethyl has another carbon
atom. The carbon atom on the ethyl is the first point of difference and has a higher atomic
number than hydrogen; therefore the ethyl takes priority over the methyl.

Rule 3

If a chain is connected to the same kind of atom twice or three times, check to see if the atom it
is connected to has a greater atomic number than any of the atoms that the competing chain is
connected to.

● If none of the atoms connected to the competing chain(s) at the same point has a greater
atomic number: the chain bonded to the same atom multiple times has the greater priority

68
 ● If however, one of the atoms connected to the competing chain has a higher atomic
number: that chain has the higher priority.

Explain the Isomerism in transitional metal compounds.

Two or more different compounds having the same formula are called isomers. Two principal
types of isomerism are known among coordination compounds. Each of which can be further
subdivided.

1. Stereoisomerism. a) Geometrical isomerism b) Optical isomerism

2. Structural Isomerism.

a) Coordination isomerism b) Ionization isomerism c) Hydrate isomerism

d) Linkage isomerism

1. Stereo isomerism
Stereoisomers have the same atoms, same sets of bonds, but differ in the relative orientation of
these bonds.

Geometric isomers are possible for both square planar and octahedral complexes, but not
tetrahedral.

Optical isomers are possible for both tetrahedral and octahedral complexes, but not square planar.

The earliest examples of stereoisomerism involve complexes of Co(III). In 1889, Jorgensen

observed purple and green salts of [CoCl2(en)2]+, which Werner later correctly identified as
the cis- and trans- geometric isomers. In 1911, the first resolution of optical isomers was reported
by Werner and King for the complexes cis-[CoX(NH3)(en)2]2+, where X=Cl- or Br-.

Geometric Isomers
The number of geometric isomers expected for common stereo chemistries are as follows:

Square Planar:
Compound type No. of isomers
Ma2b2 2 (cis- and trans-)
Mabcd 3 (use cis- and trans- relations)
here a, b, c, and d refer to mono dentate ligands.

A number of examples of these types have been isolated and characterized and they show very
different chemical and biological properties. Thus for example, cis-PtCl2(NH3)2 is an anti-cancer
agent (cis platin) whereas the trans- isomer is inactive against cancer (it is toxic), and so not useful
in Chemotherapy.

69
cis- and trans- refer to the position of 2 groups relative to each other. In the cis- isomer they are
"next to each other" i.e. at 90 degrees in relation to the central metal ion, whereas in
the trans- isomer they are "opposite each other", i.e. at 180 degrees relative to the central metal
ion.

3 geometric isomers of a square planar complex [PtBrClNH3(pyr)].

The first report of the three geometric isomers being isolated and characterised for complexes of
the type [Mabcd] was by Il'ya Chernyaev in 1928. The example above was reported by Anna
Gel'man in 1948.

Octahedral:
Compound type No. of isomers
Ma4b2 2 (cis- and trans-)
Ma3b3 2 (fac- and mer-)
MAA2b2 3 (2*cis- and 1 trans-)

here a, and b, represent monodentate ligands and AA is a bidentate ligand.

In the second example, new labels are introduced to reflect the relative positions of the ligands
around the octahedral structure. Thus; placing the 3 groups on one face of the octahedral gives
rise to the facial isomer and placing the 3 groups around the centre gives rise to the meridional
isomer.

70
[Mabcdef] is expected to give 15 geometric isomers. In the case of [PtBrClI(NO2)(NH3)(pyr)],
several of these were isolated and characterised by Anna Gel'man and reported in 1956. Optical
isomers are possible for each of these 15 forms, making a total of 30 isomers.

The cis- isomer of MAA2b2 may also exhibit optical isomerism although we will concentrate
largely on optical isomers of the type M(AA)3

Optical Isomers

Optical isomers are related as non-superimposable mirror images and differ in the direction with
which they rotate plane-polarised light. These isomers are referred to as enantiomers or
enantiomorphs of each other and their non-superimposable structures are described as being
asymmetric.

Various methods have been used to denote the absolute configuration of optical isomers such as R
or S, Λ or Δ or C and A. The IUPAC rules suggest that for general octahedral complexes C/A
scheme is convenient to use and that for bis and tris bidentate complexes the absolute configuration
be designated Lambda Λ (left-handed) and Delta Δ (right-handed).

Priorities are assigned for mononuclear coordination systems based on the standard sequence rules
developed for enantiomeric carbon compounds by Cahn, Ingold and Prelog (CIP rules). These
rules use the coordinating atom to arrange the ligands into a priority order such that the highest
atomic number gives the highest priority number (smallest CIP number). For example the
hypothetical complex [Co Cl Br I NH3 NO2 SCN]2- would assign the I- as 1, Br as 2, Cl as 3, SCN
as 4, NO2 as 5 and NH3 as 6.

71
 Here is one isomer where the I and Cl, and Br and NO2 were found to be trans- to each
other.

The reference axis for an octahedral centre is that axis containing the ligating atom of CIP priority
1 and the trans ligating atom of lowest possible priority (highest numerical value). The atoms in
the coordination plane perpendicular to the reference axis are viewed from the ligand having that
highest priority (CIP priority 1) and the clockwise and anticlockwise sequences of priority numbers
are compared. The structure is assigned the symbol C or A, according to whether the clockwise
(C) or anticlockwise (A) sequence is lower at the first point of difference. In the example shown
above this would be C.

The two optical isomers of [Co(en)3]3+ have identical chemical properties and just denoting their
absolute configuration does NOT give any information regarding the direction in which they
rotate plane-polarised light. This can ONLY be determined from measurement and then the
isomers are further distinguished by using the prefixes (-) and (+) depending on whether they
rotate left or right.

o add to the confusion, when measured at the sodium D line (589nm), the tris(1,2-
diaminoethane)M(III) complexes (M= Rh(III) and Co(III)) with IDENTICAL absolute
configuration, rotate plane polarised light in OPPOSITE directions!

72
The left-handed (Λ)-[Co(en)3]3+ isomer gives a rotation to the right and therefore corresponds to
the (+) isomer.

Since the successful resolution of an entirely inorganic ion (containing no C atoms) (hexol) only
a handful of truly inorganic complexes have been isolated as their optical isomers
e.g. (NH4)2Pt(S5)3.2H2O.

For tetrahedral complexes, R and S would be used in a similar method to tetrahedral Carbon
species and although it is predicted that tetrahedral complexes with 4 different ligands should be
able to give rise to optical isomers, in general they are too labile and can not be isolated.

Isomerism in Coordination Complexes

The existence of coordination compounds with the same formula but different
arrangements of the ligands were crucial in the development of coordination chemistry. Two or
more compounds

with the same formula but different arrangements of the atoms are called isomers. Because
isomers usually have different physical and chemical properties, it is important to know which
isomer we are dealing with if more than one isomer is possible. As we will see, coordination
compounds exhibit the same types of isomers as organic compounds, as well as several kinds of
isomers that are unique. Isomers are compounds with the same molecular formula but different
structural formulas and do not necessarily share similar properties. There are many different
classes of isomers, like stereoisomers, enantiomers, geometrical isomers, etc. (see chart below).
There are two main forms of isomerism: structural isomerism and stereoisomerism (spatial
isomerism).
Class I: Structural Isomers
Isomers that contain the same number of atoms of each kind but differ in which atoms are bonded
to one another are called structural isomers, which differ in structure or bond type. For inorganic
complexes, there are three types of structural isomers: ionization, coordination and linkage.
Structural isomers, as their name implies, differ in their structure or bonding, which are separate
from stereoisomers that differ in the spatial arrangement of the ligands are attached, but still have
the bonding properties. The different chemical formulas in structural isomers are caused either by
a difference in what ligands are bonded to the central atoms or how the individual ligands are
bonded to the central atoms. When determining a structural isomer, you look at (1) the ligands that
are bonded to the central metal and (2) which atom of the ligands attach to the central metal.

Structural Isomers:

(i) Ionization Isomerism

Ionization isomers are identical except for a ligand has exchanging places with an anion or neutral
molecule that was originally outside the coordination complex. The central ion and the other
ligands are identical. For example, an octahedral isomer will have five ligands that are identical,
but the sixth will differ. The non-matching ligand in one compound will be outside of the
coordination sphere of the other compound. Because the anion or molecule outside the
coordination sphere is different, the chemical properties of these isomers is different. A hydrate

73
isomer is a specific kind of ionization isomer where a water molecule is one of the molecules that
exchanges places.

Figure 24.4.124.4.1: Two Ionization isomers. The two isomers differ only which ligands are
actually bound to the center metal. (left) The chloride atom is bound to the cobalt as a chloro-
ligand with the bromine atom as the bromide counter ion. (right) In the other ionization isomer
the bromine atom is acting as a bromo- ligand to the cobalt with the chlorine atom acting as
the chloride counter ion. These two isomers are called
pentaamminechlorocobalt(II) bromide (left) and pentaamminebromocobalt(II) chloride (right).

The difference between the ionization isomers can be view within the context of the ions
generated when each are dissolved in solution. For example, when pentaamminbromocobalt(II)
chloride is dissolved in water, Cl−Cl− ions are generated:

CoBr(NH3)5Cl(s)→CoBr(NH3)+5(aq)+Cl−(aq)

whereas when pentaaquachlorocobalt(II) bromide is dissolved, Br−Br− ions are generated:

CoCl(NH3)5Br(s)→CoCl(NH3)+5(aq)+Br−(aq)

Notice that both anions are necessary to balance the charge of the complex, and that they differ
in that one ion is directly attached to the central metal, but the other is not.

ii) Solvate or hydrate isomerism: A SPECIAL TYPE OF IONIZATION ISOMERS

A very similar type of isomerism results from replacement of a coordinated group by a

solvent molecule (Solvate Isomerism), which in the case of water is called Hydrate Isomerism. The
best known example of this occurs for chromium chloride (CrCl3⋅6H2OCrCl3⋅6H2O) which may
contain 4, 5, or 6 coordinated water molecules (assuming a coordination number of 6). The dot
here is used essentially as an expression of ignorance to indicate that, though the parts of the
molecule separated by the dot are bonded to one another in some fashion, the exact structural
details of that interaction are not fully expressed in the resulting formula. Using Alfred Werner’s
coordination theory that indicates that several of the water molecules are actually bonded directly
(via coordinate covalent bonds) to the central chromium ion. In fact, there are several possible

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compounds that use the brackets to signify bonding in the complex and the the dots to
signify "water molecules that are not bound to the central metal, but are part of the lattice:

● [CrCl2(H2O)4]Cl⋅2H2O[CrCl2(H2O)4]Cl⋅2H2O: bright-green colored

● [CrCl(H2O)5]Cl2⋅H2O[CrCl(H2O)5]Cl2⋅H2O: grey-green colored

● [Cr(H2O)6]Cl3[Cr(H2O)6]Cl3: violet colored

These isomers have very different chemical properties and on reaction with AgNO3AgNO3 to test
for Cl−Cl− ions, would find 1, 2, and 3 Cl−Cl− ions in solution, respectively.

Upon crystallization from water, many compounds incorporate water molecules in their
crystalline frameworks. These "waters of crystallization" refers to water that is found in the
crystalline framework of a metal complex or a salt, which is not directly bonded to the metal
cation. In the first two hydrate isomers, there are water molecules that are artifacts of the
crystallization and occur inside crystals. These water of crystallization is the total weight of water
in a substance at a given temperature and is mostly present in a definite (stoichiometric) ratio.

The [Cr(H2O)6]Cl3[Cr(H2O)6]Cl3 hydrate isomer (left) is violet colored and

the [CrCl(H2O)5]Cl2⋅H2O[CrCl(H2O)5]Cl2⋅H2O hydrate isomer is green-grey colored.

iii) Coordination Isomerism

Coordination isomerism occurs compounds containing complex anionic and cationic parts can be
thought of as occurring by interchange of some ligands from the cationic part to the anionic part.
Hence, there are two complex compounds bound together, one with a negative charge and the other
with a positive charge. In coordination isomers, the anion and cation complexes of a coordination
compound exchange one or more ligands. For example,
the [Co(NH3)6][Cr(C2O4)3][Co(NH3)6][Cr(C2O4)3] compounds
and [Co(C2O4)3][Cr(NH3)6][Co(C2O4)3][Cr(NH3)6] compound are coordination isomers.

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iv) Linkage Isomerism

Linkage isomerism occurs with ambidentate ligands that are capable of coordinating in more than
one way. The best known cases involve the monodentate
ligands: SCN−/NCS−SCN−/NCS− and NO−2/ONO−NO2−/ONO−. The only difference is what atoms
the molecular ligands bind to the central ion. The ligand(s) must have more than one donor atom,
but bind to ion in only one place. For example, the (NO−2NO2−) ion is a ligand can bind to the
central atom through the nitrogen or the oxygen atom, but cannot bind to the central atom with
both oxygen and nitrogen at once, in which case it would be called a polydentate rather than
an ambidentate ligand.

Figure 24.4.224.4.2: Linkage Isomerism in the NO2NO2 ligand. This occurs when a particular
ligand is capable of coordinating to a metal in two different and distinct ways.

Class 2: Geometric Isomerism of coordination compounds

The existence of coordination compounds with the same formula but different arrangements of the
ligands were crucial in the development of coordination chemistry. Two or more compounds with
the same formula but different arrangements of the atoms are called isomers. Because isomers
usually have different physical and chemical properties, it is important to know which isomer we
are dealing with if more than one isomer is possible. Recall that in many cases more than one
structure is possible for organic compounds with the same molecular formula; examples discussed
previously include n-butane versus isobutane and cis-2-butene versus trans-2-butene. As we will
see, coordination compounds exhibit the same types of isomers as organic compounds, as well as
several kinds of isomers that are unique.

Geometric Isomers: four coordinated complex compounds( Planar Isomers)

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Metal complexes that differ only in which ligands are adjacent to one another (cis) or directly
across from one another (trans) in the coordination sphere of the metal are called geometrical
isomers. They are most important for square planar and octahedral complexes.

Because all vertices of a square are equivalent, it does not matter which vertex is occupied by the
ligand B in a square planar MA3B complex; hence only a single geometrical isomer is possible in
this case (and in the analogous MAB3 case). All four structures shown here are chemically
identical because they can be superimposed simply by rotating the complex in space:

For an MA2B2 complex, there are two possible isomers: either the A ligands can be adjacent to
one another (cis), in which case the B ligands must also be cis, or the A ligands can be across from
one another (trans), in which case the B ligands must also be trans. Even though it is possible to
draw the cis isomer in four different ways and the trans isomer in two different ways, all members
of each set are chemically equivalent:

Because there is no way to convert the cis structure to the trans by rotating or flipping the molecule
in space, they are fundamentally different arrangements of atoms in space. Probably the best-
known examples of cis and trans isomers of an MA2B2 square planar complex are cis-Pt(NH3)2Cl2,
also known as cisplatin, and trans-Pt(NH3)2Cl2, which is actually toxic rather than therapeutic.

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The anticancer drug cisplatin and its inactive trans isomer. Cisplatin is especially effective against
tumors of the reproductive organs, which primarily affect individuals in their 20s and were
notoriously difficult to cure. For example, after being diagnosed with metastasized testicular
cancer in 1991 and given only a 50% chance of survival, Lance Armstrong was cured by treatment
with cisplatin.

Square planar complexes that contain symmetrical bidentate ligands, such as [Pt(en)2]2+, have only
one possible structure, in which curved lines linking the two N atoms indicate the ethylenediamine
ligands:

Geometric Isomers: six coordinated complex compounds (Octahedral Isomers)

Octahedral complexes also exhibit cis and trans isomers. Like square planar complexes, only one
structure is possible for octahedral complexes in which only one ligand is different from the other
five (MA5B). Even though we usually draw an octahedron in a way that suggests that the four “in-
plane” ligands are different from the two “axial” ligands, in fact all six vertices of an octahedron
are equivalent. Consequently, no matter how we draw an MA5B structure, it can be superimposed
on any other representation simply by rotating the molecule in space. Two of the many possible
orientations of an MA5B structure are as follows:

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If two ligands in an octahedral complex are different from the other four, giving an
MA4B2 complex, two isomers are possible. The two B ligands can be cis or trans. Cis- and trans-
[Co(NH3)4Cl2]Cl are examples of this type of system:

Replacing another A ligand by B gives an MA3B3 complex for which there are also two possible
isomers. In one, the three ligands of each kind occupy opposite triangular faces of the octahedron;
this is called the fac isomer (for facial). In the other, the three ligands of each kind lie on what
would be the meridian if the complex were viewed as a sphere; this is called the mer isomer (for
meridional):

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UNIT-V CHEMISTRY OF ADVANCED MATERIALS

1.Nano Materials, Liquid Crystals, Super conductors, Green Chemistry

NANO MATERIALS
Introduction:
A nanometer (nm) is one thousand millionth of a meter ( i.e. 10-9). Atoms are extremely small
and the diameter of a single atom can vary from 0.1 to 0.5 nm depending on the type of the
element. For example, one carbon atom is approximately 0.15 nm in diameter. The radius of the
atom can be considered as half the distance between neighboring atoms when they are present in
the solid phase.
Nonmaterial: The material having components with in size less than 100nm at least in one
dimension are known as nonmaterials.

● Materials that are nanoscale in one dimension (and are extended in the other two dimensions)
are layers, such as thin films or surface coatings.

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● Materials that are nanoscale in two dimensions (and are extended in one dimension) include
nanowires and annotates.
● Materials that are nanoscale in three dimensions are particles, for example precipitates,
colloids and quantum dots (tiny particles of semiconductor materials). Nanocrystalline
materials, made up of nanometre-sized grains, also fall into this category.
II. SYNTHESIS OF NANOPARTICLES There are two methods for the production of
nanoparticles which is summarized below:
A) Top-down approach :The principle behind the top-down approach is to take a bulk piece of
the material and then modify it into the wanted nanostructure and subsequent stabilization of the
resulting nanosized metal nanoparticles by the addition of colloidal protecting agents. Cutting,
grinding and etching are typical fabrication techniques, which have been developed to work on
the nano scale. The sizes of the nanostructures which can be produced with top-down techniques
are between 10 to 100 nm.
B) Bottom-up approach :Bottom-up self assembly refers to construction of a structure atom by
atom, molecule-by molecule or cluster-by-cluster. Colloidal dispersion used in the synthesis of
nano particles is a good example of a bottom-up approach. An advantage of the bottom-up
approach is the better possibilities to obtain nanostructures with less defects and more
homogeneous chemical compositions.

1.Sol-Gel Methods The sol-gel process (gelation): a change from a liquid state to a gel state
through poly condensation reactions. A sol is a stable dispersion of colloidal particles or polymers
in a solvent. The particles may be amorphous or crystalline. Typical size few nm. A gel consists
of a three dimensional continuous network of the sol particles, which encloses a liquid phase
In a colloidal gel, the network is built from agglomeration of colloidal particles. In a polymer gel
the particles have a polymeric sub-structure made by aggregates of sub-colloidal particles.
During gelation covalent bonding, Vander Waal- and H-bonds are formed Particulate sols:
Gelling via agglomeration common Polymeric sols: Gelling via condensation
Sol-gel may be used to prepare materials with a variety of shapes, such as porous structures, thin
fibers, dense powders and thin films.
If the gel is dried by evaporation, then the capillary forces will result in shrinkage, the gel network
will collapse, and a xerogel is formed. If drying is performed under supercritical conditions, the
network structure may be retained and a gel with large pores may be formed. This is called an aero
gel, and the density will be very low.

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2.Chemical Reduction method: This method is also belongs to bottom up approach method.
Particularly silver nano particles were prepared by this method.
For the preparation of silver nano particles
1.Silver nitrate solution (1ppm-6ppm) taken as metal salt precursor
2. 8% sodium do decyl sulphate solution taken as metal stabilizing agent
3.hydrazene hydrate and citrate solution (2-12ppm) taken as reducing reagent
By the mixing of all the above reagents carefully in a beaker after few minutes the transparent
colorless solution is converted to pale yellow and pale red colour which indicates that formation
of silver nano particles. To remove the excess silver ions, the solution is washed three times with
de ionized water under the steam of nitrogen. These nano particles are purified by centrifugation
process. By freezing and drying, dried powdered silver nano particles will be obtained.
Metal salt solution + Metal salt precursor+ stabilizer+ Reducing agent🡪 stand for some time ---
>nano particles will be separated purification------->centrifugation----> freeze drying ---->
powdered metal nano particles will be formed
3.Brunauer-Emmett-Teller(BET method)
Nano crystalline particles of CoxFe(3-x)O4 are synthesized by combustion reaction
method using iron nitrate ,cobalt nitrate and with Asa’s fuel without template and subsequent heat
treatment. This process is simple and inexpensive. Since there is no any type of intermediate steps
like decomposition or calcinations steps. The maximum reaction temperature range is 850- 1010
degree centigrade and combustion will be completed in 30 minutes. The product is washed with
distilled water to remove byproducts and to produce pure nano particles.

4.Transmission Electron Microscope method(TEM)

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This is a shape controlled method for synthesis of colloidal platinum nano particles which is
potentially important in the field of catalysis. In general catalytic activity depends upon the size
and shape of the particles used.
For preparation of platinum nano particles A solution of platinum chloride (0.00001M) is prepared
in water and treated with 0.2 ml of 0.1 M sodium poly acryl ate. The resulting solution bubbled
with Argon gas for about 20 minutes. The platinum ions are reduced by bubbling hydrogen gas
for 5 minutes. The reaction vessel is sealed and left over night. The solution turns into light gold
colour and then these nano particles were purified and separated.
Properties of Nano materials:
1. Based on the size : By changing of size of the particles properties like m.p., b.p., solubility,
colour, transparency, and catalytic behavior were also changed .
2. Magnetic behavior: By decreasing the size of the nano particles magnetic properties will be
increase due to increase in the order of electronic spin.
3. Colour : The physical property like color is also size dependent. As the size of the particles
changes color of the material also changes. For eg. bulk gold looks like yellow, but 12nm nano
sized gold particles looks like red due to difference in wave length of the scattering light.
4. Catalytic Behavior : By the decrease in the size of the nano particles the rate of reactivity will
be increase. Therefore catalytic activity will be increase.
5. Chemical reactivity: By the decrease in the size of the nano particles the rate of reactivity will
be increase.
6. Conductivity: By the decrease in the size of the nano particles the conductivity will be increase.
Since the energy gap between valence band and conduction band is proportional to size of the
particle. As the size of particle decreases , gap decreases and then conductance increases. Nano
materials can be used as good conducting and semiconducting materials.
Applications of Nano materials
1)The potential applications of nano particales of new supercomputers. It includes zero
dimensional quantum dots, one dimensional quantum dots, planer arrays of ordered structure,
nanoscale circuits Nano particles are potentials.
2) Nano particals potential components in the generation of bimetallic nanostructure and nano
mechanical device based on DNA.
3)The magnatic nano metals particles are widely used in magnetic separation, magnetic drug
transport and magnetic optical data storage.
4) Nylon nano composites containing small amount of clay are capable withstanding high
temperature environments and used in automobile air intake covers.
5) Nano-crystalline ceramics, such as silicon nitride and silicon carbide, have been used in such
automotive applications as high strength springs, ball bearings and valve lifters, because they
can be easily formed and machined, as well as exhibiting excellent chemical and high
temperature properties. They are also used as components in high-temperature furnaces
6) Nano-engineered membranes could potentially lead to more energy-efficient water
purification processes, notably in desalination by reverse osmosis.
7)Nanosized titanium diozide and zinc oxide are currently used in sun screens. They absorb and
reflect ultraviolet (UV) rays and yet are transparent to visible at light
8)Nanocrystalline zincselenide, zincsulphide, cadmiumsulphide and lead telluride synthesized

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by sol-gel techniques are candidates for the next generation of light emitting phosphors, they
will have huge market for displays.CNTs are being investigated for low voltage field.emission
displays; their strength, sharpness, conductivity and inertness make them potentially very
efficient and long-lasting emitters.
Carbon nanotubes:
● Carbon nanotubes were first observed by Sumio Iijima in 1991.
● They are long, thin cylinders of carbon.
● These are large macromolecules that are unique for their size, shape and remarkable
physical properties.
● Carbon nanotubes are allotropes of carbon with a nanostructure having a length to diameter
ratio greater than 1, 00,000.
● They are considered as a sheet of graphite rolled in to a cylinder.
● Nanotubes have a very wide range of electronic, thermal and structural properties that
changes depending on the different kinds of nanotubes.

Types of CNTs: They are two types of cabon nanotubes depending upon the way in which they
are arranged.
1) single walled nanotubes (SWNT’S)
2) multi walled nanotubes (MWNT’S)

1)Single walled nanotubes(SWNT’S):

● Most of single walled nanotubes have a diameter of close to 1nm.

● The structure of a SWNT can be obtained by wrapping a one - atom thick layer of graphite.
● There are different types of CNTs, because the graphene sheets can be rolled in different
ways. The three types of CNTs are zigzag, Armchair, and chiral
Chiral -, armchair-, and zig-zag- SWNT.
2) Multi walled nanotubes(MWNT’S):
● Multi walled nanotubes consist of multiple rolled layers of graphite.
● The interlayer distance in multi-walled nanotubes is close to the distance between
graphene layers in graphite approximately 3.3A0
● They exhibit both metallic and semi conducting properties.
● There are two models which can be used to describe the structure of multi-walled
nanotubes.
● A) In Russian doll model, sheets of graphite are arranged in concentric cylinders

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 ● B) In the parchment model, a single sheet of graphite is rolled in around itself,
resembling a rolled news paper.

Production of CNTs:There are a number of methods of making CNTs.. Now let us few methods
presently adopted for the production of CNTs.

a) Arc Method:

● This method creates CNT’s through arc-vaporization of two carbon rods placed end to
end, separated by approximately 1 nm, in an enclosure that is usually filled with inert
gas at low pressure.
● Recent investigations have shown that it is also possible to create CNTs with the arc
method in liquid nitrogen.
● A direct current of 50 to 100A, driven by a potential difference of approximately 20
V, creates a high temperature discharge between the two electrodes.
● The discharge vaporizes the surface of one of the carbon electrodes, and forms a small
rod-shaped deposit on the other electrode.
● Producing CNTs in high yield depends on the uniformity of the plasma arc, and the
temperature of the deposit forming on the carbon electrode

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b) Laser ablation method: In 1995, Smalley's group at Rice University reported the synthesis
of carbon nanotubes by laser vaporisation.

● A pulsed or continuous laser is used to vaporize a graphite target in an oven at 1200 °C.
● The oven is filled with helium or argon gas in order to keep the pressure at 500 Torr.
● A very hot vapour plume forms, then expands and cools rapidly.
● As the vaporised species cool, small carbon molecules and atoms quickly condense to
form larger clusters, possibly including fullerenes.
● The catalysts also begin to condense, but more slowly at first, and attach to carbon
clusters and prevent their closing into cage structures. Catalysts may even open cage
structures when they attach to them.
● From these initial clusters, tubular molecules grow into single-wall carbon nanotubes
until the catalyst particles become too large, or until conditions have cooled sufficiently
that carbon no longer can diffuse through or over the surface of the catalyst particles.
● It is also possible that the particles become that much coated with a carbon layer that
they cannot absorb more and the nanotube stops growing.

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c) Chemical Vapour Deposition(CVD):

● Chemical vapour deposition (CVD) synthesis is achieved by putting a carbon source in the
gas phase and using an energy source, such as a plasma or a resistively heated coil, to
transfer energy to a gaseous carbon molecule.
● Commonly used gaseous carbon sources include methane, carbon monoxide and acetylene.
● The energy source is used to "crack" the molecule into reactive atomic carbon. Then, the
carbon diffuses towards the substrate, which is heated and coated with a catalyst (usually
a first row transition metal such as Ni, Fe or Co) where it will bind.
● Carbon nanotubes will be formed if the proper parameters are maintained.
● CVD carbon nanotube synthesis is essentially a two-step process consisting of a catalyst
preparation step followed by the actual synthesis of the nanotube.
● The catalyst is generally prepared by sputtering a transition metal onto a substrate and then
using either chemical etching or thermal annealing to induce catalyst particle nucleation.
● Thermal annealing results in cluster formation on the substrate, from which the nanotubes
will grow. Ammonia may be used as the etchant.
● The temperatures for the synthesis of nanotubes by CVD are generally within the 650-
900 oC range. Typical yields for CVD are approximately 30%.

Fullerenes
● A fullerene is any molecule composed entirely of carbon, in the form of a hollow sphere,
ellipsoid or tube.
● Spherical fullerenes are also called buckyballs, and they resemble the balls used in football
(soccer). Cylindrical fullerenes are called carbon nanotubes or buckytubes.

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 ● Fullerenes are similar in structure to graphite, which is composed of stacked graphene
sheets of linked hexagonal rings; but they may also contain pentagonal (or sometimes
heptagonal) rings
Naming: A third newely discovered allotrope of carbon is Buckminsterfullerene (C60) was
named in the honour of the American architect Richard Buckminster Fuller, the designer of the
geodesic dome. The shape C60 resembles with the domes designed by fuller.

Types of fullerenes:
Fullerenes are a family of carbon allotropes, molecules entirely composed of cabon,in the form
of hollow sphere,ellipsoid,tube or tube. Thus fullerenes are three types.
1) Spherical fullerenes: They look like a soccer ball and are often called bucky balls
2) cylindricalfullerenes: These are called carbon nanotubes or buckytubes.
3) Planer fullerenes: Graphene is an example of planer fullerene sheet.
Synthesis:
Fullerenes are prepared by vaporizing a graphite rod in helium atmosphere. Mixtures of
fullerenes like C60,C70 are formed which are separated by solvent extraction. C60 is isolated from
this mixture by column chromatography using alumina as solvent.
Structure of fullerene:
Buckminsterfullerene is the smallest fullerene molecule containing pentagonal and hexagonal
rings in which no two pentagons share an edge (which can be destabilizing, as in pentalene). It is
also the most common in terms of natural occurrence, as it can often be found in soot.
The structure of C60 is a truncated icosahedrons, which resembles an association football ball of
the type made of twenty hexagons and twelve pentagons, with a carbon atom at the vertices of
each polygon and a bond along each polygon edge.
The van der Waals diameter of a C60 molecule is about 1.1 nanometers (nm). The nucleus to
nucleus diameter of a C60 molecule is about 0.71 nm.
The C60 molecule has two bond lengths. The 6:6 ring bonds (between two hexagons) can be
considered "double bonds" and are shorter than the 6:5 bonds (between a hexagon and a
pentagon). Its average bond length is 1.4 angstroms. Silicon buckyballs have been created
around metal ions.

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Properties of fullerenes:
1.It exist as a discrete molecule.
2.C60 is a mustard colored solid when thickness of the film increases it appears brown to black.
3. It is moderately soluble in common organic solvents, specially aromatic hydrocarbons.
4. It dissolves in benzene
5.It is very tough.

Engineering applications of fullerenes:

1)Fullerenes can be easily accept electrons, therefore they may be used as charge carrier in
batteries.
2) Fullerenes can be used as organic photovoltaic’s.
3) It can also be used as a soft Ferro magnet.
4)Its spherical structure makes it suitable for the use as lubricant

LQUID CRYSTALS
Liquid Crystal:
A state of matter that is intermediate between the solid crystalline and the ordinary
(isotropic) liquid phase is known as mesomeric state and this state of matter is called liquid
crystal.
Liquid crystal materials generally have several common characteristics. Among these are a
rod-like molecular structure, rigidness of the long axis, and strong dipoles and/or easily
polarizable substituents.The distinguishing characteristic of the liquid crystalline state is the
tendency of the molecules (mesogens) to point along a common axis, called the director.
This is in contrast to molecules in the liquid phase, which have no intrinsic order. In the
solid state, molecules are highly ordered and have little translational freedom. The
characteristic orientational order of the liquid crystal state is between the traditional solid
and liquid phases and this is the origin of the term mesogenic state, used synonymously with
liquid crystal state. Note the average alignment of the molecules for each phase in the
following diagram.

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 It is sometimes difficult to determine whether a material is in a crystal or liquid crystal
state. Crystalline materials demonstrate long range periodic order in three dimensions. By
definition, an isotropic liquid has no orientational order. Substances that aren't as ordered as a
solid, yet have some degree of alignment are properly called liquid crystals.

Characteristics of Liquid Crystals

The following parameters describe the liquid crystalline structure:
1)Positional Order 2)Orientation Order 3)Bond Orientation Order
Positional order :It is refers to the extent to which an average molecule or group of molecules
shows translational symmetry (as crystalline material shows).
Orientation order: It represents a measure of the tendency of the molecules to align along the
director on a long-range basis.
Bond Orientational Order: It describes a line joining the centers of nearest-neighbor
molecules without requiring a regular spacing along that line. Thus, a relatively long-range order
with respect to the line of centers but only short range positional order along that line
Types Of Liquid Crystal :
liquid crystals can be classified into two types.They are
1) Thermo tropic liquid crystal
2)Lyotropic liquid crystal
1)Thermo tropic liquid crystal : The compounds which exhibit liquid crystalline phases as the
temperature is changed is called as Thermotropic liquid crystals
eg:poly esters, poly ethers, poly silicones.
These are further divided into three types.
1)Nematic or thread like liquid crystal 2)chiral Nematic or cholesterolic liquid crystal
3)Smectic or soap like liquid crystal 4)columnar liquid crystal

1)Nematic or thread like liquid crystal:

They have low viscosity and flow readily.Their viscosityis lower than the lquid,hence, they are
more turbid.The molecule are aggregated together in groups or swarms with their axis parallel to
one another. These molecules move side ways or up and down along their length.Each molecule
can rotate around its axis.In an electric or magnetic field the swarms of nematic crystals get
oriented in the same direction. The nematic liquid crystal phase is characterized by molecules

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that have no positional order but tend to point in the same direction (along the director).With rise
in temperature swarms diminish in size .The nametic crystals flow like lquid but due to their
orientation aout preferred axis they exhibit anisotropic behaviour.The nematic crystalin their
pure form do not conduct electricity.
Eg:P-azoxy phenotole,Anisaldazine,P-methoxy chinnamic acid.

Liquid crystals are anisotropic materials, and the physical properties of the system vary with the
average alignment with the director. If the alignment is large, the material is very anisotropic.
Similarly, if the alignment is small, the material is almost isotropic.
A special class of nematic liquid crystals is called chiral nematic. Chiral refers to the unique
ability to selectively reflect one component of circularly polarized light. The term chiral nematic
is used interchangeably with cholesteric. Refer to the section on cholesteric liquid crystals for
more information about this mesophase.

Cholesteric lquid crystals:

In this type moleculesare arranged in the same manner as those in the nematic type but its
constituents are optically active. These are named cholestric lquid crystals because the skelton of
the substances passing through this state is similar to that of cholesterol present in blood.Such
crystals are characterised by their very high optical rotation.Inthis phase the molecules prefer to
lie next to each other in a slightly skewed orientation.
Eg:Cholesteryl chloride,cholesteryl benzoate,cholesteryl cinnamate etc.

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Smectic Phases lquid crystals:
Smectic means soaps like.Smectic state is exhibited by common soaps at high temperature.All
smectics have layered structure,with well difined interlayer spacing, which can be measured by
x-ray diffraction.
The substances thatform smectic mesophase are soap like.There is small amount of orientational
as well as small amount of positional order.The molecules form planes perpendicular to the axis
of the molecules and they tend topoint along the director.There are many many types of smectic
phases base on the orientation of the director.
In the smectic-A mesophase, the director is perpendicular to the smectic plane, and there is no
particular positional order in the layer. Similarly, the smectic-B mesophase orients with the
director perpendicular to the smectic plane, but the molecules are arranged into a network of
hexagons within the layer. In the smectic-C mesophase, molecules are arranged as in the
smectic-A mesophase, but the director is at a constant tilt angle measured normally to the
smectic plane

Picture of the smectic A phase

Picture of the smectic C phase

Columnar lquid crystals:

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Columnar liquid crystals are different from the previous types because they are shaped like disks
instead of long rods. This mesophase is characterized by stacked columns of molecules. The
columns are packed together to form a two-dimensional crystalline array. The arrangement of the
molecules within the columns and the arrangement of the columns themselves leads to new
mesophases.
2) Lyotropic liquid crystal : Some compounds are transformed to a liquid crystal phase when
mixed with another substance and when the concentration of one of the components is increased.
Such compounds are called lyotropic liquid crystals.
These crystalline phases are stabilized by solvents
Eg:Sodium laurate in water, phosphotidyl choline in water.
Engineering applications of liquid crystals:
1)Liquid crystals are used in gas liquid chromatography because of their mechanical and
electrical properties lie between crystalline solids and electrical properties.
2)Liquid crystals are employed as solvents during the spectroscopic study of structure of
anisotropic molecule.
3)Cholesteric liquid crystals are detecting tumors in the human body.
4)Liquid crystals are used as electro optic materials.
5)Liquid crystals are used as radiation and pressure sensors.
6)They are used in optical switches,shutters and in thermo graphy.
Applications of liquid crystal Display:
1)Digital or Alpha numeric displays: They are used in calculators, electronic clocks, data-output
equipments, mobile telephones and laptop computers.
2)Signal Displays:They are used in traffic and industrial control systems,petrol pump indicators
and indicators used in automobile dash boards.
3)Advertising Displays: They display by suitable structuring the front and back electrods and
connecting a number of liquid crystal displays in series,many advaertising displays are
discovered.
Analog Displays: They can be used in blood pressure instruments, digital thermometers,Tv
channel indicators, PH meters,conductometers,potentiometers and other analytical instruments.
Image converters: They can be used as image intensifier especially in U.V or X-ray image
converters, large screen projectors and night vision equipment.
6)Large area picture screens:They consume less power and they do not emit light but only effect
external incident light.

GREEN CHEMISTRY

Green chemistry, also called sustainable chemistry, is a philosophy of chemical research and
engineering that encourages the design of products and processes that minimize the use and
generation of hazardous substances. Whereas environmental chemistry is the chemistry of the
natural environment, and of pollutant chemicals in nature, green chemistry seeks to reduce and
prevent pollution at its source.

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Green chemistry can be defined as “Invention design and application of chemical products
and processes to reduce or to eliminate the use and generation of hazardous substances”.

As a chemical philosophy, green chemistry applies to organic chemistry, inorganic

chemistry, biochemistry, analytical chemistry, and even physical chemistry. While green
chemistry seems to focus on industrial applications, it does apply to any chemistry choice. Click
chemistry is often cited as a style of chemical synthesis that is consistent with the goals of green
chemistry. The focus is on minimizing the hazard and maximizing the efficiency of any chemical
choice. It is distinct from environmental chemistry which focuses on chemical phenomena in the
environment.

IMPORTANCE OF GREEN CHEMISTRY

The term green chemistry was coined by Paul Anastas in 1991Paul Anastas, then of the United
States Environmental Protection Agency, and John C. Warner developed 12 principles of green
chemistry,[4] which help to explain what the definition means in practice. The principles cover
such concepts as:

● the design of processes to maximize the amount of raw material that ends up in the product;
● the use of safe, environment-benign substances, including solvents, whenever possible;
● the design of energy efficient processes;
● the best form of waste disposal: not to create it in the first place.
● Reduce the material wastage
● Incorporation of all the materials
● Low cost
● Recyclable
● Reduce the energy efficiency
● Easy to decompose
● Productivity is very high
PRINCIPLES

The 12 principles are:

1. Minimization of waste product formation: It is better to prevent waste than to treat or

clean up waste after it is formed.
2. 100% atom economy : Synthetic methods should be designed to maximize the
incorporation of all materials used in the process into the final product.
3. To avoid the use and formation of toxic chemical substances : Wherever practicable,
synthetic methodologies should be designed to use and generate substances that possess
little or no toxicity to human health and the environment.
4. Use of non toxic chemical products : Chemical products should be designed to preserve
efficacy of function while reducing toxicity.

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 5. Minimum use of auxiliary substances : The use of auxiliary substances (e.g. solvents,
separation agents, etc.) should be made unnecessary wherever possible and innocuous
when used.
6. Minimum energy consumption : Energy requirements should be recognized for their
environmental and economic impacts and should be minimized. Synthetic methods
should be conducted at ambient temperature and pressure.
7. Use of renewable sources : A raw material or feedstock should be renewable rather than
depleting wherever technically and economically practicable.
8. Minimization of no. of steps : Reduce derivatives - Unnecessary derivatization
(blocking group, protection/ deprotection, temporary modification) should be avoided
whenever possible.
9. Use of Catalytic reagents (as selective as possible) are superior to stoichiometric
reagents.
10. Life time of chemical product : Chemical products should be designed so that at the end
of their function they do not persist in the environment and break down into innocuous
degradation products.
11. Monitoring the generation of hazardous substances Analytical methodologies need to
be further developed to allow for real-time, in-process monitoring and control prior to the
formation of hazardous substances.
12. Use of chemically safer substances : Substances and the form of a substance used in a
chemical process should be chosen to minimize potential for chemical accidents,
including releases, explosions, and fires.
APPLICATIONS OF GREEN CHEMISTRY

With the advancement of science ,green chemistry has change our life .some of its important
applications are described below
1)Dry cleaning of clothes:
Perchloro ethylene is commonly used as solvent for dry cleaning .it contaminates ground water .A
technology known as micelle used liquid carban dioxide and surf for dry cleaning clothes
2) Versatile bleaching agent: It is common knowledge that paper is manufactured from
wood(which contains 70% polysaccharides and 30% lignin) for good quality paper ,the lignin must
be removed. Initially the lignin is removed by placing small pieces of wood into bath of NaOH
and sodium sulphide .by using this method 80-90% of lignin is removed, remaining is removed by
using chlorine .but chlorine reacts with ligning forms dioxins, these are harmful to humans. A
versatile bleaching agent has been developed which involves the use of hydrogen peroxide as a
agent and in presence of some activators. The hydrogen peroxide converted into hydroxyl radicals
that will remove the lignin vey easily.
3)Pharmaceuticals:
Ibuprofen is the active ingredient in many analgesic and inflammatory drugs .in 1960 it was
produced by a six steps process with an atom economy of only 40% and remaining 60% were
wasted in the formation of unwanted byproducts. In 1990 a new synthesis of it with an atom
economy 77% to 99%
4)Pesticides: DDT is one of the most well known as insecticides .these DDT’s are rapidly degrade

95
in the environment but much more toxic to mammals
By using biochemical insecticides like Harpin ,it is genetically isolated from bacteria.when
applied to the plant the harpin defense the plant from the insects.
METHODS OF SYNTHESIS OF GREEN CHEMISTRY PRODUCTS
The methods for green synthesis are

● 1. Aqueous phase method 2. Super critical fluid extraction 3.Phase transfer catalyst

1) Aqueous phase method:

Normally organic solvents are widely used in commercial and service industry,these solvents
are evaporate very easily and contaminate the air ,land,water b they are difficult to
capture and recycle.
In view of the environmental concerns caused by pollution of organic solvents and chemists
all over the world have been trying to carry out organic reactions in Aqueous phase.the
advantage of using water as a solvent is its low cost ,non inflammable and avoid of any
carcinogenic effects ,high specific heat resistance.
Knoevenagel reaction:
The condensation of carbonyl compounds with active malanoic acid in presence of weak base
pyridine is known as knoevevagel reaction. however when condensation carried out in presence
of pyridine as a base ,decarboxylation usually occurs during the condensation.this is known as
Doebner modification.

Benzaldehyde+ malanoic acid---→malanoic derivative --------→ cinnamic acid

2)Super critical fluid extraction method:

Generally organic solvents have been used in conventional solvents extra process for extaction
of food and fats ,oils ,caffine ,cholesterol also in no.of process like petro chemical
process,polymer processbut these solvents extraction processes are cause pollution of land,air
and water.to avoid the pollution problems a new process introduced in mid of 20th century i.e
Super critical fluid extaction process.

● Super critical fluid is termed as it is neither gas nor liquid but combined properties of gasses
and liquids in an interguining manner .The Super critical fluids are produced by heating of
gas above its critical temperature or compressing a liquid at above its ctritical pressure.in
the Super critical environment only on phase can exist.
● The Super critical fluids have both the gasses and liquids properties of being able to
penetrate any thing and the liquid properties of being able to dissolve the materials in to
their components.
● Super critical fluid has good solvent property, inert to the product, easy separation from
the product and low cost.

3) Phase transfer catalyst(PTC) :

PTC is heterogeneous catalyst which is used to solubilize salt which are insoluble in
organic phase solvent.The PTC can facilitate the migratin of a reaction from one phase in

96
 to another phase by reaction occur .Ionic reactants are often soluble in aqeous phase but
insoluble in organic phase in the absence of PTC .But the main function of PTC is to
transfer the anion from reagent to substrate to occur the reaction faster and also obtain
higher yield by conversion of products. make less byproducts in to eliminate the need for
expensive and dangerous solvents and also minimize the waste problems.

Super Conductors

Superconductors:
These are the materials which posses zero electrical resistance and expulse
magnetic fluxes from theirare called superconductors. Generally materials exhibits zero
resistivity at below 00 c .
The temperature at which materials exhibits zero resistivity is called its critical temperature. The
first super conductor is Hg , which exhibits super conductivity at 4.20 K discovered by Dutch
physicist Heike Kamerlingh Onnes on April 8, 1911.
It is characterized by the Meissner effect [ the complete ejection of magnetic
lines from the interior of the superconductor during its transitions into the superconducting state].
The electrical resistance of a metallic conductor decreases gradually as temperature
is lowered. In ordinary conductors, such as copper or silver, this decrease is limited by impurities
and other defects.
In 1986, it was discovered that some cuprate-perovskite ceramic materials have a
critical temperature above 90 K (−183 °C) Lead (Pb) 7.196 K ,Lanthanum (La) 4.88 K ,Tantalum
(Ta) 4.47 K, Mercury (Hg) 4.15 K Tin (Sn) 3.72 K, Indium (In) 3.41 K, Palladium (Pd)* 3.3
K, Chromium (Cr)* 3 K, Thallium (Tl) 2.38 K, Rhenium (Re) 1.697 K , Protactinium (Pa) 1.40
K Thorium (Th) 1.38 K, Aluminum (Al) 1.175K Gallium (Ga) 1.083 K, Molybdenum
(Mo) 0.915 K, Zinc (Zn) 0.85 K, Osmium (Os) 0.66 K,
Zirconium (Zr) 0.61 K

Type 1 Superconductors : Type 1 superconductors are also known as the "soft"

superconductors . They exhibit a very sharp transition temperature and
"perfect" diamagnetism .They have the ability to repel a magnetic field completely.
By increasing the external magnetic field, super conductor will loose their super conductivity
suddenly and behaves like normal conductors. The magnetic field at which super conductor
looses its super conductivity is called the magnetic field strength and is denoted by Hc . Above
Hc these materials does not obeys Meissner effect.and behaves like normal conductors.

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Type 2 Superconductors These are also known as the "hard" superconductors .By
the increasing the magnetic field strength on type 2 super conductors to reach a point ( Hc1), they
starts to loose their super conductivity slowly, and after reaching to a particular point(HC2) they
looses completely and behaves like normal conductors. The state in between Hc1 and Hc2 is
called "mixed state" behavior. At this state they behaves like magnetic materials and conductors.
Since a Type 2 will allow some penetration by an external magnetic field into its surface.
Therefore type 2 super conductors cannot obey meissner effect completely. However type 2
super conductors has much higher critical temperature compared to Type 1 superconductors
some of the more interesting Type 2 superconductors are listed below
Eg; Tl2Ba2TeCu3O8 (147 K), Tl2Ba2YCu2O6 (139k), Cd5MgO6 ( 310K)

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Properties of Superconductors :
1. They posses greater resistance at room temperature compared to other elements.
2. The critical temperature for different isotopes decreases with increase in their atomic mass.
3. By the addition of impurity to a super conductor, its critical temperature will be decreases.
4. At the super conducting state either thermal expansion or elastic properties will not takes be
change.
5. In super conducting state all the electromagnetic effects will be disappears.
6. By the application of strong magnetic field super conducting property will be spoils.
7. Zero Electric Resistance (Infinite Conductivity)
8. They posses Meissner Effect: Expulsion of magnetic field.

.
APPLICATIONS OF SUPERCONDUCTORS
1. Superconducting Transmission Lines
Since 10% to 15% of generated electricity is dissipated in resistive losses in
transmission lines, the prospect of zero loss superconducting transmission lines is
appealing.
2. In Superconducting Motors and Generators
Superconducting motors and generators could be made with a weight of
about one tenth that of conventional devices for the same output.
3. Superconducting Magnetic Energy Storage
Superconducting magnetic energy storage (SMES) stores electricity for long
periods of time in superconductive coils. SMES will be used by electrical
utilities some day.
4. Computers: If computers used superconducting parts they would be much more
faster than the computers today. 5. Josephson Devices
5. Superconductors in NMR Imaging
Superconducting magnets find application in magnetic resonance imaging (MRI) of
the human body. Besides requiring strong magnetic fields on the order of a Tesla,
magnetic resonance imaging requires extremely uniform fields across the subject and
extreme stability over time. Maintaining the magnet coils in the superconducting
state helps to achieve parts-per-million spacial uniformity over a space large enough
to hold a person, and ppm/hour stability with time.
6. Magnetically Levitated Trains
Perhaps the most famous and fascinating superconducting invention is
magnetically levitated trains, or "maglev" trains. Maglev trains have no wheels and
friction. The trains float silently on a magnetic f ield due to diamagnetic behaviour.

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 UNIT-5:- SPECTROSCOPY

Spectroscopy

It is the branch of science that deals with the study of interaction of matter
with light. (OR)
It is the branch of science that deals with the study of interaction of electromagnetic
radiation with matter.

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Electromagnetic Radiation:-

• Electromagnetic radiation consists of discrete packages of energy which are called as photons.
• A photon consists of an oscillating electric field (E) & an oscillating magnetic field
(M) which is perpendicular to each other.
• Frequency (ν): – It is defined as the number of times electrical field radiation oscillates in one
second.
– The unit for frequency is Hertz (Hz). 1 Hz = 1 cycle per second
• Wavelength (λ): – It is the distance between two nearest parts of the wave in the same
phase i.e. distance between two nearest crest and troughs.
• The relationship between wavelength & frequency can be written as: c=νλ
• As photon is subjected to energy, so
E=hν=hc/λ Visible region consists of
following:-
Violet 400 - 420 nm, Yellow 570 - 585 nm, Indigo 420 - 440 nm, Orange 585 - 620 nm, Blue
440 - 490 nm
Red 620 - 780 nm Green 490 - 570 nm
Principles of Spectroscopy:-
• The principle is based on the measurement of spectrum of a sample containing atoms /
molecules.
• Spectrum is a graph of intensity of absorbed or emitted radiation by sample verses
frequency (ν) or wavelength (λ).
• Spectrometer is an instrument design to measure the spectrum of a
compound. Absorption Spectroscopy:
An analytical technique which concerns with the measurement of absorption of
Electromagnetic radiation.
E.g. UV (185 - 400 nm) / Visible (400 - 800 nm)

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 Spectroscopy, IR Spectroscopy (0.76 - 15μm)
Emission Spectroscopy:
An analytical technique in which emission (of a particle or radiation) is
dispersed according to some property of the emission & the amount of
dispersion is measured.
E.g. Mass Spectroscopy
Interaction of EMR with Matter
1. Electronic Energy Levels:
• At room temperature the molecules are in the lowest energy levels E0.
• When the molecules absorb UV-visible light from EMR, one of the outermost bond
/ lone pair electron is promoted to higher energy state such as E1, E2, …En, etc is
called as electronic transition and the difference is as: ∆E = h ν = En - E0 where (n = 1,
2, 3, … etc) ∆E = 35 to 71 kcal/mole
2. Vibrational Energy Levels:
• These are less energy level than electronic energy levels.
• The spacing between energy levels are relatively small i.e. 0.01 to 10 kcal/mole.
• E.g. when IR radiation is absorbed, molecules are excited from one vibrational level
to another or it vibrates with higher amplitude.
3. Rotational Energy Levels:
• These energy levels are quantized & discrete.
• The spacing between energy levels is even smaller than vibrational energy levels.
∆Erotational < ∆Evibrational < ∆Eelectronic

Lambert’s Law:-
• When a monochromatic radiation is passed through a solution, the decrease in the
intensity of radiation with thickness of the solution is directly proportional to the intensity
of the incident light.
• Let I be the intensity of incident radiation. X is the thickness of the solution. Then
It= I0 e-
kt
(Or)
log (I0/I) =Kt where K = k/2.303

Beer’s Law:-
When a monochromatic radiation is passed through a solution, the decrease in the intensity
of radiation with thickness of the solution is directly proportional to the intensity of the
incident light as well as concentration of the solution. • Let I be the intensity of incident
radiation. x be the thickness of the solution. C is the concentration of the solution. Then
I0 / It = 10 ect
Therefore log (I0/It) = ect /2.303

ROTATIONAL SPECTROSCOPY (Microwave)

Principle:-

When a diatomic molecule rotates on its own axis from the centre of mass
there will be generation of rotational energy (quantized).

102
 When electromagnetic radiation is passed to diatomic molecule then the certain
amount of energy is matches with the energy of diatomic molecule (resonance) absorption
take place and get excited to higher energy levels.

The absorption takes place in the region of microwave radiation: - 3 X 106 to 3

X 1012Hz. This spectroscopy applicable for isolated gaseous molecules.

Selection Rules:-

This spectroscopy is applicable for polar molecules which possess permanent dipole

moment e.g.:- Hetero diatomic molecules like

HCl, H2O. (Rotational active)

This spectroscopy is not applicable for nonpolar molecule which does not possess
permanent dipole moment.

e.g.:- Homo atomic molecules like

H2, N2, O2. (Rotational inactive)

The selection rule for the rotational transition is ∆J= ±1

When ∆J= +1 (excitation)

When rotating body absorbs the suitable radiation it gets excited to

higher state When ∆J= -1 (de excitation)

When rotating body in higher level emits energy and come back to

ground state. From the rotational spectrum we can calculate the

energy corresponding to rotational transitions

∆ E=EJ1 –EJ2

E= BJ (J+1) cm-1

VIBRATIONAL SPECTROSCOPY (IR)

Principle: -

103
 When a molecule absorbs IR radiation the vibration (or) rotation within the molecule
causes a net change in dipole moment.

When electric field of the radiation interacts with fluctuations in the dipole moment of
molecule resonance take place and radiation get absorbed causing change in molecular
vibrations.

The spectrum of IR provides information about functional group present in the

molecule. IR radiation Range: - 400cm-1 to 4000cm-1

IR spectrum further divided into two types

A) functional group region: - 1500 – 4000cm-1

b) Finger print region: - 625-1500cm-1

Vibrational Selection Rules:-

1. Symmetrical diatomic molecules are IR Inactive. Because it does not show

permanent dipole moment
e.g.:- O2, N2

2. Unsymmetrical diatomic molecules are IR active. Because it shows permanent

dipole moment e.g.:- CN, CO2

3. Polyatomic molecules undergo more complex vibrations

A) Stretching (symmetric stretching, asymmetric stretching)

B) Bending (in plane bending, out plane bending)

4. Vibrational transitions observed in vibrational,

rotational levels. Thus, the selection rule for a harmonic oscillator

transition is ∆v = ± 1.

When ∆v=+1(excitation)

When vibrating body absorbs the suitable radiation it gets excited to higher state.
When ∆v=-1(de excitation)

When vibrating body in higher level emits energy and come back to ground state.

Energy of vibrational spectroscopy:- Ev= (V+1/2) hv

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UV – VISIBLE SPECTROSCOPY(Electronic spectroscopy)

PRINCIPLE

When electromagnetic radiation in uv – visible region passed through a compound a part

of radiation is absorbed by the compound.

After absorption of energy, the electrons in the orbital of lower energy are excited into
orbitals of higher energy this is called as electronic spectroscopy.

UV-VISIBLE RADIATION SAMPLE ELECTRONIC TRANSITION

Electronic transitions are observed in the electronic, vibrational,
rotational levels The UV radiation region extends from 10 nm to 400
nm
The visible radiation region extends from 400 nm to
800 nm. Near UV Region: 200 nm to 400 nm

Far UV Region: below 200 nm

• Far UV spectroscopy is studied under vacuum condition.

Selection rules:-
The possible electronic transitions are graphically shown as:

1. σ → σ* transition 2. π → π* transition 3. n → σ* transition 4. n → π* transition 5. σ → π*

transition
6. π → σ* transition
1. σ → σ* transition• σ electron from orbital is excited to corresponding anti-bonding orbital
σ*.

• The energy required is large for this transition.

• E.g. Methane (CH4) has C-H bond only and can undergo σ → σ* transition and
shows absorbance maxima at 125 nm.
2. π → π* transition, π electron in a bonding orbital is excited to corresponding anti-bonding

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 orbital π*.

• Compounds containing multiple bonds like alkenes, alkynes, carbonyl, nitriles,

aromatic compounds, etc undergo π → π* transitions.

• E.g. Alkenes generally absorb in the region 170 to 205 nm.

3. n → σ* transition, Saturated compounds containing atoms with lone pair of electrons

like O, N, S and halogens are capable of n → σ* transition.

• These transitions usually requires less energy than σ → σ* transitions.

• E.g. Alcohols, amines, ethers in the Region 150 – 250 nm.

4. n → π* transition, an electron from non-bonding orbital is promoted to anti-bonding π*

orbital.

• Compounds containing double bond involving hetero atoms (C=O, C≡N, N=O)
undergo such transitions.

• n → π* transitions require minimum energy and show absorption at longer

wavelength around 300 nm. E.g – carbonyl compounds

5. σ → π* transition & • π → σ* transition, these electronic transitions are forbidden

transitions & are only theoretically possible. Thus, n → π* & π → π* electronic transitions
show absorption in region above 200 nm which is accessible to UV-visible
spectrophotometer.

APPLICATIONS OF UV / VISIBLE SPECTROSCOPY

Applications: - Qualitative & Quantitative Analysis: – It is used for characterizing aromatic

compounds and conjugated olefins. – It can be used to find out molar concentration of the
solute under study.• Detection of impurities: – It is one of the important method to detect
impurities in organic solvents.• Detection of isomers are possible.• Determination of
molecular weight using Beer’s law.
Terms used in UV / Visible Spectroscopy:-

Chromophore: - The part of a molecule responsible for imparting color, are called as

chromospheres. (OR)

The functional groups containing multiple bonds capable of absorbing radiations above

200 nm due to n → π* & π → π* transitions. e.g. NO2, N=O, C=O, C=N, C≡N, C=C,

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C=S, etc

Auxochrome: - The functional groups attached to a chromophore which modifies the ability of
the chromophore to absorb light, altering the wavelength or intensity of absorption.

Absorption & Intensity Shifts

1 Bathochromic Shift (Red Shift):- When absorption maxima (λmax) of a compound

shift to longer wavelength, it is known as bathochromic shift or red shift.

The effect is due to presence of an auxochrome or by the change of solvent.

E.g. An auxochrome group like –OH, -OCH3 causes absorption of

compound at longer wavelength.

In alkaline medium, p-nitrophenol shows red shift. Because negatively

charged oxygen delocalizes more effectively than the unshared pair of electron.
Phenol λmax = 255 nm p-nitrophenol λmax = 265 nm

2 Hypsochromic Shift (Blue Shift):- When an absorption maximum (λmax) of a

compound shifts to shorter wavelength, it is known as hypsochromic shift or blue shift.

The effect is due to presence of a group causes removal of conjugation or by the change
of solvent.

Aniline shows blue shift in acidic medium, it loses

conjugation. Aniline λmax = 280 nm anilinium ion
λmax = 265 nm

3 Hyperchromic Effect: - When absorption intensity (ε) of a compound is increased, it

is known as Hyperchromic shift.

If Auxochrome introduces to the compound, the intensity of absorption increases.

Pyridine ε=2750 2-methyl pyridine ε=3560

4 Hypochromic Effect: - When absorption intensity (ε) of a compound is decreased, it

is known as hypochromic shift.

Naphthalene ε = 19000 2-methyl naphthalene ε = 10250

NUCLEAR MAGNETIC RESONANCE (NMR)

Principle:- It is the study of interaction of electromagnetic radiation (radio frequency) and

nuclei of an atom is called NMR. Nucleus contains protons and neutrons due to this nuclear
charge developed. The spinning of charged nuclei on its own axis generates electric dipole

107
 and perpendicular to it magnetic field will produce. So spinning nuclei will generate magnetic
moment.

When electromagnetic radiation of suitable wavelength passes through magnetically active

nuclei absorption take place and get excited to higher energy levels.

By this spectroscopy method we can identify the molecular structure of any

organic compounds. Range: - 107-108 Hz
Selection Rules:-
Depending on no. of protons and neutrons present in nucleus the spin (I) will
change.
Case1:- when even number of protons and neutrons

Then Spin (I) = 0 no spin, So the nuclei of atom is

NMR inactive E.g.:- 12C, 16O

Case2:- when even number of protons and odd number of neutrons (OR) odd number
protons and even number of neutrons

Then spin (I) = ½ dipolar nuclei

So the nuclei of atom is NMR

active E.g.:- 1H, 13C, 15N

Case3:- when odd number of protons and neutrons Then spin (I) ≥ 1

So the nuclei of atom is NMR

INACTIVE E.g.:- 2H, 10B

What is CHEMICAL SHIFT

The difference in the absorption position of proton (sample) with respect to TMS (tetra

methyl silane) As reference sample is called chemical shift. (𝛿)

Delta units:- 𝛿= (νs- νr)/ ν ppm

νs= frequency of sample νr= frequency of reference

ν= instrumental frequency

When external magnetic field applied to molecule two observations may happen:-

1. Opposes the external applied field

2. Reinforces the external applied field

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 1. Opposes the external applied field:-

When applied field oppose the field generated by proton. The effective field diminished.
Then the proton is said to be shielded.

Due to this absorption shift to upfield in the NMR

spectrum. This is called diamagnetic shift

2.
Reinforces the external applied field:-

When applied field reinforce the field generated by proton. The effective field aligns in the
field direction. Then the proton is said to be de shielded. Due to this absorption shift to
downfield in NMR spectrum. This This is called paramagnetic shift.

Synthesis of organic compounds

Paracetamol

Paracetamol, also known as acetaminophen or APAP,

Uses: This is a medicine used to treat pain and fever.[1] It is typically used for mild to
moderate pain relief.[1] Evidence for its use to relieve fever in children is mixed.[11][12] It is often
sold in combination with other medications, such as in many cold medications.[1] In combination
with opioid pain medication, paracetamol is also used for severe pain such as cancer pain and
pain after surgery.[13] It is typically used either by mouth or rectally but is also
available intravenously.[1][14] Effects last between two and four hours.[14]
109
Dis advantages : It is generally safe at recommended doses.[15] Serious skin rashes may rarely
occur, and too high a dose can result in liver failure.[1] It appears to be safe during pregnancy and
when breastfeeding.[1] In those with liver disease, it may still be used, but in lower
doses.[16] Paracetamol is classified as a mild analgesic.[14] It does not have significant anti-
inflammatory activity and how it works is not entirely clear.[17]
Paracetamol was discovered in 1877.[18] It is the most commonly used medication for pain and
fever in both the United States and Europe.[19] It is on the World Health Organization's List of
Essential Medicines, the most effective and safe medicines needed in a health system.[20]
Chemical properties[edit]
Paracetamol consists of a benzene ring core, substituted by one hydroxyl group and
the nitrogen atom of an amide group in the para (1,4) pattern.[108] The amide group
is acetamide (ethanamide). It is an extensively conjugated system, as the lone pair on the
hydroxyl oxygen, the benzene pi cloud, the nitrogen lone pair, the p orbital on
the carbonyl carbon, and the lone pair on the carbonyl oxygen are all conjugated. The presence
of two activating groups also make the benzene ring highly reactive
toward electrophilic aromatic substitution. As the substituents are ortho, para-directing
and para with respect to each other, all positions on the ring are more or less equally activated.
The conjugation also greatly reduces the basicity of the oxygens and the nitrogen, while making
the hydroxyl acidic through delocalisation of charge developed on the phenoxide anion.
Paracetamol is part of the class of drugs known as "aniline analgesics"; it is the only such drug
still in use today.[109] It is not considered an NSAID because it does not exhibit significant anti-
inflammatory activity (it is a weak COX inhibitor)This is despite the evidence that paracetamol
and NSAIDs have some similar pharmacological activity.
Synthesis
Original (Boots) method
The original method for production involves the nitration of phenol with sodium nitrate gives a
mixture of two isomers, from which the wanted 4-nitrophenol(bp 279 °C) can easily be separated
by steam distillation. In this electrophilic aromatic substitution reaction, phenol's oxygen is
strongly activating, thus the reaction requires only mild conditions as compared to nitration of
benzene itself. The nitro group is then reduced to an amine, giving 4-aminophenol. Finally, the
amine is acetylated with acetic anhydride. Industrially direct hydrogenation is used, but in the
laboratory scale sodium borohydride serves.

110
Green synthesis
An alternative industrial synthesis developed by Hoechst–Celanese involves direct acylation
of phenol with acetic anhydride catalyzed by HF, conversion of the ketone to
a ketoxime with hydroxylamine, followed by the acid-catalyzed Beckmann rearrangement to
give the amide.

Direct synthesis[edit]
More recently (2014) a "one-pot" synthesis from hydroquinone has been described
before the Royal Society of Chemistry.[117][118] The process may be summarized as
follows:
Hydroquinone, ammonium acetate, and acetic acid were mixed in an argon atmosphere
and heated slowly to 230 °C. The mixture was stirred at this temperature for 15 hours.
After cooling the acetic acid was evaporated and the precipitate was filtered, washed with
water and dried to give paracetamol as a white solid.
The authors go on to claim an 88% yield and 99% purity.

111
 Reactions
4-Aminophenol may be obtained by the amide hydrolysis of paracetamol. 4-
Aminophenol prepared this way, and related to the commercially available Metol,
has been used as a developer in photography by hobbyists. This reaction is also used
to determine paracetamol in urine samples: After hydrolysis with hydrochloric
acid, 4-aminophenol reacts in ammonia solution with a phenol derivate, e.g. salicylic
acid, to form an indophenol dye under oxidization by air.

IBUPROFEN

Ibuprofen is a medication in the nonsteroidal anti-inflammatory drug (NSAID) class

USES: It is used for treating pain, fever, and inflammation. periods, migraines,. It may also be
used to close a patent ductus arteriosus in a premature baby. It can be used by mouth
or intravenously. It typically begins working within an hour.
Dis advantages:
Common side effects include heartburn and a rash. At higher doses it may increases the risk
of heart failure, kidney failure, and liver failure. . Ibuprofen can also degenerate asthma While it
is unclear if it is safe in early pregnancy, it appears to be harmful in later pregnancy and
therefore is not recommended.
Ibuprofen was discovered in 1961 by Stewart Adams and initially marketed as Brufen.

● The systematic IUPAC name for ibuprofen is 2-(4-isobutylphenyl)propanoic acid

The molecular formula of ibuprofen is C13H18O2.
● Ibuprofen is a white crystalline solid with a melting point of 76oC.
● Ibuprofen is slightly soluble in water and very soluble in ethanol.
● Ibuprofen is a weak acid.
● Ibuprofen reacts like other carboxylic acids, reacting with with active metals, carbonates,
alcohols and bases.

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● The structural formula of ibuprofen is shown on the
right:
● Ibuprofen is a white crystalline solid with a melting
point of 76oC.
● Ibuprofen is slightly soluble in water and very soluble
in ethanol.
● Ibuprofen is a weak acid.
● Ibuprofen reacts like other carboxylic acids, reacting with with active metals, carbonates,
alcohols and bases.
Synthesis of Ibuprofen
Ibuprofen is synthesized from 2-methylpropylbenzene which can be made from compounds
separated from crude oil.

The skeletal formula of 2-methylpropylbenzene is shown on the right.

Notice that the only functional group is the benzene ring.
Benzene does not readily undergo addition reactions, but will undergo substitution reactions.

Compare the structure of the starting material, 2-methylpropylbenzene, with the desired product
of the synthesis reactions, ibuprofen:

starting material desired product

2-methylpropylbenzene ibuprofen

.
Therefore the synthesis of ibuprofen must involve substituting 1 hydrogen atom on the benzene
ring of the 2-methylpropylbenzene starting material for this chain.

The so-called "Green" synthesis of ibuprofen involves 3 steps.

Step 1: Acylation

In an acylation reaction, an acyl group (RCO-) is attached to the benzene ring producing a
ketone.

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2-methylpropylbenzene reacts with acetic anhydride in the presence of a catalyst (HF) to produce
a ketone:

H +
2 + F 2 H2
🡪 O

Step 2: Hydrogenation
Hydrogen is added to an organic molecule in an hydrogentation reaction.
Hydrogen gas is used to reduce the ketone to an alcohol in the presence of a catalyst (Raney
nickel):

Raney nickel
+ H2
→

Step 3: Carbonylation

Addition of CO to the alcohol to form the carboxylic acid using carbon monoxide and a catalyst
(palladium):

Pd
+ CO
→

Chemical Reactions of Ibuprofen

Reaction with Active Metals

Ibuoprofen is a carboxylic acid, it will react with active metals to produce a salt and hydrogen
gas.

ibuprofen + sodium → sodium salt of ibuprofen + hydrogen gas

2 + 2 Na(s) → 2 + H2(g)
Na+

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Reaction with Carbonates
Ibuprofen is a carboxylic acid, it will react with carbonate solutions to produce a salt, water and
carbon dioxide gas.

sodium
carbon
ibuprofen + carbonate → sodium salt of ibuprofen + water +
dioxide gas
solution

→
2 + Na2CO3(aq) + H2O(l) + CO2(g)
2
Na+

Ibuprofen is a carboxylic acid, it will react with hydrogencarbonate solutions to produce a salt,
water and carbon dioxide gas.

sodium carbon
sodium salt of
ibuprofen + hydrogencarbonate → + water + dioxide
ibuprofen
solution gas

H-O-
+ NaHCO3(aq) → + + CO2(g)
H(l)
Na+

Esterification
Ibuprofen is a carboxylic acid, it will react with alcohols to poduce an ester in an esterification
reaction.

ibuprofen + ethanol → ester + water

+ CH3CH2OH(aq) → + H2O(l)

Reaction with Base

Ibuprofen is a carboxylic acid, it will react with bases to produce a salt and water.

sodium hydroxide
ibuprofen + → sodium salt of ibuprofen + water
solution

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 + NaOH(aq) → + H-O-H(l)
Na+

ASPIRIN

ASPIRIN

■ Mix salicylic acid (solid) with acetic anhydride (liquid) and a catalytic amount of H2SO4.
■ Heat for 10 min at 900C.
■ Cool down to room temperature and add water (crystallization solvent).
■ Induce crystallization.
Filter the crystals.
Aspirin is the common name for the compound acetylsalicylic acid, widely used as a fever
reducer and as a pain killer. Salicylic acid.. To prepare aspirin, salicylic acid is reacted with an
excess of acetic anhydride. A small amount of a strong acid is used as a catalyst which speeds up
the reaction. In this experiment, phosphoric acid will be used as the catalyst. The excess acetic
acid will be quenched with the addition of water. The aspirin product is not very soluble in water
so the aspirin product will precipitate when water is added. The synthesis reaction of aspirin is
shown below:

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The melting point range of pure C and the melting point range of the salicylic acid aspirin is
138-140 C. starting material is 158-161
Procedure
1. Weighout accurately 2 g of sylicylic acid into Erlenmeyer flask. Into this transfer 5.0 mL of
acetic anhydride from a buret. Add 5 drops of 85% phosphoric acid (catalyst) to the flask.
2. Clamp the flask in a beaker of tap water supported on a water bath. Stirr well to dissolve the
salicylic acid. Heat the water to boiling, and shut off the flame. Keep the flask in the hot water
bath for 10 more minutes.
3. While the flask is still in the water bath, slowly add 2 mL of distilled water to the flask to
decompose any excess acetic anhydride.
4. After a minute, remove the flask from the water bath and add 20 mL of distilled water. Let the
flask cool to room temperature. As the solution cools, crystals of aspirin will appear.
5.. Set up a funnel place the filter paper in the funnel and transfer the aspirin crystals into the
funnel.
7. Transfer the filter paper and aspirin to a watch glass and allow to air dry .Weigh out accurately
the aspirin crystals and calculate the percentage of yield.

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